CN109763117A - A kind of activating solution and its application for electroless copper - Google Patents
A kind of activating solution and its application for electroless copper Download PDFInfo
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- CN109763117A CN109763117A CN201910126387.8A CN201910126387A CN109763117A CN 109763117 A CN109763117 A CN 109763117A CN 201910126387 A CN201910126387 A CN 201910126387A CN 109763117 A CN109763117 A CN 109763117A
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Abstract
The present invention relates to a kind of activating solution for electroless copper and its applications, and the activating solution is in terms of mass concentration including palladium ion 10-150ppm；Modified metal ion 0.1-20ppm；Reaction accelerator 5-20ppm；Surfactant 1-10ppm；Stabilizer 10-50ppm；Surplus is deionized water.The modified metal ion includes the combination of any one or at least two in gold ion, silver ion, platinum ion or nickel ion.It is added to palladium ion and modified metal ion in activating solution provided by the invention, the long service life of the activating solution can still be maintained light brown transparent at aging process 60 days, and generate without precipitating.When carrying out electroless copper using the activating solution of aging 60 days, the backlight level of gained PCB circuit board still can reach 9 grades.
Description
Technical field
The invention belongs to chemical surface treatment field, it is related to a kind of activating solution more particularly to a kind of for electroless copper
Activating solution and its application.
Background technique
In the production procedure of printed circuit board, it is non-in through-hole that the key of through-hole electroless copper is carried out in nonmetallic materials
First deposit one layer of metallic atom with catalytic activity on metal material, deposition of the electroless copper in nonmetallic materials first from
Metallic atom core with catalytic activity starts to carry out, when entire non-metal material surface is overplated with one layer of very thin metallic copper
When, chemical plating can be such that copper continuously precipitates by autocatalysis, and then obtain certain thickness electroless copper function
It can coating.
103866303 A of CN discloses a kind of chemical copper plating solution and preparation method thereof for micropore filling, the 1L change
Copper plating solution is learned by the cupric sulfate pentahydrate of 5-20g/L, the glycolic of EDTA, 5-20g/L of 10-30g/L, 0.0005-0.002g/
The sodium hydroxide of the accelerator of L, the inhibitor of 0.001-0.02g/L and 1.5-3.5g/L forms, and the chemical copper plating solution is logical
Addition accelerator is crossed, realizes chemical copper plating solution in the micropore of PCB circuit board without empty, seamless, ideally chemical plating
Copper filling, but in order to improve the homogeneity of chemical plating copper layer, it needs using the higher activating solution of concentration, and activation time and chemistry
The copper-plated time is longer.
107460456 A of CN discloses a kind of low palladium electroless copper activator and preparation method, the plating copper activator include
The palladium sulfate of 0.01-0.03g/L, the reaction accelerator of 0.005-0.02g/L, 0.001-0.01g/L surfactant,
The stabilizer of 0.001-0.05g/L, although the activator can on PCB circuit board hole wall normal sorption palladium metal, palladium
Dosage is higher, higher cost.
Therefore, it is few to develop a kind of palladium additive amount, when process circuit plate can make the hole wall of wiring board obtain uniform activation, make
The strong activator of layers of copper uniform deposition when electroless copper, raising deposition effect, and stability has important commercial value.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of activating solution for electroless copper and
Its apply, the activating solution can uniform activation wiring board, it is strong to the wetability of hole wall, and in activating solution Metal Palladium additive amount
Less, metallic copper can be uniformly deposited on hole wall when electroless copper, and the long service life of activating solution, be used after storing for a long time
It is high in the backlight level of electroless copper, gained wiring board.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of activating solution for electroless copper, the activating solution in terms of mass concentration,
Include:
The modified metal ion includes any one or at least two in gold ion, silver ion, platinum ion or nickel ion
The combination of kind, typical but non-limiting combination include the combination of gold ion and silver ion, the combination of silver ion and platinum ion, gold
Ion, the combination of platinum particles and nickel ion or the combination of gold ion, silver ion, platinum ion and nickel ion.
The present invention passes through the cooperation of palladium ion and modified metal ion, makes the load of palladium ion Yu modified metal uniform ion
On the hole wall of circuit board, in the activating and reducing process of electroless copper, palladium ion is reduced to simultaneously with modified metal ion
Metallic particles, and when the concentration of modified metal ion is lower than the concentration of palladium ion, modified metal ion can be between palladium particle
Gap forms active particle, increases the initial activation center of electroless copper reaction, and then improves activation effect, makes metallic copper more
It quickly and evenly deposits in the circuit board.
Activating solution is in terms of mass concentration in the present invention, including palladium ion 10-150ppm, for example, can be 10ppm, 20ppm,
30ppm、40ppm、50ppm、60ppm、70ppm、80ppm、90ppm、100ppm、110ppm、120ppm、130ppm、140ppm
Or 150ppm, preferably 50-100ppm；Modified metal ion 0.1-20ppm, for example, can be 0.1ppm, 1ppm, 2ppm,
4ppm, 6ppm, 8ppm, 10ppm, 12ppm, 14ppm, 16ppm, 18ppm or 20ppm, preferably 8-12ppm；Reaction accelerator
5-20ppm, for example, can be 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm,
15ppm, 16ppm, 17ppm, 18ppm, 19ppm or 20ppm, preferably 10-15ppm；Surfactant 1-10ppm, such as can
To be 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm or 10ppm, preferably 3-8ppm；Stabilizer
10-50ppm, such as can be 10ppm, 20ppm, 30ppm, 40ppm or 50ppm, preferably 20-30ppm；Surplus is water.
Preferably, the palladium ion in the activating solution is provided by palladium source, the palladium source include palladium sulfate, four ammonia palladium of sulfuric acid,
Any one in four ammonia palladium hydrate of sulfuric acid, palladium chloride, four ammonia palladium of dichloro or four ammino palladium chloride monohydrates or at least two
The combination of kind, typical but non-limiting combination include the combination of palladium sulfate and four ammonia palladium of sulfuric acid, four ammonia palladium of sulfuric acid and palladium chloride
Combination, the combination of palladium sulfate and palladium chloride, the combination of palladium sulfate, four ammonia palladium of sulfuric acid, sulfuric acid four ammonia palladium hydrate and palladium chloride,
Palladium sulfate, four ammonia palladium of sulfuric acid, four ammonia palladium hydrate of sulfuric acid, palladium chloride, the combination of four ammonia palladium of dichloro or palladium sulfate, four ammonia of sulfuric acid
The combination of palladium, sulfuric acid four ammonia palladium hydrates, palladium chloride, four ammonia palladium of dichloro and four ammino palladium chloride monohydrates.
Preferably, the gold ion is provided by Jin Yuan, and the Jin Yuan includes soluble gold-containing compound.
Preferably, the soluble gold-containing compound includes gold sodium sulfide, sulfurous acid gold potassium, chlorauride, gold chloride, four
Water tetra chlorauric acid, sodium chloraurate, two water sodium terachloraurates, potassium chloroaurate, a water gold potassium chloride, acetic acid gold, four auric potassium cyanides
Four in sodium cyanoaurite any one or at least two combination, typical but non-limiting combination include gold sodium sulfide with
The combination of sulfurous acid gold potassium, the combination of gold sodium sulfide and chlorauride, the combination of sulfurous acid gold potassium, chlorauride and gold chloride are sub-
The combination of auric sulfate potassium, chlorauride, gold chloride and sodium chloraurate, gold chloride, four water tetra chlorauric acids, sodium chloraurate, two water tetrachloros
The combination of sodium aurate and potassium chloroaurate, gold sodium sulfide, sulfurous acid gold potassium, chlorauride, gold chloride, sodium chloraurate, potassium chloroaurate
Combination or gold sodium sulfide, sulfurous acid gold potassium with acetic acid gold, chlorauride, gold chloride, four water tetra chlorauric acids, sodium chloraurate, two
The combination of water sodium terachloraurate, potassium chloroaurate, a water gold potassium chloride, acetic acid gold, four auric potassium cyanides and four sodium cyanoaurites.
Preferably, the silver ion is provided by silver-colored source, and the silver source includes soluble Ag-containing compound.
Preferably, the soluble Ag-containing compound includes silver nitrate, silver fluoride, silver perchlorate, [Ag (NH3)2] OH or
[Ag(NH3)2]NO3In any one or at least two combination, it is typical but non-limiting combination include silver nitrate and fluorination
Silver combination, the combination of silver nitrate and silver perchlorate, the combination of silver nitrate, silver fluoride and silver perchlorate, silver nitrate, silver fluoride with
[Ag(NH3)2]NO3Combination, silver nitrate, silver perchlorate and [Ag (NH3)2] OH combination or silver nitrate, silver fluoride, perchloric acid
Silver, [Ag (NH3)2] OH and [Ag (NH3)2]NO3Combination.
Preferably, the platinum ion is provided by platinum source, and the platinum source includes that chloroplatinic acid, potassium tetrachloroplatinate or chlordene close platinum
In sour potassium any one or at least two combination, it is typical but non-limiting combination include chloroplatinic acid and potassium tetrachloroplatinate
Combination, the combination or chloroplatinic acid of chloroplatinic acid and potassium hexachloroplatinate, the combination of potassium tetrachloroplatinate and potassium hexachloroplatinate.
Preferably, the nickel ion is provided by nickel source, the nickel source include nickel sulfate, six hydration nickel sulfate, nickel nitrate or
In nickel chloride any one or at least two combination, it is typical but non-limiting combination include nickel sulfate and nickel nitrate group
Close, the combination of nickel sulfate and nickel chloride, nickel sulfate, nickel nitrate and nickel chloride combination or nickel sulfate, six hydration nickel sulfate, nitric acid
The combination of nickel and nickel chloride.
Preferably, the modified metal ion is the combination of gold ion and silver ion.
Preferably, the molar ratio of the gold ion and silver ion be (1-3): (1-3), for example, can be 1:1,1:2,1:3,
2:1 or 2:3, preferably 1:2.
Preferably, the reaction accelerator includes 2-aminopyridine, 3- pyridinemethanol or 2- (4- aminomethyl phenyl) pyridine
Any one or at least two mixture, it is typical but non-limiting combination include 2-aminopyridine and 3- pyridinemethanol group
It closes, the combination or 2-aminopyridine, 3- pyridinemethanol and 2- (4- methylbenzene of 2-aminopyridine and 2- (4- aminomethyl phenyl) pyridine
Base) pyridine combination.
Preferably, the surfactant is non-ionic perfluorinated surfactant, and preferably E.I.Du Pont Company produces
Zonyl FSJ.Surfactant can reduce the surface tension of activating solution, increase activating solution to the through-hole and blind hole on wiring board
Wetability, ensure that complete covering of the activator to hole wall, so that layers of copper be made preferably to deposit in the circuit board.
Preferably, the stabilizer includes any one in formic acid, acetic acid, ethanedioic acid or malic acid or at least two
Combination, typical but non-limiting combination include the combination of formic acid and acetic acid, the combination of formic acid and ethanedioic acid, formic acid and malic acid
Combination, the combination of acetic acid and ethanedioic acid, the combination of acetic acid and malic acid, the combination of ethanedioic acid and malic acid, formic acid, acetic acid with
The combination of ethanedioic acid, the combination of formic acid, acetic acid and malic acid, acetic acid, the combination of ethanedioic acid and malic acid or formic acid, acetic acid, second
The combination of diacid and malic acid.Preferably, the stabilizer is the combination of ethanedioic acid or formic acid and ethanedioic acid or acetic acid and second
The combination of diacid or the combination of malic acid and ethanedioic acid or the combination of formic acid, acetic acid and ethanedioic acid or formic acid, malic acid and second
The combination of diacid or the combination of formic acid, acetic acid, malic acid and ethanedioic acid.
Second aspect, the present invention provides a kind of activating solutions as described in relation to the first aspect to be used for PCB circuit board electroless copper
Application.
Preferably, the application includes the following steps:
(1) activating solution will be immersed by the PCB circuit board of oil removing adjustment processing to be activated, after deionized water washing
Obtain activation PCB circuit board；
(2) PCB circuit board is activated obtained by activating and reducing agent solution reduction treatment step (1), is obtained after deionized water washing
Restore PCB circuit board；
(3) reduction PCB circuit board obtained by step (2) is immersed in chemical bronze plating liquid, electroless copper is carried out, after obtaining copper facing
PCB circuit board.
Preferably, the temperature of step (1) described activation processing is 40-60 DEG C, such as can be 40 DEG C, 45 DEG C, 50 DEG C, 55
DEG C or 60 DEG C, preferably 50-55 DEG C.
Preferably, the time of the activation processing be 0.2-5min, such as can be 0.2min, 0.5min, 1min,
2min, 3min, 4min or 5min, preferably 0.5-2min.
Preferably, the activating and reducing agent solution is the dimethylamino monoborane solution that concentration is 2-10g/L, such as can be with
It is 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L or 10g/L, the preferably concentration dimethylamino that is 4-7g/L
Monoborane solution.
Preferably, the temperature of the reduction treatment is 25-45 DEG C, such as can be 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C or 45
DEG C, preferably 30-40 DEG C.
Preferably, the time of the reduction treatment be 0.2-3min, such as can be 0.2min, 0.5min, 1min,
1.5min, 2min, 2.5min or 3min, preferably 0.5-1.5min.
Preferably, the temperature of the electroless copper is 28-40 DEG C, such as can be 28 DEG C, 30 DEG C, 32 DEG C, 35 DEG C or 40
DEG C, preferably 30-35 DEG C.
Preferably, the time of the electroless copper be 3-15min, such as can be 3min, 4min, 5min, 6min,
7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min, preferably 5-9min.
As the optimal technical scheme of application of the present invention, the application includes the following steps:
(1) it will be immersed in activating solution by the PCB circuit board of oil removing adjustment processing, be activated 0.2- at 40-60 DEG C
5min obtains activation PCB circuit board after deionized water washing；
(2) the dimethylamino monoborane solution that concentration is 2-10g/L activation obtained by 25-45 DEG C of reduction treatment step (1)
PCB circuit board 0.2-3min obtains reduction PCB circuit board after deionized water washing；
(3) reduction PCB circuit board obtained by step (2) is immersed in chemical bronze plating liquid, electroless copper 3- is carried out at 28-40 DEG C
15min obtains PCB circuit board after copper facing.
The third aspect, PCB circuit after the copper facing that the application as described in second aspect that the present invention provides a kind of is prepared
Plate.
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
Palladium ion and modified metal ion are added in activating solution provided by the invention, the addition of modified metal ion is reduced
The dosage of palladium ion, and during activating and reducing, modified metal ion and palladium ion cooperate, in plating material surface
Uniform active layer is formed, so that metallic copper can be made uniformly to be deposited on the surface of plating material in electroless copper, and is lived
The service life for changing liquid can extend, and light brown transparent, and nothing can still be maintained at aging process 60 days for gained activating solution
Precipitating generates.Electroless copper is carried out using the activating solution of aging 60 days, the backlight level of gained PCB circuit board still can reach 9 grades.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
I) activating solution
Embodiment 1
Present embodiments provide a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 10ppm, gold ion 0.05ppm, silver ion 0.05ppm, 3- pyridinemethanol 5ppm, Zonyl FSJ 1ppm, ethanedioic acid 5ppm,
Acetic acid 5ppm, surplus are deionized water.The palladium ion is provided by palladium chloride, and the gold ion is provided by chlorauride, the silver
Ion is provided by silver nitrate.
Embodiment 2
Present embodiments provide a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 50ppm, gold ion 3ppm, silver ion 3ppm, platinum ion 2ppm, 2-aminopyridine 5ppm, 2- (4- aminomethyl phenyl) pyridine
5ppm, Zonyl FSJ 3ppm, ethanedioic acid 10ppm, acetic acid 5ppm, formic acid 5ppm, surplus are deionized water.The palladium ion by
Palladium sulfate provides, and the gold ion is provided by sodium chloraurate and potassium chloroaurate, and the silver ion is provided by silver fluoride, the platinum from
Son is provided by chloroplatinic acid.
Embodiment 3
Present embodiments provide a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 80ppm, gold ion 3ppm, silver ion 3ppm, platinum ion 2ppm, nickel ion 2ppm, 2- (4- aminomethyl phenyl) pyridine 12ppm,
Zonyl FSJ 5ppm, ethanedioic acid 10ppm, acetic acid 5ppm, formic acid 5ppm, malic acid 5ppm, surplus are deionized water.The palladium
Ion is provided by palladium sulfate, palladium chloride and four ammonia palladium of sulfuric acid, and the gold ion is by gold sodium sulfide, sulfurous acid gold potassium, chlorauride
It is provided with gold chloride, the silver ion is provided by silver nitrate and silver perchlorate, and the platinum ion closes platinic acid by chloroplatinic acid and tetrachloro
Potassium provides, and the nickel ion is provided by nickel sulfate and nickel nitrate.
Embodiment 4
Present embodiments provide a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 100ppm, gold ion 4ppm, silver ion 8ppm, 3- pyridinemethanol 15ppm, Zonyl FSJ8ppm, ethanedioic acid 15ppm, acetic acid
5ppm, formic acid 5ppm, malic acid 5ppm, surplus are deionized water.The palladium ion is by four ammonia palladium hydrate of sulfuric acid and dichloro four
Ammonia palladium provides, and the gold ion is provided by four water tetra chlorauric acids and acetic acid gold, and the silver ion is by [Ag (NH3)2] OH and [Ag
(NH3)2]NO3It provides.
Embodiment 5
Present embodiments provide a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 150ppm, gold ion 5ppm, silver ion 15ppm, 3- pyridinemethanol 20ppm, Zonyl FSJ10ppm, ethanedioic acid 35ppm, second
Sour 5ppm, formic acid 5ppm, malic acid 5ppm, surplus are deionized water.The palladium ion is by palladium chloride, palladium sulfate and four ammino chlorine
Change palladium monohydrate to provide, the gold ion is provided by four sodium cyanoaurites and four auric potassium cyanides, and the silver ion is by silver perchlorate
It provides.
Embodiment 6
Present embodiments provide a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 150ppm, gold ion 15ppm, silver ion 5ppm, 3- pyridinemethanol 20ppm, Zonyl FSJ 10ppm, ethanedioic acid 35ppm,
Acetic acid 5ppm, formic acid 5ppm, malic acid 5ppm, surplus are deionized water.The palladium ion is provided by palladium chloride, the gold ion
It is provided by acetic acid gold, the silver ion is by [Ag (NH3)2] OH offer.
Embodiment 7
Present embodiments provide a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 80ppm, gold ion 4ppm, silver ion 6ppm, 2- (4- aminomethyl phenyl) pyridine 12ppm, Zonyl FSJ 5ppm, ethanedioic acid
10ppm, acetic acid 5ppm, formic acid 5ppm, malic acid 5ppm, surplus are deionized water.The palladium ion is by palladium sulfate and palladium chloride
It provides, the gold ion is provided by chlorauride and hydration tetra chlorauric acid, and the silver ion is provided by silver perchlorate, the platinum ion
It is provided by chloroplatinic acid and potassium tetrachloroplatinate, the nickel ion is provided by nickel chloride and nickel nitrate.
Comparative example 1
This comparative example provides a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 10.1ppm, 3- pyridinemethanol 5ppm, Zonyl FSJ 1ppm, ethanedioic acid 5ppm, acetic acid 5ppm, surplus is deionized water.Institute
Palladium ion is stated to be provided by palladium chloride.
Comparative example 2
This comparative example provides a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 58ppm, 3- pyridinemethanol 5ppm, 2- (4- aminomethyl phenyl) pyridine 5ppm, Zonyl FSJ 3ppm, ethanedioic acid 10ppm, acetic acid
5ppm, formic acid 5ppm, surplus are deionized water.The palladium ion is provided by palladium sulfate.
Comparative example 3
This comparative example provides a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 90ppm, 2- (4- aminomethyl phenyl) pyridine 12ppm, Zonyl FSJ 5ppm, ethanedioic acid 10ppm, acetic acid 5ppm, formic acid 5ppm,
Malic acid 5ppm, surplus are deionized water.The palladium ion is provided by palladium sulfate, palladium chloride and four ammonia palladium of sulfuric acid.
Comparative example 4
This comparative example provides a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 112ppm, 3- pyridinemethanol 15ppm, Zonyl FSJ 8ppm, ethanedioic acid 15ppm, acetic acid 5ppm, formic acid 5ppm, malic acid
5ppm, surplus are deionized water.The palladium ion is provided by four ammonia palladium hydrate of sulfuric acid and four ammonia palladium of dichloro.
Comparative example 5
This comparative example provides a kind of activating solution for electroless copper, the activating solution in terms of mass concentration including palladium from
Sub- 170ppm, 3- pyridinemethanol 20ppm, Zonyl FSJ 10ppm, ethanedioic acid 35ppm, acetic acid 5ppm, formic acid 5ppm, malic acid
5ppm, surplus are deionized water.The palladium ion is provided by palladium chloride, palladium sulfate and four ammino palladium chloride monohydrates.
1-7 of the embodiment of the present invention and comparative example 1-5 activating solution provided is carried out always in 55 DEG C of thermostat water bath
Change test, the results are shown in Table 1 for burn-in test.
Table 1
As shown in Table 1, light brown transparent state is still maintained behind embodiment 1-7 is provided activating solution aging process 60 days
And it is generated without precipitating.
The activating solution that comparative example 1 provides is living at aging process 50 days compared with Example 1 without addition modified metal ion
Change liquid to keep light brown transparent and generate without precipitating；When aging 60 days, although activating solution is still light brown transparent, have slight
Precipitating generates.
The activating solution that comparative example 2 provides is living at aging process 40 days compared with Example 2 without addition modified metal ion
Change liquid to keep light brown transparent and generate without precipitating；When aging process 50 days, although activating solution is still light brown transparent, have
Slight precipitating generates；When aging process 60 days, although activating solution is still light brown transparent, there is obvious sediment generation.
The activating solution that comparative example 3 provides is living at aging process 50 days compared with Example 3 without addition modified metal ion
Change liquid to keep light brown transparent and generate without precipitating；When aging 60 days, although activating solution is still light brown transparent, have slight
Precipitating generates.
The activating solution that comparative example 4 provides is living at aging process 40 days compared with Example 4 without addition modified metal ion
Change liquid to keep light brown transparent and generate without precipitating；When aging process 50 days, although activating solution is still light brown transparent, have
Slight precipitating generates；When aging process 60 days, although activating solution is still light brown transparent, there is obvious sediment generation.
The activating solution that comparative example 5 provides is living at aging process 40 days compared with Example 5 without addition modified metal ion
Change liquid to keep light brown transparent and generate without precipitating；When aging process 50 days, although activating solution is still light brown transparent, have
Slight precipitating generates；When aging process 60 days, although activating solution is still light brown transparent, there is obvious sediment generation.
In conclusion the present invention improves activating solution by adding palladium ion and modified metal ion in activating solution
Service life.
II) aging post activation liquid
The activating solution that 1-7 of the embodiment of the present invention and comparative example 1-5 are provided aging 60 in 55 DEG C of thermostat water bath
It, and electroless copper is carried out to PCB circuit board using the activating solution after aging.
Application examples 1
The application example provides a kind of method that the activating solution that Application Example 1 provides is used for PCB circuit board electroless copper,
The activating solution is 60 days gained activating solutions of aging in 55 DEG C of thermostat water bath, and described method includes following steps:
(1) it will be immersed in activating solution by the PCB circuit board of oil removing adjustment processing, be activated 1min at 50 DEG C, go
Activation PCB circuit board is obtained after ion water washing；
(2) the dimethylamino monoborane solution that concentration is 5g/L activation PCB circuit obtained by 35 DEG C of reduction treatment steps (1)
Plate 1min obtains reduction PCB circuit board after deionized water washing；
(3) reduction PCB circuit board obtained by step (2) is immersed in chemical bronze plating liquid, electroless copper 7min is carried out at 32 DEG C,
Obtain PCB circuit board after copper facing.
Application examples 2
The application example provides a kind of method that the activating solution that Application Example 1 provides is used for PCB circuit board electroless copper,
The activating solution is 60 days gained activating solutions of aging in 55 DEG C of thermostat water bath, and described method includes following steps:
(1) it will be immersed in activating solution by the PCB circuit board of oil removing adjustment processing, be activated 2min at 45 DEG C, go
Activation PCB circuit board is obtained after ion water washing；
(2) the dimethylamino monoborane solution that concentration is 4g/L activation PCB circuit obtained by 40 DEG C of reduction treatment steps (1)
Plate 0.5min obtains reduction PCB circuit board after deionized water washing；
(3) reduction PCB circuit board obtained by step (2) is immersed in chemical bronze plating liquid, electroless copper 9min is carried out at 30 DEG C,
Obtain PCB circuit board after copper facing.
Application examples 3
The application example provides a kind of method that the activating solution that Application Example 1 provides is used for PCB circuit board electroless copper,
The activating solution is 60 days gained activating solutions of aging in 55 DEG C of thermostat water bath, and described method includes following steps:
(1) it will be immersed in activating solution by the PCB circuit board of oil removing adjustment processing, be activated 0.5min at 55 DEG C,
Activation PCB circuit board is obtained after deionized water washing；
(2) the dimethylamino monoborane solution that concentration is 7g/L activation PCB circuit obtained by 30 DEG C of reduction treatment steps (1)
Plate 1.5min obtains reduction PCB circuit board after deionized water washing；
(3) reduction PCB circuit board obtained by step (2) is immersed in chemical bronze plating liquid, electroless copper 5min is carried out at 35 DEG C,
Obtain PCB circuit board after copper facing.
Application examples 4
The application example provides a kind of method that the activating solution that Application Example 1 provides is used for PCB circuit board electroless copper,
The activating solution is 60 days gained activating solutions of aging in 55 DEG C of thermostat water bath, and described method includes following steps:
(1) it will be immersed in activating solution by the PCB circuit board of oil removing adjustment processing, be activated 5min at 40 DEG C, go
Activation PCB circuit board is obtained after ion water washing；
(2) the dimethylamino monoborane solution that concentration is 2g/L activation PCB circuit obtained by 45 DEG C of reduction treatment steps (1)
Plate 0.2min obtains reduction PCB circuit board after deionized water washing；
(3) reduction PCB circuit board obtained by step (2) is immersed in chemical bronze plating liquid, electroless copper is carried out at 28 DEG C
15min obtains PCB circuit board after copper facing.
Application examples 5
The application example provides a kind of method that the activating solution that Application Example 1 provides is used for PCB circuit board electroless copper,
The activating solution is 60 days gained activating solutions of aging in 55 DEG C of thermostat water bath, and described method includes following steps:
(1) it will be immersed in activating solution by the PCB circuit board of oil removing adjustment processing, be activated 0.2min at 60 DEG C,
Activation PCB circuit board is obtained after deionized water washing；
(2) the dimethylamino monoborane solution that concentration is 10g/L activation PCB electricity obtained by 25 DEG C of reduction treatment steps (1)
Road plate 3min obtains reduction PCB circuit board after deionized water washing；
(3) reduction PCB circuit board obtained by step (2) is immersed in chemical bronze plating liquid, electroless copper 3min is carried out at 40 DEG C,
Obtain PCB circuit board after copper facing.
Application examples 6
The application example provides a kind of method that the activating solution that Application Example 2 provides is used for PCB circuit board electroless copper,
The activating solution is that 60 days gained activating solutions of aging, the method are identical as application examples 1 in 55 DEG C of thermostat water bath.
Application examples 7
The application example provides a kind of method that the activating solution that Application Example 3 provides is used for PCB circuit board electroless copper,
The activating solution is that 60 days gained activating solutions of aging, the method are identical as application examples 1 in 55 DEG C of thermostat water bath.
Application examples 8
The application example provides a kind of method that the activating solution that Application Example 4 provides is used for PCB circuit board electroless copper,
The activating solution is that 60 days gained activating solutions of aging, the method are identical as application examples 1 in 55 DEG C of thermostat water bath.
Application examples 9
The application example provides a kind of method that the activating solution that Application Example 5 provides is used for PCB circuit board electroless copper,
The activating solution is that 60 days gained activating solutions of aging, the method are identical as application examples 1 in 55 DEG C of thermostat water bath.
Application examples 10
The application example provides a kind of method that the activating solution that Application Example 6 provides is used for PCB circuit board electroless copper,
The activating solution is that 60 days gained activating solutions of aging, the method are identical as application examples 1 in 55 DEG C of thermostat water bath.
Application examples 11
The application example provides a kind of method that the activating solution that Application Example 7 provides is used for PCB circuit board electroless copper,
The activating solution is that 60 days gained activating solutions of aging, the method are identical as application examples 1 in 55 DEG C of thermostat water bath.
Compare application examples 1
This comparison application examples provides a kind of activating solution of offer of Comparison study example 1 for PCB circuit board electroless copper
Method, the activating solution are 60 days gained activating solutions of aging, the method and 1 phase of application examples in 55 DEG C of thermostat water bath
Together.
Compare application examples 2
This comparison application examples provides a kind of activating solution of offer of Comparison study example 2 for PCB circuit board electroless copper
Method, the activating solution are 60 days gained activating solutions of aging, the method and 1 phase of application examples in 55 DEG C of thermostat water bath
Together.
Compare application examples 3
This comparison application examples provides a kind of activating solution of offer of Comparison study example 3 for PCB circuit board electroless copper
Method, the activating solution are 60 days gained activating solutions of aging, the method and 1 phase of application examples in 55 DEG C of thermostat water bath
Together.
Compare application examples 4
This comparison application examples provides a kind of activating solution of offer of Comparison study example 4 for PCB circuit board electroless copper
Method, the activating solution are 60 days gained activating solutions of aging, the method and 1 phase of application examples in 55 DEG C of thermostat water bath
Together.
Compare application examples 5
This comparison application examples provides a kind of activating solution of offer of Comparison study example 5 for PCB circuit board electroless copper
Method, the activating solution are 60 days gained activating solutions of aging, the method and 1 phase of application examples in 55 DEG C of thermostat water bath
Together.
It detects application examples 1-11 and compares the backlight level of PCB circuit board after the copper facing that application examples 1-5 is provided, testing number
According to as shown in table 2.
Table 2
As shown in Table 2, the backlight level of PCB circuit board is 9-9.5 after the copper facing that application examples 1-11 of the present invention is provided.
The activating solution electroless copper that comparison application examples 1 is provided using comparative example 1, the back of PCB circuit board after obtained copper facing
Light grade is 7, lower than the 9 of application examples 1；The activating solution electroless copper that comparison application examples 2 is provided using comparative example 2, obtained plating
The backlight level of PCB circuit board is 7 after copper, lower than the 9 of application examples 6；The activating solution that comparison application examples 3 is provided using comparative example 3
Electroless copper, the backlight level of PCB circuit board is 7 after obtained copper facing, lower than the 9 of application examples 7；Compare the use pair of application examples 4
The activating solution electroless copper that ratio 4 provides, the backlight level of PCB circuit board is 7 after obtained copper facing, lower than the 9 of application examples 8；
The activating solution electroless copper that comparison application examples 5 is provided using comparative example 5, the backlight level of PCB circuit board is after obtained copper facing
8, lower than the 9.5 of application examples 9.
In conclusion palladium ion and modified metal ion are added in activating solution provided by the invention, the activating solution
Long service life, can still be maintained at aging process 60 days it is light brown transparent, and without precipitating generate.It uses aging 60 days
When activating solution carries out electroless copper, the backlight level of gained PCB circuit board still can reach 9 grades.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of activating solution for electroless copper, which is characterized in that the activating solution is in terms of mass concentration, including with the following group
Point:
The modified metal ion includes any one or at least two in gold ion, silver ion, platinum ion or nickel ion
Combination.
2. activating solution according to claim 1, which is characterized in that the activating solution is in terms of mass concentration, including with the following group
Point:
3. activating solution according to claim 1 or 2, which is characterized in that the palladium ion in the activating solution is provided by palladium source,
The palladium source includes palladium sulfate, four ammonia palladium of sulfuric acid, four ammonia palladium hydrate of sulfuric acid, palladium chloride, four ammonia palladium of dichloro or four ammino chlorinations
In palladium monohydrate any one or at least two combination；
Preferably, the gold ion is provided by Jin Yuan, and the Jin Yuan includes soluble gold-containing compound；
Preferably, the soluble gold-containing compound includes gold sodium sulfide, sulfurous acid gold potassium, chlorauride, gold chloride, four water four
Gold chloride, sodium chloraurate, two water sodium terachloraurates, potassium chloroaurate, a water gold potassium chloride, acetic acid gold, four auric potassium cyanides, four cyanogen
In sodium aurate any one or at least two combination；
Preferably, the silver ion is provided by silver-colored source, and the silver source includes soluble Ag-containing compound；
Preferably, the soluble Ag-containing compound includes silver nitrate, silver fluoride, silver perchlorate, [Ag (NH3)2] OH or [Ag
(NH3)2]NO3In any one or at least two combination；
Preferably, the platinum ion is provided by platinum source, and the platinum source includes chloroplatinic acid, potassium tetrachloroplatinate or potassium hexachloroplatinate
In any one or at least two combination；
Preferably, the nickel ion is provided by nickel source, and the nickel source includes nickel sulfate, six hydration nickel sulfate, nickel nitrate or chlorination
In nickel any one or at least two combination.
4. activating solution according to claim 1-3, which is characterized in that the modified metal ion be gold ion with
The combination of silver ion；
Preferably, the molar ratio of the gold ion and silver ion is (1-3): (1-3), preferably 1:2.
5. activating solution according to claim 1-4, which is characterized in that the reaction accelerator includes 2- amino pyrrole
Pyridine, 3- pyridinemethanol or 2- (4- aminomethyl phenyl) pyridine any one or at least two mixture；
Preferably, the surfactant is non-ionic perfluorinated surfactant, preferably the Zonyl of E.I.Du Pont Company's production
FSJ；
Preferably, the stabilizer include in formic acid, acetic acid, ethanedioic acid or malic acid any one or at least two group
It closes.
6. the application that a kind of activating solution as described in any one in claim 1-5 is used for PCB circuit board electroless copper.
7. application according to claim 6, which is characterized in that the application includes the following steps:
(1) activating solution will be immersed by the PCB circuit board of oil removing adjustment processing to be activated, obtain after deionized water washing
Activate PCB circuit board；
(2) PCB circuit board is activated obtained by activating and reducing agent solution reduction treatment step (1), is restored after deionized water washing
PCB circuit board；
(3) reduction PCB circuit board obtained by step (2) is immersed in chemical bronze plating liquid, carries out electroless copper, obtains PCB after copper facing
Circuit board.
8. application according to claim 6 or 7, which is characterized in that the temperature of step (1) described activation processing is 40-60
DEG C, preferably 50-55 DEG C；
Preferably, the time of the activation processing is 0.2-5min, preferably 0.5-2min；
Preferably, the activating and reducing agent solution is the dimethylamino monoborane solution that concentration is 2-10g/L, and preferably concentration is
The dimethylamino monoborane solution of 4-7g/L；
Preferably, the temperature of the reduction treatment is 25-45 DEG C, preferably 30-40 DEG C；
Preferably, the time of the reduction treatment is 0.2-3min, preferably 0.5-1.5min；
Preferably, the temperature of the electroless copper is 28-40 DEG C, preferably 30-35 DEG C；
Preferably, the time of the electroless copper is 3-15min, preferably 5-9min.
9. according to the described in any item applications of claim 6-8, which is characterized in that the application includes the following steps:
(1) it will be immersed in activating solution by the PCB circuit board of oil removing adjustment processing, be activated 0.2-5min at 40-60 DEG C,
Activation PCB circuit board is obtained after deionized water washing；
(2) the dimethylamino monoborane solution that concentration is 2-10g/L activation PCB electricity obtained by 25-45 DEG C of reduction treatment step (1)
Road plate 0.2-3min obtains reduction PCB circuit board after deionized water washing；
(3) reduction PCB circuit board obtained by step (2) is immersed in chemical bronze plating liquid, electroless copper 3- is carried out at 28-40 DEG C
15min obtains PCB circuit board after copper facing.
10. PCB circuit board after a kind of copper facing that application as claim in any one of claims 6-9 is prepared.
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| CN201910126387.8A CN109763117B (en) | 2019-02-20 | 2019-02-20 | Activating solution for electroless copper plating and application thereof |
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| CN201910126387.8A CN109763117B (en) | 2019-02-20 | 2019-02-20 | Activating solution for electroless copper plating and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643982A (en) * | 2019-11-14 | 2020-01-03 | 苏州天承化工有限公司 | Ionic palladium activation solution and preparation method and application thereof |
| CN117467990A (en) * | 2023-10-11 | 2024-01-30 | 深圳中科利尔科技有限公司 | PCB electroless copper plating method for improving toughness of copper layer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106894005A (en) * | 2015-12-21 | 2017-06-27 | 比亚迪股份有限公司 | A kind of chemical bronze plating liquid, preparation method and a kind of method of Chemical Plating of Non metal Material |
| CN107460456A (en) * | 2017-07-31 | 2017-12-12 | 苏州天承化工有限公司 | A kind of low palladium electroless copper activator and preparation method |
-
2019
- 2019-02-20 CN CN201910126387.8A patent/CN109763117B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106894005A (en) * | 2015-12-21 | 2017-06-27 | 比亚迪股份有限公司 | A kind of chemical bronze plating liquid, preparation method and a kind of method of Chemical Plating of Non metal Material |
| CN107460456A (en) * | 2017-07-31 | 2017-12-12 | 苏州天承化工有限公司 | A kind of low palladium electroless copper activator and preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643982A (en) * | 2019-11-14 | 2020-01-03 | 苏州天承化工有限公司 | Ionic palladium activation solution and preparation method and application thereof |
| CN117467990A (en) * | 2023-10-11 | 2024-01-30 | 深圳中科利尔科技有限公司 | PCB electroless copper plating method for improving toughness of copper layer |
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|---|---|
| CN109763117B (en) | 2021-09-07 |
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