CN110093598A - For protecting the tin face protective agent of chemical tin coating - Google Patents
For protecting the tin face protective agent of chemical tin coating Download PDFInfo
- Publication number
- CN110093598A CN110093598A CN201910415682.5A CN201910415682A CN110093598A CN 110093598 A CN110093598 A CN 110093598A CN 201910415682 A CN201910415682 A CN 201910415682A CN 110093598 A CN110093598 A CN 110093598A
- Authority
- CN
- China
- Prior art keywords
- tin
- protective agent
- coating
- face protective
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
Abstract
The invention discloses a kind of for protecting the tin face protective agent of chemical tin coating, which includes following components according to concentration: citrate 0.5-10g/L；Phosphate 0.5-50g/L；Phytic acid 1-5g/L；Thiocarbamide 0.2-2g/L；Above four kinds of components form protective agent after being dissolved with water；Protectant pH value is adjusted between 2.5-3.5 with ammonium hydroxide or phosphoric acid again；Finally tin face protective agent can be formed with pure water constant volume；Under normal temperature condition, tin plating workpiece is impregnated to 0.5-5min in the tin face protective agent can be completed protection；The tin face protective agent has good tin coating defencive function, and coating can be made not black at normal temperature, non-yellowing under high temperature, while not influencing the solderability of coating；In addition the tin face protective agent has good stability, and is not easy muddiness.
Description
Technical field
The present invention relates to the tin coatings of wiring board technology field more particularly to a kind of printed wiring board to protect protectant match
Side.
Background technique
Chemical pure tin coating has been applied to the field of surface treatment of automobile line plate or IC support plate for a long time, this has benefited from its institute
The many merits having, tin face planarization is good, have excellent electric conductivity and solderability, can multiple welding, tin layers be free of lead, it is right
The features such as environmental nonpollution, Storage period is long (1 year), and processing procedure is simple, and working environment is good.
But tin is amphoteric metal, is easy to cause tin face to change colour under acid or alkaline environment, influences its welding performance,
Or occurs the case where coating jaundice after high temperature reflux.
General chemical plating stannum and its alloy layer occur on Copper base material, tin ion under the action of thiocarbamide, with copper from
Displacement reaction occurs for son, and after completion of the reaction, product proposes that tank liquor is washed, and often the tin plating protective agent of remaining acidity can allow
Tin face occur it is heterochromatic, so it is general it is tin plating after the completion of have one of tin face protection technique prevent tin face discoloration.Traditional tin face
The disadvantages of protection uses sodium phosphate protective agent, and undesirable but there are protecting effects, bath life is short, and protective agent is easy clouding.
Summary of the invention
Shortcoming present in view of the above technology, the invention discloses a kind of for protecting the tin face of chemical tin coating
Protective agent, the protective agent have good tin coating defencive function, coating can be made not black at normal temperature, do not sent out under high temperature
Huang, while the solderability of coating is not influenced, in addition；The tin face protective agent has good stability, and is not easy muddiness.
To achieve the above object, the present invention provides a kind of chemical plating stannum formula of printed wiring board, according to concentration include with
Lower component:
Citrate 0.5-10g/L
Phosphate 0.5-50g/L
Phytic acid 1-5g/L
Thiocarbamide 0.2-2g/L；
Above four kinds of components form solution with after the dissolution of the water of the 1/2-2/3 with volume according to the amount；1- is used again
Protectant pH value is adjusted between 2.5-3.5 by the ammonium hydroxide or phosphoric acid of 80g/L；Finally with pure water be settled to volume i.e.
Tin face protective agent can be formed；
Under normal temperature condition, tin plating workpiece is impregnated to 0.5-5mi n in the tin face protective agent can be completed protection；The tin face
Protective agent has good tin coating defencive function, and coating can be made not black at normal temperature, non-yellowing under high temperature, while not shadow
Ring the solderability of coating；In addition the tin face protective agent has good stability, and is not easy muddiness.
Wherein, the phosphate is one of phosphate, dibasic alkaliine or dihydric phosphate or a variety of, the salt of composition
Metal ion is ammonium root, sodium ion or potassium ion.
Wherein, the citrate is protectant complexing agent, and buffer, stannous ion, which can be complexed, to be prevented from precipitating；
Citric acid is salt of weak acid simultaneously, has good pH value pooling feature；The phosphate is film forming matter, in faintly acid item
Under part, in the chemical composition coating of one layer of acid tin phosphate of tin coating Surface Creation, while also having both pH value pooling feature；Phytic acid is
Corrosion inhibiter also has corrosion inhibitive function, prevents tin coating by excessive etch other than it can generate conversion film with tin face；Thiocarbamide is
Copper ion chelator, chemical tin carry out generally on copper face, and coating and its protective agent contain certain copper, and thiocarbamide can be with
The oxidizing potential for reducing copper prevents copper ion from attacking tin coating；The protective agent is adjusted to using ammonium hydroxide or phosphoric acid to adjust pH value
Between 2.5-3.5.
Wherein, the citrate be sodium citrate, potassium citrate, it is one or more in ammonium citrate；And the citric acid
The concentration of salt is in 0.5-10g/L.
The beneficial effects of the present invention are: compared with prior art, provided by the present invention for protecting the tin of chemical tin coating
Face protective agent, has the advantage that
1) tin face can be effectively protected.Phosphate can react in acid condition with tin face in protective agent grows phosphorus
Tin face is effectively protected in hydrochlorate conversion film.But too strong acid often attack tin face, general chemical tin thickness only only has
0.8-1.2 μm, attack slightly can make tin layers partially thin, and in addition too strong acidity proposes higher requirement to cleaning, if cleaning
It does not remove, will cause tin face nigrescence instead.And the invention uses pH value for the section of 2.5-3.5, conversion film can be made to be successfully generated,
But it is unlikely to excessive attack tin layers, and phytic acid is generally used to as corrosion inhibiter in the invention, and tin face can be prevented by shoulder
It is thin.
2) protective agent is more stable.Traditional tin face protective agent uses one-component, and protective agent environmental change is bigger, than
It such as says the mixed stannous ion of concentration, pH value, foreign metal ion, especially protective agent, tetravalent tin is generated after peroxidating,
And tetravalent tin be easy to cause protectant muddiness, and protective agent is caused to fail.The present invention is containing there are many chelating agent such as citric acid, phytic acid
Deng the reduction potential of stannous ion can be effectively reduced, stannous ion is prevented quickly to be oxidized to tetravalent tin, keep protective agent
Clarification.The presence of thiocarbamide can reduce the oxidizing potential of copper ion, and thiocarbamide can generate cupprous chelate with copper ion,
It prevents copper ion from replacing with tin face, and prevents copper ion from aoxidizing Bivalent Tin.
3) protective agent pH stable.Tank liquor is using citrate, phytic acid, phosphate and uses phosphoric acid or ammonium hydroxide tune
PH value is saved, above section component, because it is salt of weak acid, all has certain pH value other than there are the functions such as complexing function, conversion film
Pooling feature can make bath ratio is more stable to maintain within the scope of certain acidity.
4) function is not influenced.By the Electroless tin coating that the protective agent is protected, the solderability of coating is not influenced, is passed through in time
High-temperature baking, the stringent test of high temperature and humidity is obvious to coating protective effect, and solderability is unaffected.
5) protective agent has good tin coating defencive function, coating can be made not black at normal temperature, under high temperature not
Jaundice, while the solderability of coating is not influenced, in addition；The tin face protective agent has good stability, and is not easy muddiness.
Detailed description of the invention
Fig. 1 is the tin layers solderability curve graph protected without tin face protective agent of the invention；
Fig. 2 is the tin layers solderability curve graph protected by example 3.
Specific embodiment
In order to more clearly state the present invention, the present invention is further described below with reference to example.
Of the invention is a kind of for protecting the tin face protective agent of chemical tin coating, includes following components according to concentration:
Citrate: 0.5-10g/L；
Phosphate: 0.5-50g/L；
Phytic acid: 1-5g/L；
Thiocarbamide: 0.2-2g/L；
Above four kinds of components form solution with after the dissolution of the water of the 1/2-2/3 with volume according to the amount；1- is used again
Protectant pH value is adjusted between 2.5-3.5 by the ammonium hydroxide or phosphoric acid of 80g/L；Finally with pure water be settled to volume i.e.
Tin face protective agent can be formed；It is between the 1/2-2/3 with volume there is illustrated water consumption；
Under normal temperature condition, tin plating workpiece is impregnated to 0.5-5mi n in the tin face protective agent can be completed protection；The tin face
Protective agent has good tin coating defencive function, and coating can be made not black at normal temperature, non-yellowing under high temperature, while not shadow
Ring the solderability of coating；In addition the tin face protective agent has good stability, and is not easy muddiness.
Wherein, the phosphate is one of phosphate, dibasic alkaliine or dihydric phosphate or a variety of, the salt of composition
Metal ion is ammonium root, sodium ion or potassium ion.
Wherein, the citrate is protectant complexing agent, and buffer, stannous ion, which can be complexed, to be prevented from precipitating；
Citric acid is salt of weak acid simultaneously, has good pH value pooling feature；The phosphate is film forming matter, in faintly acid item
Under part, in the chemical composition coating of one layer of acid tin phosphate of tin coating Surface Creation, while also having both pH value pooling feature；Phytic acid is
Corrosion inhibiter also has corrosion inhibitive function, prevents tin coating by excessive etch other than it can generate conversion film with tin face；Thiocarbamide is
Copper ion chelator, chemical tin carry out generally on copper face, and coating and its protective agent contain certain copper, and thiocarbamide can be with
The oxidizing potential for reducing copper prevents copper ion from attacking tin coating；The protective agent is adjusted to using ammonium hydroxide or phosphoric acid to adjust pH value
Between 2.5-3.5.
Wherein, the citrate be sodium citrate, potassium citrate, it is one or more in ammonium citrate.
Compared to the prior art, provided by the invention a kind of for protecting the tin face protective agent of chemical tin coating, have such as
Lower advantage:
1) tin face can be effectively protected.Phosphate can react in acid condition with tin face in protective agent grows phosphorus
Tin face is effectively protected in hydrochlorate conversion film.But too strong acid often attack tin face, general chemical tin thickness only only has
0.8-1.2 μm, attack slightly can make tin layers partially thin, and in addition too strong acidity proposes higher requirement to cleaning, if cleaning
It does not remove, will cause tin face nigrescence instead.And the invention uses pH value for the section of 2.5-3.5, conversion film can be made to be successfully generated,
But it is unlikely to excessive attack tin layers, and phytic acid is generally used to as corrosion inhibiter in the invention, and tin face can be prevented by shoulder
It is thin.
2) protective agent is more stable.Traditional tin face protective agent uses one-component, and protective agent environmental change is bigger, than
It such as says the mixed stannous ion of concentration, pH value, foreign metal ion, especially protective agent, tetravalent tin is generated after peroxidating,
And tetravalent tin be easy to cause protectant muddiness, and protective agent is caused to fail.The present invention is containing there are many chelating agent such as citric acid, phytic acid
Deng the reduction potential of stannous ion can be effectively reduced, stannous ion is prevented quickly to be oxidized to tetravalent tin, keep protective agent
Clarification.The presence of thiocarbamide can reduce the oxidizing potential of copper ion, and thiocarbamide can generate cupprous chelate with copper ion,
It prevents copper ion from replacing with tin face, and prevents copper ion from aoxidizing Bivalent Tin.
3) protective agent pH stable.Tank liquor is using citrate, phytic acid, phosphate and uses phosphoric acid or ammonium hydroxide tune
PH value is saved, above section component, because it is salt of weak acid, all has certain pH value other than there are the functions such as complexing function, conversion film
Pooling feature can make bath ratio is more stable to maintain within the scope of certain acidity.
4) function is not influenced.By the Electroless tin coating that the protective agent is protected, the solderability of coating is not influenced, is passed through in time
High-temperature baking, the stringent test of high temperature and humidity is obvious to coating protective effect, and solderability is unaffected.
In order to absolutely prove the advantage of the invention, common two kinds of protective agents and parameter illustrate as a comparison in the industry for use,
The recipe ingredient for using the invention simultaneously, carries out performance comparative illustration.It uses printed wiring board as substrate, is protected with commercially available chemical tin
After protecting the heavy tin of agent progress chemistry, protected using following tin face, contrast effect.
Comparative example one: phosphoric acid: 5g/L, surplus are water；
Comparative example two: sodium phosphate: 10g/L, surplus are water；
Embodiment 3,4,5,6 is the tin face protective agent prepared using this technology；
Comparative example one is because acid stronger, and it is rare to use in the industry, and uses embodiment two relatively conventional, protection
Although agent is alkaline, after the completion of chemical tin process, surface is highly acid, and chemical composition coating still can be generated.
In addition, comparing the effect of some components in the present invention with comparative example 7,8.
Detailed comparing result is as follows:
◎: serious；Ο: general；Δ: without significant change；
It to sum up compares, has protectant tank liquor of citrate, phytic acid and thiocarbamide after using to a certain degree in tank liquor, according to
Clear state can be so kept, and coating anti-tarnishing ability is obviously reinforced；Meanwhile also compared Wuxi face protected and
Influence of 3 tin of the present embodiment protection to solderability (using standard: IPC/ECAJ-STD-003C-2014), almost without obvious shadow
It rings, the wetting curve comparison diagram of solderability such as attached drawing 1 and attached drawing 2.The buoyancy correction of weighing time t0 of Fig. 1 was less than 1 second, and from starting to moisten
90% theoretical wetting power it has been more than or equal to after wet to 5 seconds, Fig. 2 is also in this way, buoyancy correction of weighing time t0 was less than 1 second, and from opening
Wetting begin to the theoretical wetting power for being more than or equal to 90% after 5 seconds, according to IPC/ECAJ-STD-003C-2014, the two is all satisfied
A group standard.
To sum up, the tin face protection protective agent of the invention can be effectively protected tin face, improve its anti-tarnishing ability, and protect
Shield agent has good stability, and also has no significant effect to the solderability of tin layers.
Disclosed above is only several specific embodiments of the invention, but the present invention is not limited to this, any ability
What the technical staff in domain can think variation should all fall into protection scope of the present invention.
Claims (4)
1. a kind of for protecting the tin face protective agent of chemical tin coating, which is characterized in that according to concentration include following components:
Citrate 0.5-10g/L
Phosphate 0.5-50g/L
Phytic acid 1-5g/L
Thiocarbamide 0.2-2g/L；
Above four kinds of components form solution with after the dissolution of the water of the 1/2-2/3 with volume according to the amount；Again with 1-80g/L's
Protectant pH value is adjusted between 2.5-3.5 by ammonium hydroxide or phosphoric acid；Finally it is settled to pure water to be formed with volume
Tin face protective agent；
Under normal temperature condition, tin plating workpiece is impregnated to 0.5-5min in the tin face protective agent can be completed protection；Tin face protection
Agent has good tin coating defencive function, and coating can be made not black at normal temperature, non-yellowing under high temperature, while not influencing to plate
The solderability of layer；In addition the tin face protective agent has good stability, and is not easy muddiness.
2. according to claim 1 for protecting the tin face protective agent of chemical tin coating, which is characterized in that the phosphate
For one or more of phosphate, dibasic alkaliine or dihydric phosphate, the salt metal ion of composition is ammonium root, sodium ion
Or potassium ion.
3. according to claim 1 for protecting the tin face protective agent of chemical tin coating, which is characterized in that the lemon
Hydrochlorate is protectant complexing agent, and buffer, stannous ion, which can be complexed, to be prevented from precipitating；Citric acid is salt of weak acid simultaneously, is had
Good pH value pooling feature；The phosphate is film forming matter, under mildly acidic conditions, in tin coating Surface Creation one
The chemical composition coating of layer acid tin phosphate, while also having both pH value pooling feature；Phytic acid is corrosion inhibiter, in addition to that can generate with tin face
Other than conversion film, also there is corrosion inhibitive function, prevent tin coating by excessive etch；Thiocarbamide is copper ion chelator, and chemical tin is general
It is carried out on copper face, coating and its protective agent contain certain copper, and thiocarbamide can reduce the oxidizing potential of copper, prevent copper
Ion attack tin coating；The protective agent is adjusted between 2.5-3.5 using ammonium hydroxide or phosphoric acid to adjust pH value.
4. according to claim 1 for protecting the tin face protective agent of chemical tin coating, which is characterized in that the citric acid
Salt is sodium citrate, potassium citrate, one or more in ammonium citrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910415682.5A CN110093598A (en) | 2019-05-18 | 2019-05-18 | For protecting the tin face protective agent of chemical tin coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910415682.5A CN110093598A (en) | 2019-05-18 | 2019-05-18 | For protecting the tin face protective agent of chemical tin coating |
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| CN110093598A true CN110093598A (en) | 2019-08-06 |
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| CN201910415682.5A Pending CN110093598A (en) | 2019-05-18 | 2019-05-18 | For protecting the tin face protective agent of chemical tin coating |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111926332A (en) * | 2020-07-16 | 2020-11-13 | 深圳市点石源水处理技术有限公司 | Tin surface protective agent and preparation method and application thereof |
| CN112517859A (en) * | 2020-11-24 | 2021-03-19 | 太仓史密斯理查森精密制造有限公司 | Environment-friendly anti-discoloration corrosion-resistant tin plating preparation process for chaplet |
| CN113755851A (en) * | 2021-09-10 | 2021-12-07 | 珠海市板明科技有限公司 | Tin surface protective agent and film stripping liquid for circuit board production |
| CN115418643A (en) * | 2022-10-13 | 2022-12-02 | 深圳市板明科技股份有限公司 | Inorganic membrane-removing liquid containing tin-protecting additive and using method thereof |
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| CN106939417A (en) * | 2017-04-28 | 2017-07-11 | 深圳市创智成功科技有限公司 | The chemical plating stannum formula of printed wiring board |
| CN107365986A (en) * | 2017-07-11 | 2017-11-21 | 东莞市富默克化工有限公司 | A kind of tin plating technique of chemical tin inorganic agent and application the chemical tin inorganic agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111926332A (en) * | 2020-07-16 | 2020-11-13 | 深圳市点石源水处理技术有限公司 | Tin surface protective agent and preparation method and application thereof |
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| CN112517859A (en) * | 2020-11-24 | 2021-03-19 | 太仓史密斯理查森精密制造有限公司 | Environment-friendly anti-discoloration corrosion-resistant tin plating preparation process for chaplet |
| CN113755851A (en) * | 2021-09-10 | 2021-12-07 | 珠海市板明科技有限公司 | Tin surface protective agent and film stripping liquid for circuit board production |
| CN115418643A (en) * | 2022-10-13 | 2022-12-02 | 深圳市板明科技股份有限公司 | Inorganic membrane-removing liquid containing tin-protecting additive and using method thereof |
| CN115418643B (en) * | 2022-10-13 | 2023-10-31 | 深圳市板明科技股份有限公司 | Inorganic film removing liquid containing tin-protecting additive and use method thereof |
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Application publication date: 20190806 |
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