CN101684554B - Chemical copper plating solution for polyimide film and surface chemical copper plating method thereof - Google Patents
Chemical copper plating solution for polyimide film and surface chemical copper plating method thereof Download PDFInfo
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- CN101684554B CN101684554B CN2008102163173A CN200810216317A CN101684554B CN 101684554 B CN101684554 B CN 101684554B CN 2008102163173 A CN2008102163173 A CN 2008102163173A CN 200810216317 A CN200810216317 A CN 200810216317A CN 101684554 B CN101684554 B CN 101684554B
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Abstract
The invention provides a chemical copper plating solution for a polyimide film and a surface chemical copper plating method thereof, wherein the chemical copper plating solution is a water solution containing copper salt, ascorbic acid or soluble ascorbic acid salt, a complexing agent, a metal catalyst, a stabilizer and a pH buffering agent. The pH value of the chemical copper plating solution is 5.5-8.0, and the concentration of the stabilizer is not higher than 50milligrams/liter. The chemical copper plating solution provided by the invention is a neutral copper plating solution, adopts the nontoxic environment-friendly ascorbic acid or soluble ascorbic acid salt as a reducer, is suitable for the surface chemical copper plating of the polyimide film, and has good effect on environment protection.
Description
[technical field]
The present invention relates to the electroless plating technology field, relate in particular to a kind of chemical bronze plating liquid and surface chemical plating copper method thereof of Kapton.
[background technology]
Polyimide material has good insulation performance property and stopping property; And the outstanding properties such as the thermostability that also have other are high, can be high temperature resistant and utmost point low temperature, satisfactory mechanical property, thermal expansivity low, nontoxic; Especially have low specific inductivity, can reduce current interference and energy consumption between the lead.So polyimide has vast application prospect at microelectronic.Electroless plating technology receives wider application owing to having cheapness property and normal-temperature operation property in electronics industry and microelectronics industry.Kapton can pass through induced with laser, nano-TiO
2Method such as photochemical catalysis, surface-treated spike on the kind of surface carries out electroless copper afterwards like silver, copper, gold etc.
Along with development of integrated circuits, the electroless copper technology develops to pollution-freeization direction.But mostly traditional chemical bronze plating liquid is to contain the alkaline copper plating bath of reductive agents such as formaldehyde, hypophosphite, oxoethanoic acid; Formaldehyde has toxicity; Environmental pollution is very big; And alkaline copper plating bath can change the structure of Kapton, makes its surface-treated, therefore is not suitable for the electroless copper of polyimide surface.
In addition; Disclose in the prior art with dimethyamine borane (Dimethylamine borane; Hereinafter to be referred as DMAB) as the acidity and the neutral chemical bronze plating liquid of reductive agent; Though this copper plating bath is applicable to Kapton, but DMAB cost an arm and a leg and also poisonous, the borate that obtains discharges has negative impact to environment.Therefore, development of integrated circuits still needs neutral chemical bronze plating liquid environmental protection, that be applicable to Kapton.
[summary of the invention]
The present invention is directed to chemical bronze plating liquid of the prior art and be not suitable for chemical plating polyimide film surface copper, shortcoming that environmental pollution is big; A kind of chemical bronze plating liquid of Kapton is provided; Said chemical bronze plating liquid is the aqueous solution that contains mantoquita, xitix or solubility ascorbate salt, complexing agent, metal catalyst, stablizer, pH buffer reagent; The pH value of said chemical bronze plating liquid is 5.5～8.0, and the concentration of said stablizer is not higher than 50 mg/litre.
The present invention is directed to chemical bronze plating liquid of the prior art and be not suitable for chemical plating polyimide film surface copper, shortcoming that environmental pollution is big; The electroless copper plating method on a kind of Kapton surface also is provided; Comprise that the Kapton that will introduce spike directly contacts with chemical bronze plating liquid provided by the present invention, cleaning, drying obtain plating piece.
Adopt chemical bronze plating liquid provided by the present invention and electroless copper plating method; Wherein said chemical bronze plating liquid is neutral copper plating bath; The xitix or the solubility ascorbate salt that adopt nontoxic, environmental protection are applicable to chemical plating polyimide film surface copper as reductive agent, have good environment protecting.
[embodiment]
In order to make the object of the invention, technical scheme and advantage clearer, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that embodiment described herein only in order to explain the present invention, does not limit the present invention.
The invention provides a kind of chemical bronze plating liquid of Kapton; Said chemical bronze plating liquid is the aqueous solution that contains mantoquita, xitix or solubility ascorbate salt, complexing agent, metal catalyst, stablizer, pH buffer reagent; The pH value of said chemical bronze plating liquid is 5.5-8.0, and the concentration of said stablizer is not higher than 50 mg/litre.
According to chemical bronze plating liquid provided by the present invention, wherein, concentration 5～30 grams per liters of said mantoquita; The concentration of said xitix or solubility ascorbate salt is 2～13 grams per liters; The concentration of said complexing agent is 15～70 grams per liters; The concentration of said metal catalyst is 0.1～5 grams per liter; The concentration of said stablizer is 0.05～30 mg/litre; The concentration of said pH buffer reagent is 7～40 grams per liters.
Wherein, said mantoquita is used to provide the cupric ion of electroless copper.Said mantoquita is a various mantoquita known in those skilled in the art, is selected from copper sulfate, cupric chloride, the cupric nitrate one or more.
Said xitix or solubility ascorbate salt are the reductive agent of said chemical bronze plating liquid.Said xitix or nontoxic, the environmental protection of solubility ascorbate salt can be reduced cupric ion under neutrallty condition, be applicable to the electroless copper of polyimide surface.Said xitix or solubility ascorbate salt are selected from one or more in xitix, calcium ascorbate, the xitix zinc.
Said complexing agent be well known in the art various can with the compound of cupric ion complexing; The present invention does not have particular requirement, for example can be selected from Hydrocerol A, solubility Citrate trianion, tartrate, soluble tartar hydrochlorate, oxysuccinic acid, solubility malate, YD 30, the solubility edetate one or more.
Said metal catalyst is nickeliferous water-soluble salt, and the adding of said metal catalyst can effectively improve binding force of cladding material.Metal catalyst can be selected from one or more in single nickel salt, nickelous chloride, the nickel acetate.
The adding of said stablizer can reduce the spontaneous decomposition of chemical bronze plating liquid, improve the stability of chemical bronze plating liquid effectively, also can regulate plating rate simultaneously, makes copper deposit shinny, obviously improves the quality of coating.The concentration of stablizer is not higher than 50 mg/litre in the said chemical bronze plating liquid, can reduce plating speed in order to avoid too much stablizer exists, in addition when stoping electroless plating copper in the deposition reaction on Kapton surface.Said stablizer can be selected from 2, one or more in 2 '-dipyridyl, yellow prussiate of potash, phenanthroline and verivate thereof, dimercaptosuccinic acid, dithio two Succinic Acid, thiocarbamide, mercaptobenzothiazole, the inferior sulfydryl oxalic acid.
Said pH buffer reagent is an all kinds of buffer reagent known in those skilled in the art, and the adding of said pH buffer reagent can effectively hinder owing to add acid, alkali on a small quantity and make the variation of pH of chemical bronze plating liquid.Among the present invention, preferably adopt borate buffer.
According to chemical bronze plating liquid provided by the present invention, also contain tensio-active agent in the said chemical bronze plating liquid.The adding of said tensio-active agent helps the effusion of Kapton open bubble, reduces the coating porosity.Said tensio-active agent is the common various tensio-active agents of those skilled in the art, for example can be selected from X 2073, sodium lauryl sulphate, n-octyl sodium sulfate, the polyoxyethylene type tensio-active agent wherein one or more.Said surfactant concentrations is 0.05～2 grams per liter.
In the chemical bronze plating liquid provided by the present invention, the pH value of said chemical bronze plating liquid is 5.5～8.0.The pH value of regulating said chemical bronze plating liquid adopts conventional method; For example can regulate through adding acid-base modifier; Described acid-base modifier is a various bronsted lowry acids and bases bronsted lowry known in those skilled in the art, for example can be sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, Pottasium Hydroxide or ammoniacal liquor.All preferably adopt sulfuric acid, ammoniacal liquor to regulate the pH value of said chemical bronze plating liquid as acid-base modifier in the embodiment of the invention.
The present invention also provides the electroless copper plating method on a kind of Kapton surface, comprises the Kapton of introducing spike is directly contacted with chemical bronze plating liquid provided by the present invention that cleaning, drying obtain plating piece.
The electroless copper plating method of being carried according to the present invention, the method for wherein said introducing spike for example can be surface-modification method or optically catalytic TiO 2 method for well known to a person skilled in the art technology.Said spike is selected from a kind of in copper, gold and silver, nickel, the palladium.Electroless copper plating method provided by the present invention can carry out electroless copper to the Kapton surface of any introducing spike; The all preferred Kapton (Kapton200-H that introduces spike copper through polyimide surface modification method that adopts in the embodiment of the invention; TorayDupont), but be not limited to this as the sample of electroless copper.
According to electroless copper plating method provided by the present invention; The said Kapton that will introduce spike is a whole bag of tricks known in those skilled in the art with the method that chemical bronze plating liquid provided by the present invention directly contacts; The present invention does not have particular requirement, for example can impregnated in for the Kapton that will introduce spike in the said chemical bronze plating liquid.The time of said contact is 10～70 minutes, is preferably 20～60 minutes; In order to improve the speed of electroless plating, the temperature of said chemical bronze plating liquid is 20-70 ℃ during contact, is preferably 30-60 ℃.According to electroless copper plating method provided by the present invention, in order to prevent effectively that copper when deposition from existing with the copper powder form and with Kapton bonding force difference and the cuprous generation of inhibited oxidation, said contact also needs under whipped state, carry out.
The method of electroless copper provided by the invention, the said Kapton that will introduce spike also need be removed the oxygen in the chemical bronze plating liquid with before chemical bronze plating liquid provided by the present invention contacts.The whole bag of tricks that the method for deoxygenation is used always for those skilled in the art for example can be for removing the oxygen in the chemical bronze plating liquid, the preferred rare gas element bubblings in chemical bronze plating liquid such as nitrogen, argon gas that adopt among the present invention through bubbling.
According to electroless copper plating method provided by the present invention, to clean through the Kapton surface of electroless copper, drying, can obtain plating piece.Said cleaning step is the Kapton of water flushing process electroless copper, and the time of said cleaning and number of times be restriction not, only needs the residue chemical bronze plating liquid that Kapton is surperficial to clean and gets final product.The water that is adopted is various water of the prior art, and like municipal tap water, deionized water, zero(ppm) water, pure water or their mixture, the present invention is preferably deionized water.Said drying step is a various drying step known in those skilled in the art; Said exsiccant method can adopt the method for well known to a person skilled in the art; Like vacuum-drying, seasoning, forced air drying, the preferred nitrogen that adopts is to through the Kapton air blast of electroless copper 1-10 minute among the present invention.
Below specify the chemical bronze plating liquid and the surface chemical plating copper method thereof of Kapton provided by the present invention through embodiment and Comparative Examples.
Except that the Kapton of introducing spike copper, the raw material that other adopted all is available commercially in the embodiment of the invention.The method that said polyimide is introduced spike copper is a surface-modification method, and concrete steps are following:
1. pre-treatment: preparation absolute ethyl alcohol and acetone volume ratio are 500 milliliters of the degreasing fluids of 3:1; Kapton (Kapton200-H with 40mm * 40mm; Toray Dupont) is positioned in this degreasing fluid ultrasonic cleaning 20 minutes, cleans up drying then with deionized water; Prepare 5 mol potassium hydroxide solutions, the Kapton room temperature that this potassium hydroxide solution drips after skimming treatment was placed 5 minutes, clean up with deionized water then, and dry, obtain the Kapton of surface portion modification;
2. Copper Ion Exchange: the copper-bath of preparing 0.05 mol; Kapton after the above-mentioned modification is put into this copper-bath; Soaking at room temperature 20 minutes cleans up with deionized water then, obtains the Kapton of surface portion Copper Ion Exchange.
3. cupric ion reduction: prepare 0.1 mol dimethylamino borane solution, the Kapton of above-mentioned surface portion Copper Ion Exchange is put into the dimethylamino borane solution of having prepared, 50 ℃ were soaked 20 minutes down, clean up with deionized water then.
Can obtain introducing the Kapton of spike copper through above-mentioned processing.
Embodiment 1
Present embodiment is used for explaining the chemical bronze plating liquid and the surface chemical plating copper method thereof of Kapton provided by the present invention.
The preparation of chemical bronze plating liquid: the anhydrous cupric sulfate of 8 grams, the xitix of 3.2 grams, the YD 30 of 25 grams, 7 milligrams yellow prussiate of potash, the X 2073 of 0.5 gram, the six hydration nickel sulfate of 0.8 gram, 0.5 milligram thiocarbamide and the boric acid of 15 grams are dissolved in the deionized water, are mixed with 1 liter chemical bronze plating liquid.
Using sulfuric acid or ammoniacal liquor to regulate pH value above-mentioned chemical bronze plating liquid is 6.8, and is warming up to 45 ℃, with nitrogen bubbling in this chemical bronze plating liquid, the Kapton of introducing spike copper is soaked 40 minutes in above-mentioned chemical bronze plating liquid.Kapton is taken out,, adopted the nitrogen air blast then 4 minutes, obtain the polyimide plating piece, be designated as A1 with deionized water rinsing 1 minute.
Embodiment 2
Present embodiment is used for explaining the chemical bronze plating liquid and the surface chemical plating copper method thereof of Kapton provided by the present invention.
Adopt the Kapton of handling above-mentioned introducing spike copper with embodiment 1 identical method, difference is:
The preparation of chemical bronze plating liquid: the anhydrous cupric sulfate of 20 grams, the xitix of 8 grams, the YD 30 of 60 grams, 7 milligrams yellow prussiate of potash, the X 2073 of 0.5 gram, the six hydration nickel sulfate of 3.6 grams, 8 milligrams thiocarbamide and the boric acid of 30 grams are dissolved in the deionized water, are mixed with 1 liter chemical bronze plating liquid.
The polyimide plating piece that obtains according to the method described above is designated as A2.
Embodiment 3
Present embodiment is used for explaining the chemical bronze plating liquid and the surface chemical plating copper method thereof of Kapton provided by the present invention.
Adopt the Kapton of handling above-mentioned introducing spike copper with embodiment 1 identical method, difference is:
The preparation of chemical bronze plating liquid: the anhydrous cupric sulfate of 8 grams, the xitix of 3.2 grams, the Rochelle salt of 20 grams, the n-octyl sodium sulfate of 0.5 gram, the Nickel dichloride hexahydrate of 0.9 gram, 0.5 milligram thiocarbamide and the boric acid of 15 grams are dissolved in the deionized water, are mixed with 1 liter chemical bronze plating liquid.
The polyimide plating piece that obtains according to the method described above is designated as A3.
Embodiment 4
Present embodiment is used for explaining the chemical bronze plating liquid and the surface chemical plating copper method thereof of Kapton provided by the present invention.
Adopt the Kapton of handling above-mentioned introducing spike copper with embodiment 1 identical method, difference is:
The preparation of chemical bronze plating liquid: the anhydrous cupric sulfate of 8 grams, the xitix of 3.2 grams, the YD 30 of 25 grams, 7 milligrams yellow prussiate of potash, the six hydration nickel sulfate of 0.8 gram, 0.5 milligram thiocarbamide and the boric acid of 15 grams are dissolved in the deionized water, are mixed with 1 liter chemical bronze plating liquid.
The polyimide plating piece that obtains according to the method described above is designated as A4.
Embodiment 5
Present embodiment is used for explaining the chemical bronze plating liquid and the surface chemical plating copper method thereof of Kapton provided by the present invention.
Adopt the Kapton of handling above-mentioned introducing spike copper with embodiment 1 identical method, difference is:
The preparation of chemical bronze plating liquid: the anhydrous cupric sulfate of 4.5 grams, the xitix of 1.5 grams, the Rochelle salt of 12 grams, the n-octyl sodium sulfate of 0.03 gram, the Nickel dichloride hexahydrate of 0.08 gram, 0.04 milligram thiocarbamide and the boric acid of 6 grams are dissolved in the deionized water, are mixed with 1 liter chemical bronze plating liquid.
The polyimide plating piece that obtains according to the method described above is designated as A5.
Comparative Examples 1
This Comparative Examples is used for explaining the chemical bronze plating liquid and the surface chemical plating copper method thereof of the Kapton of prior art.
Adopt the Kapton of handling above-mentioned introducing spike copper with embodiment 1 identical method, difference is: the preparation of chemical bronze plating liquid: in the chemical bronze plating liquid of preparation, add ammoniacal liquor, regulating the pH value is 12.0.
The polyimide plating piece that obtains according to the method described above is designated as D1.
Comparative Examples 2
This Comparative Examples is used for explaining the chemical bronze plating liquid and the surface chemical plating copper method thereof of the Kapton of prior art.
Adopt the Kapton of handling above-mentioned introducing spike copper with embodiment 1 identical method, difference is: the preparation of chemical bronze plating liquid: with 3.2 gram xitix in the 5.0 gram dimethyamine borane alternative embodiments 1.
The polyimide plating piece that obtains according to the method described above is designated as D2.
Comparative Examples 3
This Comparative Examples is used for explaining the chemical bronze plating liquid and the surface chemical plating copper method thereof of the Kapton of prior art.
Adopt the Kapton of handling above-mentioned introducing spike copper with embodiment 1 identical method, difference is: the preparation of chemical bronze plating liquid: with 0.5 milligram of thiocarbamide in 60 milligrams of thiocarbamide alternative embodiments 1.
The polyimide plating piece that obtains according to the method described above is designated as D3.
Performance test
Measure embodiment, the sample A1～A5 of Comparative Examples, the thickness of D1～D3, adopt the thickness of film thickness gauge (CMI900, Oxford Instr Ltd.) test Kapton surface copper film, it is as shown in table 1 to measure the result.
Table 1 sample test result
Can know that from the test result of table 1 coating that the chemical bronze plating liquid of the Kapton that the embodiment of the invention provided and surface chemical plating copper method thereof obtain is thicker, and surperficial uniform and delicate.
Can know from the test result comparison of A1～A5 and D1-D3, adopt xitix or solubility ascorbate salt in the chemical bronze plating liquid provided by the present invention, be neutral copper plating bath as reductive agent, can be at polyimide at the plated with copper layer.And adopt alkaline copper plating bath among the D1, and the Kapton surface there is corrosive nature, the quality of coating that obtains is poor; Though have coating to form among the D2, but owing to adopt dimethyamine borane to make reductive agent, not only the dimethyamine borane cost is very high, and adopts this reductive agent can discharge a large amount of borate contaminate environment; Owing to the too high levels of stablizer in the chemical bronze plating liquid, metal is in the deposition reaction on Kapton surface, so there is not coating to form at all when stoping electroless plating among the D3.
Can know from the test result comparison of A1～A3 and A4, adopt in the preferred chemical bronze plating liquid of the present invention and contain tensio-active agent, can reduce the coating voidage, plated with copper layer, and coating uniform and delicate more easily.
Can know from the test result comparison of A1～A3 and A5, adopt the proper concentration of each composition in the preferred chemical bronze plating liquid of the present invention, more easily plated with copper layer on Kapton.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (11)
1. the chemical bronze plating liquid of a Kapton; It is characterized in that: said chemical bronze plating liquid is the aqueous solution that contains mantoquita, xitix or solubility ascorbate salt, complexing agent, metal catalyst, stablizer, pH buffer reagent; The pH value of said chemical bronze plating liquid is 5.5～8.0, and the concentration of said stablizer is not higher than 50 mg/litre; Said metal catalyst is nickeliferous water-soluble salt; Said stablizer is selected from 2, one or more in 2 '-dipyridyl, yellow prussiate of potash, phenanthroline and verivate thereof, dimercaptosuccinic acid, dithio two Succinic Acid, thiocarbamide, mercaptobenzothiazole, the inferior sulfydryl oxalic acid.
2. chemical bronze plating liquid according to claim 1; It is characterized in that: in the said chemical bronze plating liquid, the concentration of mantoquita is 5～30 grams per liters, and the concentration of xitix or solubility ascorbate salt is 2～13 grams per liters; The concentration of complexing agent is 15～70 grams per liters; The concentration of metal catalyst is 0.1～5 grams per liter, and the concentration of stablizer is 0.05～30 mg/litre, and the concentration of pH buffer reagent is 7～40 grams per liters.
3. chemical bronze plating liquid according to claim 1 is characterized in that: said mantoquita is selected from one or more in copper sulfate, cupric chloride, the cupric nitrate.
4. chemical bronze plating liquid according to claim 1 is characterized in that: said xitix or solubility ascorbate salt are selected from one or more in xitix, calcium ascorbate, the xitix zinc.
5. chemical bronze plating liquid according to claim 1 is characterized in that: said complexing agent is selected from one or more in Hydrocerol A, solubility Citrate trianion, tartrate, soluble tartar hydrochlorate, oxysuccinic acid, solubility malate, YD 30, the solubility edetate.
6. chemical bronze plating liquid according to claim 1 is characterized in that: said nickeliferous water-soluble salt is selected from one or more in single nickel salt, nickelous chloride, the nickel acetate.
7. chemical bronze plating liquid according to claim 1 is characterized in that: also contain tensio-active agent in the said chemical bronze plating liquid, said surfactant concentrations is 0.05～2 grams per liter.
8. the electroless copper plating method on a Kapton surface comprises each described chemical bronze plating liquid of Kapton and claim 1-7 of introducing spike is directly contacted that cleaning, drying obtain plating piece.
9. electroless copper plating method according to claim 8 is characterized in that: the method for said introducing spike is polyimide surface modification method or nano titanium dioxide photocatalysis method, and said spike is selected from a kind of in copper, gold and silver, nickel, the palladium.
10. electroless copper plating method according to claim 8 is characterized in that: the temperature of said chemical bronze plating liquid is 20～70 ℃, and be 10～70 minutes said duration of contact.
11. electroless copper plating method according to claim 8 is characterized in that: the Kapton of said introducing spike also need be removed the oxygen in the chemical bronze plating liquid with before chemical bronze plating liquid contacts.
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| CN102277567B (en) * | 2011-07-26 | 2013-04-17 | 陕西师范大学 | Chemical copper plating solution for micropore filling |
| CN103422078B (en) * | 2012-05-22 | 2016-04-27 | 比亚迪股份有限公司 | A kind of chemical bronze plating liquid and preparation method thereof |
| CN103668138B (en) * | 2012-09-24 | 2016-08-17 | 比亚迪股份有限公司 | A kind of chemical bronze plating liquid and electroless copper plating method |
| CN103966582B (en) * | 2014-04-04 | 2016-06-22 | 丽水学院 | The chemical bronze plating liquid of copper coating and using method for Kapton |
| CN104005009B (en) * | 2014-06-16 | 2016-08-17 | 北京化工大学 | The preparation of a kind of integrated molding has the method for the polyimides flexibility glue-free copper coated plate of ultra-thin layers of copper |
| JP6201153B2 (en) * | 2014-09-11 | 2017-09-27 | 石原ケミカル株式会社 | Nickel colloidal catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method |
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| CN107371338B (en) | 2016-05-13 | 2019-08-20 | 苏州卫鹏机电科技有限公司 | A kind of preparation method of the printed wiring board of ultra-thin metal layer |
| TWI606126B (en) * | 2016-12-19 | 2017-11-21 | Suzhou Weipeng Electrical Technology Co Ltd | Preparation method of polybenzimide non-glue flexible printed circuit board |
| CN107217246A (en) * | 2017-06-12 | 2017-09-29 | 南通赛可特电子有限公司 | A kind of electroless copper copper salt solution and preparation method thereof |
| CN107299337A (en) * | 2017-06-12 | 2017-10-27 | 南通赛可特电子有限公司 | A kind of chemical copper plating solution stabilization agent and preparation method thereof |
| CN110923677B (en) * | 2019-11-06 | 2021-07-16 | 中山大学 | Metal-patterned transparent photosensitive polyimide film and preparation method and application thereof |
| CN112111731B (en) * | 2020-11-23 | 2021-02-09 | 苏州天承化工有限公司 | Chemical copper plating solution and preparation method and application thereof |
| CN114939226B (en) * | 2022-07-25 | 2022-11-25 | 中南大学 | Pancreatin inactivation stent drainage tube applied to pancreaticojejunostomy and preparation method thereof |
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| CN87102861A (en) * | 1986-04-25 | 1987-12-09 | 矿山安全设备公司 | Electroless copper and plating bath thereof |
| CN101078111A (en) * | 2006-05-26 | 2007-11-28 | 佛山市顺德区汉达精密电子科技有限公司 | Chemical copper plating solution and technique thereof |
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| CN87102861A (en) * | 1986-04-25 | 1987-12-09 | 矿山安全设备公司 | Electroless copper and plating bath thereof |
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