CN108866521A - A kind of chemical bronze plating liquid - Google Patents
A kind of chemical bronze plating liquid Download PDFInfo
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- CN108866521A CN108866521A CN201811025133.9A CN201811025133A CN108866521A CN 108866521 A CN108866521 A CN 108866521A CN 201811025133 A CN201811025133 A CN 201811025133A CN 108866521 A CN108866521 A CN 108866521A
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- China
- Prior art keywords
- plating liquid
- chemical bronze
- bronze plating
- copper
- parts
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- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/422—Plated through-holes or plated via connections characterised by electroless plating method; pretreatment therefor
Abstract
The present invention provides a kind of chemical bronze plating liquids.The chemical bronze plating liquid includes the component of following parts by weight：1-10 parts of cupric salt, 0.1-10 parts of divalent nickel salt, 2-50 parts of reducing agent, 20-100 parts of complexing agent, 0.0001-0.02 parts of stabilizer and pH adjusting agent；The stabilizer includes at least two in thiocarbamide, bipyridyl and 2-mercaptobenzothiazole, and does not include cyanide.The copper deposits densification that chemical bronze plating liquid provided by the invention is formed is smooth, and hole is smaller；It can be effectively reduced the surface roughness of electroplated layer after being electroplated, improve brightness.
Description
Technical field
The invention belongs to wiring board technical field of producing, and in particular to a kind of chemical bronze plating liquid.
Background technique
Printed wiring board (PCB) presses the folding resistance of material according to it, can be divided into hard wiring board, flexibility (or flexible)
Wiring board and three kinds of flexible and hard combined circuit board.Wherein, the surface conductance material of hard wiring board is usually electrolytic copper foil；And it is flexible
The surface conductance material of wiring board is usually rolled copper foil, is primarily due to rolled copper foil with characteristics such as preferable ductility.
Rigid Flex is then as needed using electrolytic copper foil or rolled copper foil as surface conductance material.
Hole metallization (PTH) and electro-coppering are to make two necessary steps of wiring board, wherein electroless copper is wiring board
One of common method of hole metallization, for do plate effect (including in hole metallization and plate surface situation) play it is particularly critical
Effect.Flexible circuit board has higher requirements commonly used in high-grade accurate printed circuit field, the appearance final for wiring board.
But the performance that chemical bronze plating liquid currently on the market is primarily upon is usually stability of solution, deposition rate, backlight, reliability
Etc. indexs, and seldom pay close attention to the quality of chemical plating copper layer on PCB copper foil.In practical applications, it is found by the applicant that traditional chemistry
When copper plating bath is applied to rolled copper foil and electrolytic copper foil wiring board hole metallization, copper foil (especially rolled copper foil) will lead to rear
It is coarse that plate face is led to the problem of in continuous electroplating process, plate face dumb light after plating, display surface is rough and uneven in surface under microscope.
Rolled copper foil is more prone to produce the reason of rear surface problem of rough is electroplated than electrolytic copper foil：The latter's crystalline arrangement is whole
Together, formed coating and the surface finally formed after surface treatment are more smooth；The former makes laminated crystalline tissue due to processing technology
Structure recrystallizes again, though ductility is preferable, copper foil surface will appear irregular splitting and rough structure.But
It is how to reduce the surface roughness after printed wiring board is electroplated to there is no effective method, is this field urgent problem to be solved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of chemical bronze plating liquid.By the chemical plating
The copper deposits densification that copper liquid is formed is smooth, and hole is smaller, can be effectively reduced the surface roughness of electroplated layer after plating, improves
Brightness.
For this purpose, the present invention uses following technical scheme：
The present invention provides a kind of chemical bronze plating liquid, the component including following parts by weight：
1-10 parts of cupric salt, 0.1-10 parts of divalent nickel salt, 2-50 parts of reducing agent, 20-100 parts of complexing agent, stabilizer
0.0001-0.02 parts and pH adjusting agent；
The stabilizer includes at least two in thiocarbamide, bipyridyl and 2-mercaptobenzothiazole, and does not include cyanide.
It should be noted that heretofore described " cyanide " is to refer to ionize out cyanide ion in aqueous solution
(CN-) substance, such as Cymag, potassium cyanide.
Cyanide is the most common stabilizer of chemical bronze plating liquid, but cyanide category extremely toxic substance, exist in use process compared with
Big security risk；And inventors discovered through research that, the copper deposits that chemical bronze plating liquid containing cyanide is formed often table
Face out-of-flatness, hole is larger, leads to electroplated layer rough surface after plating, brightless, influences product quality.The present invention does not use
Cyanide, and select at least two in thiocarbamide, bipyridyl and 2-mercaptobenzothiazole to be used cooperatively, in conjunction with cupric salt and
Divalent nickel salt, the copper deposits densification that obtained chemical bronze plating liquid is formed is smooth, and hole is smaller, and layer surface light is electroplated after plating
Bright, roughness is lower, and appearance is good.
In the present invention, the parts by weight of the cupric salt can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts,
4.0 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts etc..
The parts by weight of the reducing agent can be 2 parts, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22
Part, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts or 50 parts etc..
The parts by weight of the complexing agent can be 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40
Part, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts, 92 parts, 95 parts, 98 parts
Or 100 parts etc..
The parts by weight of the stabilizer can be 0.0001 part, 0.0002 part, 0.0003 part, 0.0004 part, 0.0005
Part, 0.0006 part, 0.0007 part, 0.0008 part, 0.0009 part, 0.001 part, 0.002 part, 0.003 part, 0.004 part, 0.005
Part, 0.006 part, 0.007 part, 0.008 part, 0.009 part, 0.01 part, 0.011 part, 0.012 part, 0.013 part, 0.014 part,
0.015 part, 0.016 part, 0.017 part, 0.018 part, 0.019 part or 0.02 part etc..
As the preferred technical solution of the present invention, the chemical bronze plating liquid is based on mass concentration, including following component：
Cupric salt 1-10g/L, divalent nickel salt 0.1-10g/L, reducing agent 2-50g/L, complexing agent 20-100g/L, stabilization
Agent 0.0001-0.02g/L and pH adjusting agent, solvent are water.
In the present invention, the mass concentration of the cupric salt can be 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L,
3.5g/L、4.0g/L、4.5g/L、5g/L、5.5g/L、6g/L、6.5g/L、7g/L、7.5g/L、8g/L、8.5g/L、9g/L、
9.5g/L or 10g/L etc..
The mass concentration of the reducing agent can be 2g/L, 3g/L, 5g/L, 8g/L, 10g/L, 12g/L, 15g/L, 18g/
L, 20g/L, 22g/L, 25g/L, 28g/L, 30g/L, 32g/L, 35g/L, 38g/L, 40g/L, 42g/L, 45g/L, 48g/L or
50g/L etc..
The mass concentration of the complexing agent can be 20g/L, 22g/L, 25g/L, 28g/L, 30g/L, 32g/L, 35g/L,
38g/L、40g/L、45g/L、50g/L、55g/L、60g/L、65g/L、70g/L、75g/L、80g/L、82g/L、85g/L、88g/
L, 90g/L, 92g/L, 95g/L, 98g/L or 100g/L etc..
The mass concentration of the stabilizer can be 0.0001g/L, 0.0002g/L, 0.0003g/L, 0.0004g/L,
0.0005g/L、0.0006g/L、0.0007g/L、0.0008g/L、0.0009g/L、0.001g/L、0.002g/L、0.003g/L、
0.004g/L、0.005g/L、0.006g/L、0.007g/L、0.008g/L、0.009g/L、0.01g/L、0.011g/L、
0.012g/L, 0.013g/L, 0.014g/L, 0.015g/L, 0.016g/L, 0.017g/L, 0.018g/L, 0.019g/L or
0.02g/L etc..
As the preferred technical solution of the present invention, the pH of the chemical bronze plating liquid is 11-12.5；Such as can be 11,
11.1,11.2,11.3,11.4,11.5,11.6,11.7,11.8,11.9,12,12.1,12.2,12.3,12.4 or 12.5 etc..
As the preferred technical solution of the present invention, the cupric salt is selected from copper chloride, cupric sulfate pentahydrate, copper nitrate, wine
One of stone acid copper or copper acetate or at least two combination, the typical but non-limiting example of the combination has：Copper chloride
The combination of combination, copper chloride and copper nitrate, the combination of copper chloride and cupric tartrate, cupric sulfate pentahydrate and nitre with cupric sulfate pentahydrate
The combination of sour copper, the combination of cupric sulfate pentahydrate and copper acetate, the combination of copper nitrate and cupric tartrate, cupric tartrate and copper acetate
Combination etc.；Preferably cupric sulfate pentahydrate.
As the preferred technical solution of the present invention, the divalent nickel salt is six hydration nickel sulfate and/or nickel chloride.
As the preferred technical solution of the present invention, the reducing agent is formaldehyde and/or sodium hypophosphite, preferably formaldehyde.
As the preferred technical solution of the present invention, the complexing agent be selected from tartaric acid, tartrate, ethylenediamine tetra-acetic acid,
Edetate, citric acid, citrate, N-hydroxyethyl-ethylenediamine triacetic acid, N-hydroxyethyl-ethylenediamine triacetate, three
One of ethanol amine, nitrilotriacetic acid or nitrilotriacetic acid salt or at least two combination, the combination is typical but non-limiting reality
Example has：The combination of tartaric acid and ethylenediamine tetra-acetic acid, the combination of tartrate and citrate, tartrate and N- ethoxy second
The combination of ethylenediamine triacetic acid, the combination of tartrate and triethanolamine, edetate and citrate combination, second two
Amine tetraacetate and the combination of N-hydroxyethyl-ethylenediamine triacetate, the combination of edetate and nitrilotriacetic acid salt, lemon
Combination, triethanolamine and the combination of nitrilotriacetic acid etc. of lemon hydrochlorate and N-hydroxyethyl-ethylenediamine triacetate；Preferably tartaric acid
Potassium sodium.
As the preferred technical solution of the present invention, the stabilizer further includes ferrocyanide.
It should be noted that iron atom and cyano form stable ferrous cyanide ion Fe (CN) in ferrocyanide6 4-,
It is not belonging to heretofore described cyanide.
As the preferred technical solution of the present invention, any one ingredient in the stabilizer is in the chemical bronze plating liquid
Mass content be not less than 0.005ppm.
Each ingredient of stabilizer can play a role under suitable ratio, but when the content of a certain ingredient is too low, then can
Destroy the matching relationship between each ingredient.
As the preferred technical solution of the present invention, the pH adjusting agent is sodium hydroxide and/or potassium hydroxide.
Compared with prior art, the invention has the advantages that：
Chemical bronze plating liquid provided by the invention can be used for rolling copper (RA copper), cathode copper (ED copper), macromolecule resin and glass
The copper deposits densification of the material surfaces such as fibre, formation is smooth, and hole is smaller, can reduce the rough surface of electroplated layer after plating
Degree improves brightness.
Detailed description of the invention
Fig. 1 a is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that embodiment 1 provides is formed on calendering copper surface；
Fig. 1 b is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that embodiment 1 provides is formed on cathode copper surface；
Fig. 1 c is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that embodiment 1 provides is formed in FR4 resin surface
Piece；
Fig. 1 d is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that embodiment 1 provides is formed on glass surface；
Fig. 1 e is the chemical bronze plating liquid that provides of embodiment 1 after the electroless copper deposition layer electro-coppering that calendering copper surface is formed
Metallograph；
Fig. 1 f is the chemical bronze plating liquid that provides of embodiment 1 after the electroless copper deposition layer electro-coppering that cathode copper surface is formed
Metallograph；
Fig. 2 a is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that comparative example 1 provides is formed on calendering copper surface；
Fig. 2 b is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that comparative example 1 provides is formed on cathode copper surface；
Fig. 2 c is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that comparative example 1 provides is formed in FR4 resin surface
Piece；
Fig. 2 d is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that comparative example 1 provides is formed on glass surface；
Fig. 2 e is the chemical bronze plating liquid that provides of comparative example 1 after the electroless copper deposition layer electro-coppering that calendering copper surface is formed
Metallograph；
Fig. 2 f is the chemical bronze plating liquid that provides of comparative example 1 after the electroless copper deposition layer electro-coppering that cathode copper surface is formed
Metallograph；
Fig. 3 a is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that comparative example 2 provides is formed on calendering copper surface；
Fig. 3 b is the chemical bronze plating liquid that provides of comparative example 2 after the electroless copper deposition layer electro-coppering that calendering copper surface is formed
Metallograph；
Fig. 3 c is the chemical bronze plating liquid that provides of comparative example 2 after the electroless copper deposition layer electro-coppering that cathode copper surface is formed
Metallograph；
Fig. 4 a is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that embodiment 2 provides is formed on calendering copper surface；
Fig. 4 b is the chemical bronze plating liquid that provides of embodiment 2 after the electroless copper deposition layer electro-coppering that calendering copper surface is formed
Metallograph；
Fig. 4 c is the chemical bronze plating liquid that provides of embodiment 2 after the electroless copper deposition layer electro-coppering that cathode copper surface is formed
Metallograph；
Fig. 5 a is the chemical bronze plating liquid that provides of comparative example 3 after the electroless copper deposition layer electro-coppering that calendering copper surface is formed
Metallograph；
Fig. 5 b is the chemical bronze plating liquid that provides of comparative example 3 after the electroless copper deposition layer electro-coppering that cathode copper surface is formed
Metallograph；
Fig. 6 a is the SEM photograph for the electroless copper deposition layer that the chemical bronze plating liquid that embodiment 3 provides is formed on calendering copper surface；
Fig. 6 b is the chemical bronze plating liquid that provides of embodiment 3 after the electroless copper deposition layer electro-coppering that calendering copper surface is formed
Metallograph；
Fig. 6 c is the chemical bronze plating liquid that provides of embodiment 3 after the electroless copper deposition layer electro-coppering that cathode copper surface is formed
Metallograph；
Fig. 7 a is the chemical bronze plating liquid that provides of comparative example 4 after the electroless copper deposition layer electro-coppering that calendering copper surface is formed
Metallograph；
Fig. 7 b is the chemical bronze plating liquid that provides of comparative example 4 after the electroless copper deposition layer electro-coppering that cathode copper surface is formed
Metallograph.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.Art technology
Personnel understand the present invention it will be clearly understood that the specific embodiment is only to aid in, and should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of chemical bronze plating liquids, based on mass concentration, including following component：
Cupric sulfate pentahydrate 10g/L, six hydration nickel sulfate 8g/L, formaldehyde 3g/L, sodium potassium tartrate tetrahydrate 80g/L, thiocarbamide 0.01g/
L, bipyridyl 0.0001g/L and pH adjusting agent；
Wherein, solvent is deionized water, and pH adjusting agent is sodium hydroxide, pH value of solution 12.0.
Rolled copper foil pcb board, electrolytic copper foil pcb board, FR4 resin plate and pcb board with through-hole (are had naked on hole wall respectively
The glass of dew) after necessary pre-treatment, it is placed in plating 6min in chemical bronze plating liquid provided in this embodiment, forms chemical copper
Sedimentary is cleaned, dry, then surface topography is observed with scanning electron microscope (SEM), as a result respectively such as Fig. 1 a- Fig. 1 d institute
Show.Continue the electroless copper deposition layer surface electro-coppering in rolled copper foil pcb board and electrolytic copper foil pcb board, is seen with metallographic microscope
The surface topography of copper electroplating layer is examined, as a result as shown in Fig. 1 e and 1f.
Chemical bronze plating liquid provided in this embodiment is formed in calendering copper and cathode copper surface it can be seen from Fig. 1 a and Fig. 1 b
Electroless copper deposition layer it is fine and close smooth；Chemical bronze plating liquid provided in this embodiment is in FR4 resin surface shape it can be seen from Fig. 1 c
At electroless copper deposition layer it is finer and close, hole is smaller；Chemical bronze plating liquid provided in this embodiment is in hole wall it can be seen from Fig. 1 d
The electroless copper deposition layer that glass surface is formed is finer and close, and intercrystalline gap is smaller.In this implementation it can be seen from Fig. 1 e and Fig. 1 f
After the electroless copper deposition layer surface electro-coppering that the chemical bronze plating liquid that example provides is formed, copper electroplating layer surface-brightening, roughness is lower.
Comparative example 1
The difference from embodiment 1 is that being free of bipyridyl in chemical bronze plating liquid, thiocarbamide content is 0.0101g/L.
According to the method for embodiment 1, the chemical bronze plating liquid provided using comparative example 1 is respectively in calendering copper, cathode copper, FR4
Resin and hole wall glass surface form electroless copper deposition layer, and surface topography is respectively as shown in Fig. 2 a- Fig. 2 d.Continue in calendering copper
With the electroless copper deposition layer surface electro-coppering of cathode copper, the surface topography of copper electroplating layer is as shown in figure 2 e and 2f.
The chemical bronze plating liquid that comparative example 1 provides it can be seen from Fig. 2 a and Fig. 2 b is formed in calendering copper and cathode copper surface
Electroless copper deposition layer have honeycomb structure, it is not fine and close；The chemical bronze plating liquid that comparative example 1 provides it can be seen from Fig. 2 c exists
The electroless copper deposition layer hole that FR4 resin surface is formed is larger, not fine and close；The chemistry that comparative example 1 provides it can be seen from Fig. 2 d
Copper plating bath has apparent gap in the intercrystalline for the electroless copper deposition layer that hole wall glass surface is formed.It can be with by Fig. 2 e and Fig. 2 f
Find out, after the electroless copper deposition layer surface electro-coppering that the chemical bronze plating liquid that comparative example 1 provides is formed, copper electroplating layer surface is thick
It is rough, it is brightless.
Comparative example 2
The difference from embodiment 1 is that also containing the Cymag of 0.001g/L in chemical bronze plating liquid.
According to the method for embodiment 1, the chemical bronze plating liquid provided using comparative example 2 is respectively on calendering copper and cathode copper surface
Form electroless copper deposition layer, wherein the surface topography for rolling the electroless copper deposition layer of copper is as shown in Figure 3a.Continue calendering copper and
The electroless copper deposition layer surface electro-coppering of cathode copper, the surface topography of copper electroplating layer is as shown in figures 3 b and 3 c.
The electroless copper deposition layer that the chemical bronze plating liquid that comparative example 2 provides it can be seen from Fig. 3 a is formed on calendering copper surface
It is not fine and close with honeycomb structure；The change formed it can be seen from Fig. 3 b and Fig. 3 b in the chemical bronze plating liquid that comparative example 2 provides
After learning copper deposits electroplating surface copper, copper electroplating layer rough surface is not bright.
Embodiment 2
The present embodiment provides a kind of chemical bronze plating liquids, based on mass concentration, including following component：
Cupric sulfate pentahydrate 8g/L, six hydration nickel sulfate 1g/L, formaldehyde 5g/L, disodium ethylene diamine tetraacetate 40g/L, thiocarbamide
0.0002g/L, 2-mercaptobenzothiazole 0.01g/L and pH adjusting agent；
Wherein, solvent is deionized water, and pH adjusting agent is sodium hydroxide, pH value of solution 11.8.
According to the method for embodiment 1, using chemical bronze plating liquid provided in this embodiment respectively in calendering copper and cathode copper table
Face forms electroless copper deposition layer, wherein rolls the surface topography of electroless copper deposition layer of copper as shown in fig. 4 a.Continue in calendering copper
With the electroless copper deposition layer surface electro-coppering of cathode copper, the surface topography of copper electroplating layer is as shown in figure 4 b and 4 c.
The electroless copper deposition layer that chemical bronze plating liquid provided in this embodiment is formed on calendering copper surface it can be seen from Fig. 4 a
It is fine and close smooth；The electroless copper deposition layer table formed it can be seen from Fig. 4 b and Fig. 4 c in chemical bronze plating liquid provided in this embodiment
After the electro-coppering of face, copper electroplating layer surface-brightening, roughness is lower.
Comparative example 3
The difference from example 2 is that being free of thiocarbamide in chemical bronze plating liquid, 2-mercaptobenzothiazole content is 0.0102g/
L。
According to the method for embodiment 1, the chemical bronze plating liquid provided using comparative example 3 is respectively on calendering copper and cathode copper surface
Electroless copper deposition layer is formed, the electroless copper deposition layer surface electro-coppering in calendering copper and cathode copper, the surface of copper electroplating layer are continued
Pattern is as shown in figure 5a and 5b.
The electroless copper deposition layer surface formed it can be seen from Fig. 5 a and Fig. 5 b in the chemical bronze plating liquid that comparative example 3 provides
After electro-coppering, copper electroplating layer rough surface is not bright.
Embodiment 3
The present embodiment provides a kind of chemical bronze plating liquids, based on mass concentration, including following component：
Cupric sulfate pentahydrate 6g/L, six hydration nickel sulfate 10g/L, formaldehyde 13g/L, sodium citrate 65g/L, bipyridyl
0.001g/L, 2-mercaptobenzothiazole 0.005g/L and pH adjusting agent；
Wherein, solvent is deionized water, and pH adjusting agent is sodium hydroxide, pH value of solution 12.5.
According to the method for embodiment 1, using chemical bronze plating liquid provided in this embodiment respectively in calendering copper and cathode copper table
Face forms electroless copper deposition layer, wherein the surface topography for rolling the electroless copper deposition layer of copper is as shown in Figure 6 a.Continue in calendering copper
With the electroless copper deposition layer surface electro-coppering of cathode copper, the surface topography of copper electroplating layer is as shown in figs. 6b and 6c.
The electroless copper deposition layer that chemical bronze plating liquid provided in this embodiment is formed on calendering copper surface it can be seen from Fig. 6 a
It is fine and close smooth；The electroless copper deposition layer table formed it can be seen from Fig. 6 b and Fig. 6 c in chemical bronze plating liquid provided in this embodiment
After the electro-coppering of face, copper electroplating layer surface-brightening, roughness is lower.
Comparative example 4
Difference with embodiment 3 is, 2-mercaptobenzothiazole is free of in chemical bronze plating liquid, and bipyridyl content is
0.006g/L。
According to the method for embodiment 1, the chemical bronze plating liquid provided using comparative example 4 is respectively on calendering copper and cathode copper surface
Electroless copper deposition layer is formed, the electroless copper deposition layer surface electro-coppering in calendering copper and cathode copper, the surface of copper electroplating layer are continued
Pattern is as illustrated in figs. 7 a and 7b.
The electroless copper deposition layer surface formed it can be seen from Fig. 7 a and Fig. 7 b in the chemical bronze plating liquid that comparative example 4 provides
After electro-coppering, copper electroplating layer rough surface is not bright.
Embodiment 4
The present embodiment provides a kind of chemical bronze plating liquids, based on mass concentration, including following component：
Copper chloride 1g/L, nickel chloride 0.5g/L, sodium hypophosphite 30g/L, triethanolamine 30g/L, thiocarbamide 0.001g/L, connection pyrrole
Pyridine 0.0001g/L, 2-mercaptobenzothiazole 0.01g/L and pH adjusting agent；
Wherein, solvent is deionized water, and pH adjusting agent is sodium hydroxide, pH value of solution 12.0.
The change that chemical bronze plating liquid provided in this embodiment is formed on calendering copper, cathode copper, FR4 resin and hole wall glass surface
It is fine and close smooth to learn copper deposits, hole is smaller；Electroplated layer surface-brightening after plating, roughness are lower.
Embodiment 5
The present embodiment provides a kind of chemical bronze plating liquids, based on mass concentration, including following component：
Cupric sulfate pentahydrate 2g/L, six hydration nickel sulfate 2g/L, formaldehyde 10g/L, sodium potassium tartrate tetrahydrate 20g/L, thiocarbamide 0.001g/
L, bipyridyl 0.0001g/L, potassium ferrocyanide 0.001g/L and pH adjusting agent；
Wherein, solvent is deionized water, and pH adjusting agent is sodium hydroxide, pH value of solution 11.0.
The change that chemical bronze plating liquid provided in this embodiment is formed on calendering copper, cathode copper, FR4 resin and hole wall glass surface
It is fine and close smooth to learn copper deposits, hole is smaller；Electroplated layer surface-brightening after plating, roughness are lower.
Embodiment 6
The present embodiment provides a kind of chemical bronze plating liquids, based on mass concentration, including following component：
Cupric sulfate pentahydrate 5g/L, six hydration nickel sulfate 5g/L, formaldehyde 6g/L, sodium potassium tartrate tetrahydrate 50g/L, thiocarbamide 0.0002g/
L, 2-mercaptobenzothiazole 0.01g/L, potassium ferrocyanide 0.001g/L and pH adjusting agent；
Wherein, solvent is deionized water, and pH adjusting agent is sodium hydroxide, pH value of solution 11.5.
The change that chemical bronze plating liquid provided in this embodiment is formed on calendering copper, cathode copper, FR4 resin and hole wall glass surface
It is fine and close smooth to learn copper deposits, hole is smaller；Electroplated layer surface-brightening after plating, roughness are lower.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of chemical bronze plating liquid, which is characterized in that the chemical bronze plating liquid includes the component of following parts by weight：
1-10 parts of cupric salt, 0.1-10 parts of divalent nickel salt, 2-50 parts of reducing agent, 20-100 parts of complexing agent, stabilizer 0.0001-
0.02 part and pH adjusting agent；
The stabilizer includes at least two in thiocarbamide, bipyridyl and 2-mercaptobenzothiazole, and does not include cyanide.
2. chemical bronze plating liquid according to claim 1, which is characterized in that the chemical bronze plating liquid is based on mass concentration, packet
Include following component：
Cupric salt 1-10g/L, divalent nickel salt 0.1-10g/L, reducing agent 2-50g/L, complexing agent 20-100g/L, stabilizer
0.0001-0.02g/L and pH adjusting agent, solvent are water.
3. chemical bronze plating liquid according to claim 1 or 2, which is characterized in that the pH of the chemical bronze plating liquid is 11-
12.5。
4. chemical bronze plating liquid according to claim 1-3, which is characterized in that the cupric salt is selected from chlorination
One of copper, cupric sulfate pentahydrate, copper nitrate, cupric tartrate or copper acetate or at least two combination, preferably five water sulfuric acid
Copper.
5. chemical bronze plating liquid according to claim 1-4, which is characterized in that the divalent nickel salt is six hydration sulphur
Sour nickel and/or nickel chloride.
6. chemical bronze plating liquid according to claim 1-5, which is characterized in that the reducing agent be formaldehyde and/or
Sodium hypophosphite, preferably formaldehyde.
7. chemical bronze plating liquid according to claim 1-6, which is characterized in that the complexing agent be selected from tartaric acid,
Tartrate, ethylenediamine tetra-acetic acid, edetate, citric acid, citrate, N-hydroxyethyl-ethylenediamine triacetic acid, N-
One of hydroxyethylethylene diamine tri-acetic acid salt, triethanolamine, nitrilotriacetic acid or nitrilotriacetic acid salt or at least two combination, it is excellent
It is selected as sodium potassium tartrate tetrahydrate.
8. chemical bronze plating liquid according to claim 1-7, which is characterized in that the stabilizer further includes ferrous cyanogen
Compound.
9. chemical bronze plating liquid according to claim 1-8, which is characterized in that any one in the stabilizer
Mass content of the ingredient in the chemical bronze plating liquid is not less than 0.005ppm.
10. -9 described in any item chemical bronze plating liquids according to claim 1, which is characterized in that the pH adjusting agent is hydroxide
Sodium and/or potassium hydroxide.
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| CN112301736A (en) * | 2020-11-18 | 2021-02-02 | 沈阳工业大学 | Preparation method of copper-tin composite coating on surface of short carbon fiber |
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| CN108866521B (en) | 2021-07-16 |
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