CN103147075B - A kind of water-soluble copper facing protective material and preparation method thereof - Google Patents
A kind of water-soluble copper facing protective material and preparation method thereof Download PDFInfo
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- CN103147075B CN103147075B CN201110404309.3A CN201110404309A CN103147075B CN 103147075 B CN103147075 B CN 103147075B CN 201110404309 A CN201110404309 A CN 201110404309A CN 103147075 B CN103147075 B CN 103147075B
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Abstract
The present invention relates to a kind of water-soluble copper facing protective material and preparation method thereof.Take water as solvent, solute rare-earth salts and organic inhibitor is made to generate rare-earth complex skeleton in copper coatings, surface organic inhibitor is combined with the rare-earth complex skeleton of copper coatings and generates self-assembled film, finally passes through physical adsorption outward at self-assembly rete, covers one deck organic high molecular layer.The three-dimensional films Rotating fields of formation copper coatings like this, to effectively prevent in air obnoxious flavour to the corrosion of copper coatings, improve salt spray resistance and the Anti-tarnish property of copper coatings, the non-polar molecule group of self-assembled film end can significantly improve the oilness of copper coatings, reduce contact engaging and separating force, and do not affect its electroconductibility and welding property.
Description
Technical field
The present invention relates to a kind of copper coatings protective material and preparation method thereof, this surface protectant is applicable to the protective material of communications industry wave filter or printed-wiring board (PWB) copper coatings.
Background technology
The device such as the cover plate of widely used communication module, cavity and junctor in communications industry, adopts silver-plated method to make more.Along with rising steadily of the silver-colored valency in the world, the silver plating process that tradition adopts transforms to the copper-plating technique of relative inexpensiveness, but because the reactive behavior of metallic copper is far above silver, easy and moisture content, SO in atmosphere
2, H
2s, NO
2deng medium effect, and generate corrosion product or oxide compound, the contact resistance of communication device is increased, cause electrical signal instability or interrupt, even accidents caused.Therefore copper-plated protection question is unanimously the important problem that people are making great efforts to capture.
Current solution copper facing protection question, main employing two kinds of methods:
First method is the closure strengthening copper coatings micropore.Adopt organic solvent type protective material; utilize organic solvent good solubility energy; the inhibiter be dissolved in wherein is brought into copper coatings hole place; after organic solvent volatilization; namely inhibiter is attached to hole place; copper coatings is formed and effectively closes---the obnoxious flavour composition in isolated air, thus reach protection object.But, the organic solvent adopted in the method, for halogen-containing volatile liquid, because it exists destruction to atmospheric ozone layer, disabled---from January 1st, 2011, country's (China belongs to one of signatory country) of all signings " Montreal treaty ", all forbids producing and using this kind of organic solvent.
Second method lays particular emphasis on surface passivation.Adopt the single passivation of glyoxaline compound, generate the passive oxidation film of one deck even compact in copper coatings, the obnoxious flavour composition in isolated air, reaches protection object.This method, although the passive oxidation film even compact that copper coatings can be made to generate, because its rete is thicker, considerably increases the contact resistance of electrical contact surface, and the salt spray resistance of copper facing product surface is poor, therefore be not suitable for the higher electronic component of some electrical performance demands.
Summary of the invention
The object of the invention is to, overcome the difficult problem that copper facing protection exists, copper facing protective material that a kind of environment-friendly high-efficiency is provided and preparation method thereof.
The present invention is achieved in that
With water as solvent, rare-earth salts, organic inhibitor, organic polymer and tensio-active agent are solute, and each component proportion is:
A. mass ratio shared by rare-earth salts is 0.5 ~ 2%;
B. mass ratio shared by organic inhibitor is 20 ~ 25%;
C. mass ratio shared by organic polymer is 10 ~ 20%;
D. the mass ratio shared by tensio-active agent is 15 ~ 20%;
E. surplus is water.
Described rare-earth salts, refers to the composite of two kinds of lanthanide metal salts;
Described organic inhibitor, refers to the composite of at least two kinds of materials in nitrogen azole, imidazoles, arylimidazoles, organic amine compound.Nitrogen azole and imidazoles composite time proportioning be 1: 1, nitrogen azole and organic amine composite time proportioning be 1: 2, imidazoles and organic amine composite time proportioning be 1: 2;
Described organic amine compound is RNH
2, R
2nH, R
3in N one or both, the equal proportion mixture of three kinds, R molecular formula is C
nh
2n+1, wherein n>=6;
Described organic polymer, refers to polyethylene wax;
Described tensio-active agent, refers to alkyl ether tensio-active agent;
Described water, refers to industrial deionized water.
The protectant preparation method of water-soluble copper facing of the present invention, carries out according to following steps:
A. in reactor, add the deionized water of 40 ~ 60% calculated amount, be heated to 45 ~ 50 DEG C;
B. accurately take the rare-earth salts of calculated amount, add 45 ~ 50 DEG C of deionized waters, be stirred to dissolving, obtain colourless transparent solution A;
C. accurately take the organic inhibitor of calculated amount, add reaction soln, at 45 ~ 50 DEG C, be stirred to dissolving, obtain yellow solution B;
D. accurately take the tensio-active agent (also known as " OP10 ") of calculated amount, be heated at 40 ~ 45 DEG C and dissolve completely, obtain deep yellow clear solution C;
E. solution C is poured in solution B while hot, at 40 ~ 45 DEG C, stir 15min, obtain faint yellow emulsion D;
F. accurately take the organic polymer of calculated amount, add solution D, obtain faint yellow viscous fluid, after stirring 45min at 40 ~ 45 DEG C, add balance deionized water constant volume wherein, continue to be stirred to viscous fluid evenly fine and smooth, obtain product.
The protectant using method of this water-soluble copper facing, carry out according to following step:
A. the water-bath of protective material stoste is heated to 40 ~ 45 DEG C, makes protective material stoste be the solution of even viscous flow;
B. deionized water is heated to 40 ~ 45 DEG C, after pour in the protective material stoste heated, be stirred to protective material stoste and be diluted as the oyster white working fluid that concentration is 10 ~ 20%;
C. clean workpiece to be protected is soaked 90 ~ 180s in 40 ~ 45 DEG C of protective material working fluids;
D. the workpiece doing overprotection agent is cleaned 2 ~ 3 times in 35 ~ 40 DEG C of deionized waters, then control the rinse water in dry workpiece blind hole;
E. the rinse water on workpiece blind hole and surface is blown away with pressurized air;
F. the workpiece after cleaning being dried up toasts 30 ~ 45min in 80 ~ 120 DEG C of baking ovens;
G.. the workpiece after oven dry is placed 2 ~ 4h in room temperature.
This protectant mechanism of action is:
1. rare earth ion can form a series of complex compound with inorganic and organic ligand in aqueous, and because these rare earth ions have larger volume, from the space requirement of part arrangement, complex compound will have higher ligancy.Rare-earth complex and the maximum difference of transition element as complex compounds such as Zn, Cr of d district are the complex compounds that rare earth ion can generate high ligancy.Ligancy 4 and 6 is feature ligancies of d district transition element, but the ligancy of rare earth element is often greater than 6, has 7,8,9,10, even up to 12.And inside protective material solution, there is a large amount of containing n-donor ligands (as BTA); the coordination ability of these parts and rare earth ion is stronger; define the complex compound of BTA, rare earth ion in the solution; and BTA also can with copper complexing, surface formed polymerization shape Cu (I) BTA complex compound.Add after rare earth ion, form BTA, the complex compound of rare earth ion can in copper surface adsorption, also can with copper generation complexing, change the structure of film, cover last layer complex compound skeleton in copper coatings, reach first and heavily protect object.
2. after rare-earth complex covers complex compound skeleton to copper coatings; because rare-earth complex volume is larger; also have a small amount of copper atom in copper coatings and cannot generate protective membrane with rare-earth complex; face this situation; we have employed the relatively little organic inhibitor of volume and carry out complexing by self-assembling technique to the copper atom of gap or ion, reach second and heavily protect object.
3. through double protection; copper coatings has generated one deck complex compound protective membrane; the organic polymer polyethylene wax with the Surface Modification Effect is now adopted to form thin film at outermost layer; this layer film forms weak reactive force by electrostatic adhesion, physical adsorption and copper coatings, reaches triple protection object.
4. Action of Surfactant: the aqueous solution state of organic inhibitor and rare-earth salts is very unstable; the easy layering of solution; surface active agent OP10 is adopted to promote to dissolve organic inhibitor; then polyethylene wax adjustment solution state is adopted; make protective material concentrated solution and working fluid state uniform and stable, coating shiny appearance without current mark.
The invention has the advantages that:
1. significantly improve copper coatings protective capacities: prove through GB/T2423.17 neutral salt spray test, the copper facing module salt-fog resistant test through the process of this protective material can reach 24h, relatively without the copper facing module of protection, considerably improves salt spray resistance; In sulfurous gas, hydrogen sulfide and Outdoor exposure test, also there is splendid Anti-tarnishing, anticorrosion ability.
2. stable electric property: under making copper facing module be in lubrication protection, alleviates the detrimentally affect that operation uses and environment produces it, ensure that the electroconductibility of communication module, and do not affect its welding property.
3. safety and environmental protection: the present invention take deionized water as solvent, not containing hazardous and noxious substances such as heavy metal chromium, mercury, lead, cadmium, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers, have passed Switzerland logical mark SGS and detects, meet ROHS examination criteria.
The present invention has abandoned the protectant organic solvent of traditional solvent-borne; take water as solvent; utilize surface self-organization technology; one deck firmly three-dimensional films Rotating fields is generated in copper coatings; objectionable constituent in air and copper coatings are kept apart; thus realize the protection of the environment-friendly high-efficiency of copper coatings, improve salt spray resistance and the Anti-tarnish property of copper facing communication module, its electric property and welding property can be ensured simultaneously.Production technique of the present invention is simple, and easy to use, environmental friendliness, reduces cost, has saved social resources.
Accompanying drawing explanation
The protectant mechanism of action schematic diagram of Fig. 1 the present invention
Embodiment:
Describe three embodiments below, the present invention will be further described
Fig. 1 shows protectant protective mechanism of the present invention:
1. rare earth ion generates the complex compound of rare earth ion in aqueous, and BTA also can with copper complexing, surface formed polymerization shape Cu (I) BTA complex compound.After adding rare earth ion, form BTA.The complex compound of rare earth ion can in copper surface adsorption, also can with copper generation complexing, change the structure of film, cover last layer complex compound skeleton in copper coatings, reach first and heavily protect object.
2. after rare-earth complex covers complex compound skeleton to copper coatings; because rare-earth complex volume is larger; also have a small amount of copper atom in copper coatings and cannot generate protective membrane with rare-earth complex; face this situation; adopt the relatively little organic inhibitor of volume to carry out complexing by self-assembling technique to the copper atom of gap or ion, reach second and heavily protect object.
3. through double protection; copper coatings has generated one deck complex compound protective membrane; the organic polymer polyethylene wax with the Surface Modification Effect is now adopted to form thin film at outermost layer; this layer film forms weak reactive force by electrostatic adhesion, physical adsorption and copper coatings, reaches triple protection object.
Embodiment 1 prepares the protective material of 1000g.
Each component batching is carried out: rare-earth salts Lanthanum trichloride 6g, Neodymium trichloride 6g by following mass ratio; Organic inhibitor benzotriazole 75g, imidazoles 75g, polyethylene wax 100g, surfactant OP-10 150g, all the other are deionized water 588g.
The process for preparation of this embodiment is:
1. in reactor, add the deionized water of 40%, be heated to 45 ~ 50 DEG C;
2. accurately take rare-earth salts Lanthanum trichloride and each 6g of Neodymium trichloride, add above-mentioned deionized water, be stirred to dissolving, obtain colourless transparent solution A;
3. accurately take organic inhibitor benzotriazole 75g and add reaction soln, be stirred to dissolving at 45 ~ 50 DEG C, obtain yellow solution B;
4. accurately take organic inhibitor imidazoles 75g, surfactant OP-10 150g, at 40 ~ 45 DEG C after mixing, be heated to mixture and dissolve completely, obtain deep yellow clear solution C;
5. solution C is poured in solution B while hot, at 40 ~ 45 DEG C, stir 15min, obtain faint yellow emulsion D;
6. accurately take organic polymer polyethylene wax 100g, add solution D, obtain faint yellow viscous fluid, after stirring 45min at 40 ~ 45 DEG C, add balance deionized water wherein and be settled to 1000g, continue to be stirred to viscous fluid evenly fine and smooth, obtain product.
7. filling.
The protectant using method of copper facing of the present embodiment, carry out according to following step:
A. the water-bath of protective material stoste is heated to 40 ~ 45 DEG C, makes protective material stoste be the solution of even viscous flow;
B. deionized water is heated to 40 ~ 45 DEG C, after pour in the protective material stoste heated, be stirred to protective material stoste and be diluted as the oyster white working fluid that concentration is 10 ~ 20%;
C. clean workpiece to be protected is soaked 90 ~ 180s in 40 ~ 45 DEG C of protective material working fluids;
D. the workpiece doing overprotection agent is cleaned 2 ~ 3 times in 35 ~ 40 DEG C of deionized waters, then control the rinse water in dry workpiece blind hole;
E. the rinse water on workpiece blind hole and surface is blown away with pressurized air;
F. the workpiece after cleaning being dried up toasts 30 ~ 45min in 80 ~ 120 DEG C of baking ovens;
G.. the workpiece after oven dry is placed 2 ~ 4h in room temperature, packaging accumulating.
Embodiment 2 prepares 1000g protective material.
Each component batching is carried out: rare-earth salts Yttrium trichloride 2.5g, Neodymium trichloride 2.5g according to following mass ratio; Organic inhibitor benzotriazole 75g, lauryl amine 150g, polyethylene wax 150g, surfactant OP-10 200g, all the other are deionized water 420g.
The process for preparation of this embodiment is:
1. in reactor, add the deionized water of 60%, be heated to 45 ~ 50 DEG C;
2. accurately take rare-earth salts Yttrium trichloride and each 2.5g of Neodymium trichloride, add 45 ~ 50 DEG C of deionized waters, be stirred to dissolving, obtain colourless transparent solution A;
3. accurately take organic inhibitor benzotriazole 75g and add reaction soln, be stirred to dissolving at 45 ~ 50 DEG C, obtain yellow solution B;
4. accurately take organic inhibitor lauryl amine 150g, surfactant OP-10 200g, at 40 ~ 45 DEG C after mixing, be heated to mixture and dissolve completely, obtain deep yellow clear solution C;
5. solution C is poured in solution B while hot, at 40 ~ 45 DEG C, stir 15min, obtain faint yellow emulsion D;
6. accurately take organic polymer polyethylene wax 150g, add solution D, obtain faint yellow viscous fluid, after stirring 45min at 40 ~ 45 DEG C, add balance deionized water wherein and be about settled to 1000g, continue to be stirred to viscous fluid evenly fine and smooth, obtain product.
7. filling.
The using method of the present embodiment is identical with embodiment 1.
Embodiment 3 prepares 1000g protective material.
Each component batching is carried out: rare-earth salts Yttrium trichloride 10g, Lanthanum trichloride 10g according to following ratio; Organic inhibitor benzotriazole 50g, phenylimidazole 50g, lauryl amine 100g, polyethylene wax 200g, surfactant OP-10 180g, all the other are deionized water 400g.
The process for preparation of this embodiment is:
1. in reactor, add the deionized water of 50%, be heated to 45 ~ 50 DEG C;
2. accurately take rare-earth salts Yttrium trichloride and each 5g of Lanthanum trichloride, add 45 ~ 50 DEG C of deionized waters, be stirred to dissolving, obtain colourless transparent solution A;
3. accurately take organic inhibitor benzotriazole 50g and add reaction soln, be stirred to dissolving at 45 ~ 50 DEG C, obtain yellow solution B;
4. accurately take organic inhibitor phenylimidazole 50g, lauryl amine 100g, surfactant OP-10 200g, at 40 ~ 45 DEG C after mixing, be heated to mixture and dissolve completely, obtain deep yellow clear solution C;
5. solution C is poured in solution B while hot, at 40 ~ 45 DEG C, stir 15min, obtain faint yellow emulsion D;
6. accurately take organic polymer polyethylene wax 200g, add solution D, obtain faint yellow viscous fluid, after stirring 45min at 40 ~ 45 DEG C, add balance deionized water wherein and be about settled to 1000g, continue to be stirred to viscous fluid evenly fine and smooth, obtain product.
7. filling.
The using method of the present embodiment is identical with embodiment 1.
Claims (4)
1. a water-soluble copper facing protective material, is characterized in that: with water as solvent, and rare-earth salts, organic inhibitor, organic polymer and tensio-active agent are solute, and each component proportion is:
A. mass ratio shared by rare-earth salts is 0.5 ~ 2%;
B. mass ratio shared by organic inhibitor is 20 ~ 25%;
C. mass ratio shared by organic polymer is 10 ~ 20%;
D. the mass ratio shared by tensio-active agent is 15 ~ 20%;
E. surplus is water;
Described rare-earth salts, refers to the composite of two kinds of lanthanide metal salts;
Described organic inhibitor, refers to the composite of at least two kinds of components in imidazoles, organic amine compound; This organic amine compound is RNH
2, R
2nH, R
3in N one or both, the equal proportion mixture of three kinds, R molecular formula is C
nh
2n+1, wherein n>=6;
Described organic polymer, refers to polyethylene wax;
Described tensio-active agent, refers to alkyl ether tensio-active agent;
Described water, refers to industrial deionized water.
2. water-soluble copper facing protective material according to claim 1, is characterized in that, the composite weight proportion of several organic inhibition is: imidazoles and organic amine composite time proportioning be 1: 2.
3. the protectant preparation method of water-soluble copper facing according to claim 1, is characterized in that, carry out according to following step:
A. in reactor, add the deionized water of 40 ~ 60% calculated amount, be heated to 45 ~ 50 DEG C;
B. accurately take the rare-earth salts of calculated amount, add above-mentioned deionized water, be stirred to dissolving, obtain colourless transparent solution A;
C. accurately take the organic inhibitor of calculated amount, add the colourless transparent solution A of above-mentioned steps b, be stirred to dissolving at 45 ~ 50 DEG C, obtain yellow solution B;
D. accurately take the tensio-active agent of calculated amount, be heated at 40 ~ 45 DEG C and dissolve completely, obtain deep yellow clear solution C;
E. solution C is poured in solution B while hot, at 40 ~ 45 DEG C, stir 15min, obtain faint yellow emulsion D;
F. accurately take the organic polymer of calculated amount, add solution D, obtain faint yellow viscous fluid, after stirring 45min at 40 ~ 45 DEG C, add balance deionized water constant volume wherein, continue to be stirred to viscous fluid evenly fine and smooth, obtain product.
4. the protectant using method of water-soluble copper facing according to claim 1, is characterized in that, carry out according to following step:
A. the water-bath of protective material stoste is heated to 40 ~ 50 DEG C, makes protective material stoste be the solution of even viscous flow;
B. pour into after deionized water being heated to 40 ~ 50 DEG C in the protective material stoste heated, be stirred to protective material stoste and be diluted as the oyster white working fluid that concentration is 10 ~ 20%;
C. clean workpiece to be protected is soaked 90 ~ 180s in 42 ~ 50 DEG C of protective material working fluids;
D. the workpiece doing overprotection agent is cleaned 2 ~ 3 times in 35 ~ 40 DEG C of deionized waters, then control the rinse water in dry workpiece blind hole;
E. the rinse water on workpiece blind hole and surface is blown away with pressurized air;
F. the workpiece after cleaning being dried up toasts 30 ~ 45min in 80 ~ 120 DEG C of baking ovens;
G.. the workpiece after oven dry is placed 2 ~ 4h in room temperature.
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|---|---|---|---|
| CN201110404309.3A CN103147075B (en) | 2011-12-07 | 2011-12-07 | A kind of water-soluble copper facing protective material and preparation method thereof |
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| CN103147075B true CN103147075B (en) | 2016-04-27 |
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| CN103436888B (en) * | 2013-08-23 | 2015-07-01 | 南京理工大学 | High temperature copper corrosion inhibitor containing benzimidazole and preparation method of high temperature copper corrosion inhibitor |
| CN104818480B (en) * | 2015-04-28 | 2018-05-11 | 太仓市林源电线电缆有限公司 | A kind of proof copper-wire braided line protective agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6068711A (en) * | 1994-10-07 | 2000-05-30 | Mcmaster University | Method of increasing corrosion resistance of metals and alloys by treatment with rare earth elements |
| CN101514457A (en) * | 2009-04-02 | 2009-08-26 | 西安创联华特表面处理技术有限责任公司 | Multi-purpose metal surface protectant and preparation method thereof |
-
2011
- 2011-12-07 CN CN201110404309.3A patent/CN103147075B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6068711A (en) * | 1994-10-07 | 2000-05-30 | Mcmaster University | Method of increasing corrosion resistance of metals and alloys by treatment with rare earth elements |
| CN101514457A (en) * | 2009-04-02 | 2009-08-26 | 西安创联华特表面处理技术有限责任公司 | Multi-purpose metal surface protectant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| BTA及其复配铜缓蚀剂的研究进展;张娟等;《材料导报》;20080930;第22卷(第9期);第1-2页 * |
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