It moves back tin combination liquid and moves back tin method
Technical field
The present invention relates to wiring board processing technique field, in particular to one kind moves back tin combination liquid and moves back tin method.
Background technique
In printed wiring board manufacturing, substrate is first generally subjected to electro-coppering, graphic plating is then carried out in layers of copper
Tin or tin alloy later etch the layers of copper that do not protected by tin layers, and retain the tin layers for being plated to figure or tin alloy layers and its cover
The bottom copper of lid.It needs to remove the tin layers of copper excess surface and tin alloy layers after the completion of etching work procedure, that is, moves back tin process.
Currently, it is traditional move back tin combination liquid and generally include fluorine-containing type etching agent, organic acid type etching agent and nitric acid type move back tin
Agent.But fluorine-containing type etching agent can release toxic fluoro-gas in process of production, and since fluoride is easy attack corruption
The glass fiber component for losing board substrate insulating layer, causes substrate to be easily damaged, while fluorine-containing type etching agent moves back moving back after tin
Tin waste liquid is difficult to handle.Not only cost of material is at high cost for organic acid type etching agent, and contains large amount of organic in tin removal waste liquor, place
It is big to manage difficulty.Violent chemical reaction occurs for nitric acid type etching agent nitric acid and tin, copper metal during moving back tin, releases a large amount of
Nitrogen oxide NOx smog and pollute workshop and ambient enviroment, work in such circumstances for a long time and human body physical and mental health caused to hurt
Evil.And contain a large amount of nitric acid in tin removal waste liquor, therefore the liquid waste processing difficulty discharged after recycling metal in tin removal waste liquor is big.
Summary of the invention
The purpose of the present invention is to provide it is a kind of it is environmentally protective move back tin combination liquid and move back tin method, to solve the prior art
The problems in.
In order to solve the above technical problems, the present invention, which provides one kind, moves back tin combination liquid, moves back tin A liquid including what is individually stored and move back
Tin B liquid, in which: it is described move back tin A liquid include following weight percent each component: sulfuric acid 30-40%, hydrogen peroxide 1~5%,
Organic acid 5~10%, bleeding agent 0.5~1.5%, corrosion inhibiter 1~3%, promotor 0.5~1.5%, deionized water surplus;Institute
State each component for moving back that tin B liquid includes following weight percent: ferric trichloride 5~15%, benzotriazole 2~8%, citric acid
0.5~5%, deionized water surplus.
In a wherein embodiment, the weight percent for moving back tin A liquid and moving back tin B liquid is 1:(0.2~1.2).
It is described to move back each component that tin A liquid includes following weight percent: sulfuric acid 35%, mistake in a wherein embodiment
Hydrogen oxide 2%, organic acid 8%, bleeding agent 1%, corrosion inhibiter 2%, promotor 1%, deionized water surplus;It is described to move back tin B liquid packet
Each component containing following weight percent: ferric trichloride 10%, benzotriazole 5%, citric acid 3%, deionized water surplus.
In a wherein embodiment, the organic acid is selected from methane sulfonic acid, acetic acid, propionic acid, acrylic acid, ethanedioic acid, third
In diacid, succinic acid, glutaric acid, adipic acid maleic acid, glycolic, lactic acid, malic acid and citric acid, sulfamic acid and niacin
It is one or more.
In a wherein embodiment, the organic acid is selected from one of acetic acid, methane sulfonic acid and sulfamic acid or more
Kind.
In a wherein embodiment, the bleeding agent is selected from propylene glycol, ethylene glycol monobutyl ether, non-ionic surface active
One of agent, anionic surfactant or multiple combinations.
In a wherein embodiment, the bleeding agent is selected from one or both of propylene glycol, ethylene glycol monobutyl ether group
It closes.
In a wherein embodiment, the corrosion inhibiter is selected from imidazoles, 2-methylimidazole, 1,2- diethyl imidazolium, benzo
One of imidazoles, triazole and benzotriazole, methylbenzotrazole, tetrazole, 5- methyl benzo tetrazole, 5- aminotetrazole
Or it is several.
In a wherein embodiment, the corrosion inhibiter is selected from one or more of imidazoles, tetrazole, benzotriazole
Combination.
In a wherein embodiment, the promotor be selected from ethylenediamine, monoethanolamine, cyclohexylamine, N- methylethanolamine,
N- ehtylethanolamine, N- butylethanolamine, N, N- dimethylethanolamine, diethanol amine, N methyldiethanol amine, triethanolamine,
One of isopropanolamine, hydroxyethyl piperazine or multiple combinations.
In a wherein embodiment, the promotor be selected from one of monoethanolamine, cyclohexylamine or triethanolamine or
Multiple combinations.
The present invention also provides one kind to move back tin method, combines liquid using tin is moved back described in item as above, comprising the following steps:
S1, at 10~50 DEG C of temperature, by tin plating copper-clad plate be soaked in it is described move back the moving back 30 in tin A liquid of tin combination liquid~
It 120 seconds, completes to move back tin for the first time, obtains copper sheet;
S2, the copper sheet is washed using deionized water;
S3, at 10~50 DEG C of temperature, the copper sheet after washing is soaked in and described moves back the moving back in tin B liquid of tin combination liquid
15~30 seconds.
As shown from the above technical solution, the advantages and positive effects of the present invention are:
It is of the invention move back tin combination liquid include individually store move back tin A liquid and move back tin B liquid, first pass through and move back tin A liquid to tin layers
It carries out quickly and largely strips work, then tin layers and the copper-tin alloy of copper junction are stripped by moving back tin B liquid, i.e., it is complete
Tin work is moved back on copper-clad plate material.And move back tin combination liquid and stripping metallic tin or when tin alloy layers, it is fast to move back tin speed, moves back tin mistake
Non smoke volatilization generates in journey, solves and moves back tin combination liquid in use to the pollution problem of air.Liquid waste processing after moving back tin
Simply, it solves the problems, such as waste liquid to water resource pollution, moves back the environmentally protective of tin combination liquid to realize.
Detailed description of the invention
Fig. 1 is the flow chart that the present invention moves back tin method.
Specific embodiment
The exemplary embodiment for embodying feature of present invention and advantage will describe in detail in the following description.It should be understood that
The present invention can have various variations in different embodiments, neither depart from the scope of the present invention, and theory therein
Bright and diagram inherently is illustrated as being used, rather than to limit the present invention.
Principle and structure in order to further illustrate the present invention carry out the preferred embodiment of the present invention now in conjunction with attached drawing detailed
It describes in detail bright.
The present invention provides one kind and moves back tin combination liquid, carries out moving back Xi Chu to plate suitable for printed circuit board manufacturing process
Reason.This, which moves back tin combination liquid, can be used for stripping metallic tin and tin alloy layers on printed circuit board.
Wherein, tin alloy can be terne metal, can also be sn-ag alloy, sn-bi alloy, tin cadmium alloy, tin-indium alloy
Or other alloys.
In addition, carried out on the plate for cover copper it is tin plating after, also will form 0.05-0.10 micron thickness between copper and tin engaging portion
Copper-tin alloy layer.It is understood that cover the plate terne coating of copper, then it can also shape between copper and terne metal engaging portion
At copper-lead-tin.Also in this way, will not repeat them here between other tin alloys and the engaging portion of copper.
Tin combination liquid is moved back when stripping metallic tin and tin alloy coat in the present invention, it is fast to move back tin speed, and move back tin process
Middle non smoke volatilization generates, and solves and moves back tin combination liquid in use to the pollution problem of air.Liquid waste processing letter after moving back tin
It is single, it solves the problems, such as waste liquid to water resource pollution, moves back the environmentally protective of tin combination liquid to realize.
It this is described in detail in detail below moves back tin combination liquid and move back tin principle.
Moving back tin combination liquid includes that moving back of individually storing and moves back tin B liquid at tin A liquid, moves back tin A liquid and moves back the weight percent of tin B liquid
For 1:(0.2~1.2).
Wherein, moving back tin A liquid includes sulfuric acid, hydrogen peroxide, organic acid, bleeding agent, corrosion inhibiter, promotor and deionized water.
This move back tin A liquid move back tin key reaction formula it is as follows:
Sn+H2SO4+H2O2=SnSO4+2H2O
Cu+H2SO4+H2O2=CuSO4+2H2O
Formula can be seen that the reaction and generate without gas from the reactions above, and the component of effluent after moving back tin is simple, and most of is sulphur
Sour stannous, only a small amount of copper ion.Stannous sulfate cooperation reclaimer can recycle most tin, tin metal recycling
Waste liquid afterwards can also reuse, and then realize and move back the environmentally protective of tin combination liquid.
In the reaction, the reaction speed of tin and sulfuric acid, hydrogen peroxide is fast, can reach 5-10 [mu.
In above-mentioned reaction, the main function of sulfuric acid is to react with metallic tin and dissolve tin, hydrogen peroxide as oxidant,
Tin and copper can be oxidized to stannous oxide and copper oxide, sulfuric acid reacts with stannous oxide and copper oxide and dissolves tin and copper and tin conjunction
Gold.
Organic acid inhibits the solution rate of copper for improving Theil indices in solution.Organic acid be selected from methane sulfonic acid, acetic acid,
Propionic acid, acrylic acid, ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid maleic acid, glycolic, lactic acid, malic acid and lemon
One of acid, sulfamic acid and niacin are a variety of.
Bleeding agent makes this move back tin combination liquid and is easier to infiltration tin or tin alloy for reducing the surface tension for moving back tin combination liquid.
Bleeding agent is selected from one of propylene glycol, ethylene glycol monobutyl ether, nonionic surfactant, anionic surfactant or a variety of
Combination.Nonionic surfactant such as OP-10, fatty alcohol polyoxyethylene ether, anionic surfactant such as detergent alkylate sulphur
Hydrochlorate, lauryl sodium sulfate.
Corrosion inhibiter is for inhibiting corrosion of metal.Corrosion inhibiter is selected from imidazoles, 2-methylimidazole, 1,2- diethyl imidazolium, benzene
And imidazoles, triazole and benzotriazole, methylbenzotrazole, tetrazole, 5- methyl benzo tetrazole, one in 5- aminotetrazole
Kind is several.
Promotor is used for stable peroxide hydrogen, and then improves and move back tin speed, reduces tin ion Precipitation.Promotor is selected from
Ethylenediamine, monoethanolamine, cyclohexylamine, N- methylethanolamine, N- ehtylethanolamine, N- butylethanolamine, N, N- dimethyl ethanol
One of amine, diethanol amine, N methyldiethanol amine, triethanolamine, isopropanolamine, hydroxyethyl piperazine or multiple combinations.
Move back tin A liquid to complete etching work procedure after tin layers carry out moving back tin, and move back tin A liquid be basically completed it is big on copper-clad plate material
The stripping of part tin.
Moving back tin B liquid includes ferric trichloride, benzotriazole, citric acid and deionized water.This moves back tin B liquid and moves back the main anti-of tin
Answer formula as follows:
2FeCl3+ Sn=SnCl2+2FeCl2
2FeCl3+ Cu=CuCl2+2FeCl2
Wherein, ferric trichloride dissolution tin and copper, to complete the stripping of the copper-tin alloy of tin layers and copper junction.
Benzotriazole and copper form complex compound as protective film, prevent the corrosion of copper, and then reach the corruption for inhibiting copper
The effect of erosion.
Citric acid and copper complexing and bright copper face.
After moving back tin A liquid to the stripping for covering on tin copper sheet most of tin layers, moves back tin B liquid and further strip and cover on tin copper sheet
Tin and tin alloy in small-bore, guarantee the quality of final printed circuit board.
Moving back tin combination liquid includes that moving back of individually storing and moves back tin B liquid at tin A liquid, first pass through move back tin A liquid tin layers are carried out it is quick
And largely strip work, then strip to tin layers and the copper-tin alloy of copper junction by moving back tin B liquid, i.e. completion copper-clad plate
Tin work is moved back on material.
This move back tin combination liquid to move back tin method as follows:
S1, at 10~50 DEG C of temperature, tin plating copper-clad plate is soaked in and moves back tin combination liquid and moves back in tin A liquid 30~120 seconds,
It completes to move back tin for the first time, obtains copper sheet;
S2, copper sheet is washed using deionized water;
S3, at 10~50 DEG C of temperature, the copper sheet after washing is soaked in and moves back tin combination liquid and moves back 15~30 in tin B liquid
Second.
Moving back tin carries out stripping work to a large amount of tin layers of tin plating copper-clad plate by moving back tin A liquid for the first time, after washing
Tin layers and the copper-tin alloy of copper junction are stripped by moving back tin B liquid again.Using two-step method, respectively to the tin and tin on surface layer
Layer and the copper-tin alloy of copper junction are stripped, and are adequately protected copper, be ensure that the quality of wiring board.
The content of each component is introduced by the following examples.
Embodiment 1
For preparing and move back tin A liquid and move back each 1kg of tin B liquid, moves back tin combination liquid each component and content is as follows:
Move back tin A liquid:
The present embodiment 1 moves back tin A liquid making method, comprising the following steps:
A1 measures 98% concentrated sulfuric acid of 163.04mL, is slowly added in deionized water while stirring, it is molten to obtain sulfuric acid
Liquid;
A2 measures 17.73mL hydrogen peroxide, is added in sulfuric acid solution, obtains mixed solution |;
A3 measures 33.80mL methane sulfonic acid, and 4.83mL propylene glycol and 9.80mL monoethanolamine are added in sulfuric acid solution,
Stirring is allowed to uniformly mixed, obtains mixed solution II;
A3, weighs 10.00g tetrazole, and mixed solution is added | in, stirring makes tetrazole dissolve and be uniformly mixed, then plus
Enter mixed solution II to continue to stir, be uniformly mixed, and deionized water, which is added, makes weight 1Kg to get to moving back tin A liquid.
Move back tin B liquid:
Ferric trichloride 50.00g
Benzotriazole 20.00g
Citric acid 30.00g
Deionized water surplus.
The present embodiment 1 moves back tin B liquid making method, comprising the following steps:
A1, weighs the ferric trichloride of 50.00g, and the benzotriazole of 20.00g is dissolved in deionized water, is mixed
Solution III;
A2 measures the citric acid of 30.00mL, is added in above-mentioned mixed solution III, is uniformly mixed, and deionized water is added to make
Weight is 1Kg to get to moving back tin B liquid.
It is 1:(0.2~1.2 that basis, which moves back tin A liquid with the weight percent for moving back tin B liquid, when in use) it carries out moving back tin.
Embodiment 2
For preparing and move back tin A liquid 1 and move back each 1kg of tin B liquid, moves back tin combination liquid each component and content is as follows:
Move back tin A liquid:
Move back tin B liquid:
Ferric trichloride 150.00g
Benzotriazole 80.00g
Citric acid 3.00g
Deionized water surplus.
Moving back for the present embodiment and moves back the preparation method reference implementation example 1 of tin B liquid at tin A liquid, and details are not described herein.
It is 1:(0.2~1.2 that basis, which moves back tin A liquid with the weight percent for moving back tin B liquid, when in use) it carries out moving back tin.
Embodiment 3
For preparing and move back tin A liquid and move back each 1kg of tin B liquid, moves back tin combination liquid each component and content is as follows:
Move back tin A liquid:
Move back tin B liquid:
Ferric trichloride 80.00g
Benzotriazole 40.00g
Citric acid 12.00g
Deionized water surplus.
Moving back for the present embodiment and moves back the preparation method reference implementation example 1 of tin B liquid at tin A liquid, and details are not described herein.
It is 1:(0.2~1.2 that basis, which moves back tin A liquid with the weight percent for moving back tin B liquid, when in use) it carries out moving back tin.
Embodiment 4
For preparing and move back tin A liquid and move back each 1kg of tin B liquid, moves back tin combination liquid each component and content is as follows:
Move back tin A liquid:
Move back tin B liquid:
Ferric trichloride 120.00g
Benzotriazole 6.00g
Citric acid 24.00g
Deionized water surplus.
Moving back for the present embodiment and moves back the preparation method reference implementation example 1 of tin B liquid at tin A liquid, and details are not described herein.
It is 1:(0.2~1.2 that basis, which moves back tin A liquid with the weight percent for moving back tin B liquid, when in use) it carries out moving back tin.
Embodiment 5
For preparing and move back tin A liquid and move back each 1kg of tin B liquid, moves back tin combination liquid each component and content is as follows:
Move back tin A liquid:
Move back tin B liquid:
Ferric trichloride 100.00g
Benzotriazole 30.00g
Citric acid 18.00g
Deionized water surplus.
Moving back for the present embodiment and moves back the preparation method reference implementation example 1 of tin B liquid at tin A liquid, and details are not described herein.
It is 1:(0.2~1.2 that basis, which moves back tin A liquid with the weight percent for moving back tin B liquid, when in use) it carries out moving back tin.
Embodiment 6
For preparing and move back tin A liquid and move back each 1kg of tin B liquid, moves back tin combination liquid each component and content is as follows:
Move back tin A liquid:
Move back tin B liquid:
Ferric trichloride 100.00g
Benzotriazole 30.00g
Citric acid 18.00g
Deionized water surplus.
Moving back for the present embodiment and moves back the preparation method reference implementation example 1 of tin B liquid at tin A liquid, and details are not described herein.
It is 1:(0.2~1.2 that basis, which moves back tin A liquid with the weight percent for moving back tin B liquid, when in use) it carries out moving back tin.
Embodiment 7
For preparing and move back tin A liquid and move back each 1kg of tin B liquid, moves back tin combination liquid each component and content is as follows:
Move back tin A liquid:
Move back tin B liquid:
Ferric trichloride 100.00g
Benzotriazole 30.00g
Citric acid 18.00g
Deionized water surplus.
Moving back for the present embodiment and moves back the preparation method reference implementation example 1 of tin B liquid at tin A liquid, and details are not described herein.
It is 1:(0.2~1.2 that basis, which moves back tin A liquid with the weight percent for moving back tin B liquid, when in use) it carries out moving back tin.
Embodiment 8
For preparing and move back tin A liquid and move back each 1kg of tin B liquid, moves back tin combination liquid each component and content is as follows:
Move back tin A liquid:
Move back tin B liquid:
Ferric trichloride 100.00g
Benzotriazole 30.00g
Citric acid 18.00g
Deionized water surplus.
Moving back for the present embodiment and moves back the preparation method reference implementation example 1 of tin B liquid at tin A liquid, and details are not described herein.
It is 1:(0.2~1.2 that basis, which moves back tin A liquid with the weight percent for moving back tin B liquid, when in use) it carries out moving back tin.
Embodiment 9
For preparing and move back tin A liquid and move back each 1kg of tin B liquid, moves back tin combination liquid each component and content is as follows:
Move back tin A liquid:
Move back tin B liquid:
Ferric trichloride 100.00g
Benzotriazole 30.00g
Citric acid 18.00g
Deionized water surplus.
Moving back for the present embodiment and moves back the preparation method reference implementation example 1 of tin B liquid at tin A liquid, and details are not described herein.
It is 1:(0.2~1.2 that basis, which moves back tin A liquid with the weight percent for moving back tin B liquid, when in use) it carries out moving back tin.
Comparative example 1
Its tin stripping liquid includes each component of following weight percent:
68% nitric acid 50%, ferric nitrate 10%, benzotriazole 5%, restrainer lan-826 3%, deionized water
Surplus.
Comparative example 2
Tin commodity are moved back in market sale, are nitric acid-ferric nitrate system.
Comparative example 3
Tin commodity are moved back in market sale, are nitric acid system.
Tin plating copper-clad plate (tin plating thickness 5-10um) is cut into 50mm × 50mm size, as test substrate, is used
Tin speed and erosion amount of copper are moved back in the tin combination liquid test of moving back prepared, and observe copper-clad plate face phenomenon.It is combined using the tin that moves back of embodiment 1-9
The tin stripping liquid of liquid and comparative example 1-3 carry out moving back tin at a temperature of 30 DEG C.The tin combination liquid that moves back of embodiment 1-9 is moved back using of the invention
Tin method carries out moving back tin, and comparative example 1 carries out moving back tin according to its corresponding method.
After moving back tin, by the weight of the test substrate before and after calculation processing, etching speed is calculated according to the following formula.
Move back tin speed (μm/minute)=[weight (g)-treated weight (g)] before processing ÷ substrate area (m2)÷
7.28(g/cm3) ÷ processing time (minute);
Sting copper speed (μm/minute)=[weight (g)-treated weight (g)] before processing ÷ substrate area (m2)÷
8.92(g/cm3) ÷ processing time (minute)
Test result is as shown in table 1.
Table 1
As can be seen from the above table, of the invention to move back tin combination liquid to move back tin speed fast, and non smoke volatilization produces during moving back tin
It is raw, it solves and moves back tin combination liquid in use to the pollution problem of air.Liquid waste processing after moving back tin is simple, solves waste liquid pair
The problem of water resource pollution, moves back the environmentally protective of tin combination liquid to realize.
As shown from the above technical solution, the advantages and positive effects of the present invention are:
It is of the invention move back tin combination liquid include individually store move back tin A liquid and move back tin B liquid, first pass through and move back tin A liquid to tin layers
It carries out quickly and largely strips work, then tin layers and the copper-tin alloy of copper junction are stripped by moving back tin B liquid, i.e., it is complete
Tin work is moved back on copper-clad plate material.And tin combination liquid is moved back when stripping metallic tin or tin alloy layers, it is fast to move back tin speed, and move back tin
Non smoke volatilization in the process generates, and solves and moves back tin combination liquid in use to the pollution problem of air.At waste liquid after moving back tin
Reason is simple, solves the problems, such as waste liquid to water resource pollution, moves back the environmentally protective of tin combination liquid to realize.
Although describing the present invention with reference to several exemplary embodiments, it is to be understood that, term used be explanation and
Term exemplary, and not restrictive.Due to the present invention can be embodied in a variety of forms without departing from invention spirit or
Essence, it should therefore be appreciated that above embodiment is not limited to any of the foregoing details, and should be defined by the appended claims
The whole change and modification widely explained, therefore fallen into claim or its equivalent scope in spirit and scope all should be with
Attached claim is covered.