阅读说明：本技术 一种化学镀铜液、化学镀铜膜及其制备方法 (A kind of chemical bronze plating liquid, chemical plating copper film and preparation method thereof ) 是由 李晓红 宋通 邵永存 王科 章晓冬 刘江波 于 2019-09-24 设计创作，主要内容包括：本发明提供一种化学镀铜液、化学镀铜膜及其制备方法,所述化学镀铜液中添加了氨基酸和/或氨基酸衍生物,该氨基酸和/或氨基酸衍生物的加入,除了可以提高镀液的稳定性之外,还能提升增延剂的效果,使制备得到的化学镀铜膜具有很高的延展性,进而增加PCB的互联可靠性,尤其适用于FPC的制造。另外,本发明所述化学镀铜液还具有稳定性好、镀速高等优点,且所述化学镀铜液不含氰化物,对环境污染小。(The present invention provides a kind of chemical bronze plating liquid, chemical plating copper film and preparation method thereof, amino acid and/or amino acid derivativges are added in the chemical bronze plating liquid, the addition of the amino acid and/or amino acid derivativges, other than the stability that plating solution can be improved, the effect for increasing and prolonging agent can also be promoted, make the chemical plating copper film being prepared that there is very high ductility, and then increase the interconnection reliability of PCB, is particularly suitable for the manufacture of FPC.In addition, chemical bronze plating liquid of the present invention also has many advantages, such as that stability is good, plating speed is high, and the chemical bronze plating liquid is free of cyanide, and environmental pollution is small.)

1. a kind of chemical bronze plating liquid, which is characterized in that the chemical bronze plating liquid includes following component:

2. chemical bronze plating liquid according to claim 1, which is characterized in that the chemical bronze plating liquid further includes sodium hydroxide And/or potassium hydroxide；

Preferably, the pH of the chemical bronze plating liquid is 12-13.

3. chemical bronze plating liquid according to claim 1 or 2, which is characterized in that it is described increasing prolong agent be selected from soluble nickel salt, can In dissolubility molysite, soluble ferrite or bipyridyl any one or at least two combination；

Preferably, the soluble nickel salt is selected from six hydration nickel sulfate and/or nickel chloride；

Preferably, in the chemical bronze plating liquid, the content of nickel ion is 100-500mg/L in the soluble nickel salt；

Preferably, the soluble ferric iron salt in ferric sulfate, iron chloride or ferric nitrate any one or at least two group It closes；

Preferably, in the chemical bronze plating liquid, the content of iron ion is 10-100mg/L in the soluble ferric iron salt；

Preferably, the soluble ferrite in ferrous sulfate, frerrous chloride or ferrous nitrate any one or at least Two kinds of combination；

Preferably, in the chemical bronze plating liquid, the content of the soluble ferrite ferrous ions is 10-100mg/L；

Preferably, the bipyridyl is 2,2'- bipyridyl；

Preferably, in the chemical bronze plating liquid, the content of the bipyridyl is 0.01-50mg/L.

4. chemical bronze plating liquid according to claim 1-3, which is characterized in that the amino acid be selected from glycine, In arginine, threonine, lysine or glutamic acid any one or at least two combination；

Preferably, the amino acid derivativges are selected from N- benzyl glycine, n,N-Dimethylglycine, the bright ammonia of glycine-DL- Acid, D- leucyl--glycyl-glycine, BOC- (R) -2- (2- thienyl)-glycine, L-arginine L MALIC ACID, N- Any one in benzoyl-L-threonine, N- methyl L-lysine or 3- hydroxy-3-methyl glutamic acid or at least two Combination.

5. chemical bronze plating liquid according to claim 1-4, which is characterized in that the water soluble bivalent nantokite is selected from In copper chloride, cupric sulfate pentahydrate, copper nitrate, cupric tartrate or copper acetate any one or at least two combination, preferably Cupric sulfate pentahydrate；

Preferably, the reducing agent be formaldehyde, sodium hypophosphite or glyoxylic acid in any one or at least two combination, Preferably formaldehyde.

6. chemical bronze plating liquid according to claim 1-5, which is characterized in that the complexing agent be selected from tartaric acid, Tartrate, citric acid, citrate, N-hydroxyethyl-ethylenediamine triacetic acid, N-hydroxyethyl-ethylenediamine triacetate, three ethyl alcohol In amine, nitrilotriacetic acid or nitrilotriacetic acid salt any one or at least two combination, preferably sodium potassium tartrate tetrahydrate.

7. a kind of chemical plating copper film, which is characterized in that the chemical plating copper film is by chemistry as claimed in any one of claims 1 to 6 Copper plating bath plating obtains.

8. a kind of preparation method of chemical plating copper film according to claim 7, which is characterized in that the preparation method packet It includes: unplated piece being contacted with chemical bronze plating liquid as claimed in any one of claims 1 to 6, is cleaned, is dry, obtains the chemical plating Copper film.

9. preparation method according to claim 8, which is characterized in that the temperature of the chemical bronze plating liquid is 28-40 DEG C；

Preferably, any one of the unplated piece in pcb board, FPC, IC support plate or semiconductor material；

Preferably, the time of the contact is 3min-1h；

Preferably, oxygen and/or air are passed through into chemical bronze plating liquid in the contact process；

Preferably, the mode of the cleaning is to be cleaned using deionized water；

Preferably, the mode of the drying is drying and/or drying.

10. preparation method according to claim 8 or claim 9, which is characterized in that first live to unplated piece before the contact Change；

Preferably, the activation includes: to be activated using activating solution to unplated piece；

Preferably, the activating solution is ionic palladium activating solution or colloidal pd activation solution.

Technical field

The present invention relates to wiring board production technical fields, and in particular to a kind of chemical bronze plating liquid, chemical plating copper film and its system Preparation Method.

Background technique

In printed-circuit board manufacturing technology, by electroless copper processing procedure, one layer of electroless copper is formed on dielectric substrate Layer, serves as the articulamentum of dielectric substrate and electro-coppering.With being continuously increased for the flexible circuit board market (FPC), manufacturing process There has also been strict requirements further with performance indicator.Critical processes one of of the chemical-copper-plating process as FPC, are also faced with product The demand of optimization and upgrading.In order to meet the needs of FPC is flexible, resistant to bending, chemical plating copper layer must also have the spy of high ductibility Point.

The copper film ductility formed using conventional chemical copper plating bath and technique is not good enough, in terms of may cause FPC reliability Some defects.At the same time, contain cyanide in existing chemical bronze plating liquid, environmental pollution is big, is unfavorable for electroless copper skill more Development of the art to pollution-freeization direction.

CN104250732B discloses a kind of electroless copper mixture and preparation method thereof, in the electroless copper mixture Containing soluble copper salt, complexing agent, stabilizer, reducing agent and surfactant, also contains in the electroless copper mixture and receive Rice silica.The electroless copper mixture that the invention provides, by increasing nano-silica newly in common electroless copper system SiClx can effectively improve the wearability and anti-corrosive properties of copper plate, but at the same time, copper film prolongs in obtained chemical plating copper piece Malleability is deteriorated.

CN103668138A discloses a kind of chemical bronze plating liquid, including mantoquita, complexing agent, pH adjusting agent, reducing agent, gland are fast Purine and nickel potassium cyanide；When carrying out electroless copper using the chemical bronze plating liquid that the invention provides, the extension of coating can be effectively improved Property and toughness.But the chemical bronze plating liquid will cause the wastewater treatment containing EDTA after the completion of chemical plating using EDTA as primary complexing agent It is difficult.

Therefore, a kind of chemical bronze plating liquid of environmental protection is developed, and high ductibility can be prepared using the chemical bronze plating liquid Learning copper plating film is the difficulty and challenge put in face of people.

Summary of the invention

In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of chemical bronze plating liquid, chemical plating copper film and its Preparation method.Chemical bronze plating liquid stability of the present invention is good, plating speed is high, and is free of cyanide, and environmental pollution is small, meanwhile, The chemical plating copper film ductility that it is prepared is high, can increase the interconnection reliability of PCB, be particularly suitable for the manufacture of FPC.

To achieve this purpose, the present invention adopts the following technical scheme:

In a first aspect, the present invention provides a kind of chemical bronze plating liquid, the chemical bronze plating liquid includes following component:

Chemical bronze plating liquid stability of the present invention is good, plating speed is high, and is free of cyanide, and environmental pollution is small, meanwhile, The chemical plating copper film ductility being prepared is high.

Amino acid and/or amino acid derivativges are added in chemical bronze plating liquid of the present invention, the amino acid and/or amino The addition of acid derivative can improve the stability of plating solution, moreover it is possible to promote the effect for increasing and prolonging agent, make the electroless copper being prepared Film has very high ductility, and then can increase the interconnection reliability of PCB, is particularly suitable for the manufacture of FPC.

In the present invention, the ratio of each component should be controlled within the above range, just can guarantee that the chemical bronze plating liquid is steady in this way It is fixed effective, and the chemical plating copper film ductility with higher being prepared.

It should be noted that the solvent of chemical bronze plating liquid of the present invention is deionized water.

The water soluble bivalent nantokite 1-10g/L, such as can be 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/ L, 8g/L, 9g/L or 10g/L etc..

Reducing agent 2-50g/L, for example, can be 2g/L, 3g/L, 5g/L, 8g/L, 9g/L, 10g/L, 11g/L, 12g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L or 50g/L etc..

Complexing agent 20-100g/L, for example, can be 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, 55g/L, 60g/L, 65g/L, 70g/L, 75g/L, 80g/L, 85g/L, 90g/L, 95g/L or 100g/L etc..

Agent 0.001-500mg/L is prolonged in increasing, such as can be 0.001mg/L, 0.002mg/L, 0.005mg/L, 0.008mg/ L、0.01mg/L、0.015mg/L、0.02mg/L、0.05mg/L、0.1mg/L、0.2mg/L、0.5mg/L、1mg/L、2mg/L、 3mg/L、5mg/L、10mg/L、15mg/L、20mg/L、30mg/L、50mg/L、80mg/L、100mg/L、120mg/L、150mg/ L, 180mg/L, 200mg/L, 250mg/L, 300mg/L, 350mg/L, 400mg/L, 450mg/L or 500mg/L etc..

Amino acid and/or amino acid derivativges 0.001-100mg/L, for example, can be 0.001mg/L, 0.003mg/L, 0.005mg/L、0.008mg/L、0.01mg/L、0.015mg/L、0.02mg/L、0.05mg/L、0.1mg/L、0.2mg/L、 0.5mg/L、1mg/L、2mg/L、3mg/L、5mg/L、10mg/L、15mg/L、20mg/L、30mg/L、40mg/L、50mg/L、 60mg/L, 70mg/L, 80mg/L, 90mg/L or 100mg/L etc..

Preferably, the chemical bronze plating liquid further includes sodium hydroxide and/or potassium hydroxide.

Preferably, the pH of the chemical bronze plating liquid is 12-13, for example, can be 12.1,12.2,12.3,12.4,12.5, 12.6,12.7,12.8,12.9 or 13 etc..

It should be noted that the present invention is to adjust the chemical bronze plating liquid using sodium hydroxide and/or potassium hydroxide PH range.

Preferably, agent appointing in soluble nickel salt, soluble ferric iron salt, soluble ferrite or bipyridyl, is prolonged in the increasing It anticipates a kind of or at least two combinations.

It is preferably soluble nickel salt, soluble ferric iron salt or soluble ferrite that agent is prolonged in increasing of the present invention, is due to these Metal cation in soluble-salt can be under the facilitation of amino acid or amino acid derivativges and copper ion realization is coprecipitated Product, obtains copper alloy film plating layer, can be effectively improved the ductility of chemical plating copper layer in this way, at the same time, in soluble-salt Metal cation can also improve plating speed, improve coating quality.

The application preferably can also be used as increasing to prolong agent by bipyridyl, be the copper crystal grain that can make to be formed due to the addition of bipyridyl Finer and close, lattice defect is few, and plating film-strength is high, and ductility is obviously improved.

Amino acid (and/or its derivative) must be existed simultaneously in chemical bronze plating liquid of the present invention and is increased prolongs agent, it is preceding Person primarily serves stable plating solution and adjusts the effect of plating speed, and the latter primarily serves the effect of enhancing coating ductility, and the two is mutual Cooperation, it is indispensable, it is synergistic.

Preferably, the soluble nickel salt is selected from six hydration nickel sulfate and/or nickel chloride.

Preferably, in the chemical bronze plating liquid, the content of nickel ion is 100-500mg/L in the soluble nickel salt, Such as can be 100mg/L, 120mg/L, 150mg/L, 180mg/L, 200mg/L, 250mg/L, 300mg/L, 350mg/L, 400mg/L, 450mg/L or 500mg/L etc..

Preferably, the soluble ferric iron salt in ferric sulfate, iron chloride or ferric nitrate any one or at least two Combination.

Preferably, in the chemical bronze plating liquid, the content of iron ion is 10-100mg/L, example in the soluble ferric iron salt Such as can be 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L or 100mg/L etc..

Preferably, the soluble ferrite in ferrous sulfate, frerrous chloride or ferrous nitrate any one or At least two combination.

Preferably, in the chemical bronze plating liquid, the content of the soluble ferrite ferrous ions is 10-100mg/ L, for example, can be 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L or 100mg/L etc..

Preferably, the bipyridyl is 2,2'- bipyridyl.

Preferably, in the chemical bronze plating liquid, the content of the bipyridyl is 0.01-50mg/L, such as be can be 0.01mg/L、0.02mg/L、0.05mg/L、0.1mg/L、0.2mg/L、0.3mg/L、0.5mg/L、1mg/L、2mg/L、5mg/L、 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L, 35mg/L, 40mg/L, 45mg/L or 50mg/L etc..

Preferably, any one of the amino acid in glycine, arginine, threonine, lysine or glutamic acid Or at least two combination.

Preferably, it is bright to be selected from N- benzyl glycine, n,N-Dimethylglycine, glycine-DL- for the amino acid derivativges Propylhomoserin, D- leucyl--glycyl-glycine, BOC- (R) -2- (2- thienyl)-glycine, L-arginine L MALIC ACID, Any one in N- benzoyl-L-threonine, N- methyl L-lysine or 3- hydroxy-3-methyl glutamic acid or at least two Combination.

Preferably, the water soluble bivalent nantokite is selected from copper chloride, cupric sulfate pentahydrate, copper nitrate, cupric tartrate or acetic acid In copper any one or at least two combination, preferably cupric sulfate pentahydrate.

Preferably, the reducing agent is any one in formaldehyde, sodium hypophosphite or glyoxylic acid or at least two Combination, preferably formaldehyde.

Preferably, the complexing agent is selected from tartaric acid, tartrate, citric acid, citrate, N-hydroxyethyl-ethylenediamine three Any one in acetic acid, N-hydroxyethyl-ethylenediamine triacetate, triethanolamine, nitrilotriacetic acid or nitrilotriacetic acid salt or at least two The combination of kind, preferably sodium potassium tartrate tetrahydrate.

Second aspect, the present invention also provides a kind of chemical plating copper film, the chemical plating copper film is by as described in relation to the first aspect Chemical bronze plating liquid plating obtain.

The third aspect, the preparation method for the chemical plating copper film that the present invention also provides a kind of as described in second aspect are described Preparation method includes: to contact unplated piece with chemical bronze plating liquid as described in relation to the first aspect, clean, is dry, obtains the chemistry Copper plating film.

Preferably, the temperature of the chemical bronze plating liquid is 28-40 DEG C, such as can be 28 DEG C, 29 DEG C, 30 DEG C, 31 DEG C, 32 DEG C, 33 DEG C, 34 DEG C, 35 DEG C, 36 DEG C, 37 DEG C, 38 DEG C, 39 DEG C or 40 DEG C etc..

Preferably, any one of the unplated piece in pcb board, FPC, IC support plate or semiconductor material.

Preferably, the time of the contact be 3min-1h, such as can be 3min, 5min, 8min, 10min, 13min, 15min, 18min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 1h etc..

Preferably, oxygen and/or air are passed through into chemical bronze plating liquid in the contact process.

Preferably, the mode of the cleaning is to be cleaned using deionized water.

Preferably, the mode of the drying is drying and/or drying.

Preferably, first unplated piece is activated before the contact.

Preferably, the activation includes: to be activated using activating solution to unplated piece.

Preferably, the activating solution is ionic palladium activating solution or colloidal pd activation solution.

Preferably, the preparation method comprises the following steps:

(1) first unplated piece is immersed in ionic palladium activating solution or colloidal pd activation solution and is activated；

(2) then the unplated piece that surface activation process is crossed is immersed in chemical bronze plating liquid again and carries out plating, during plating It is passed through oxygen and/or air into chemical bronze plating liquid, utilizes deionized water to clean after the completion of plating, and dried up or dried, Obtain the chemical plating copper film.Wherein, plating time 3min-1h, bath temperature is 28-40 DEG C when plating.

Compared with the existing technology, the invention has the following advantages:

(1) amino acid and/or amino acid derivativges are added in chemical bronze plating liquid of the present invention, the amino acid and/or The addition of amino acid derivativges, other than the stability that plating solution can be improved, moreover it is possible to promote the effect for increasing and prolonging agent, make to be prepared into The chemical plating copper film arrived has very high ductility, and then can increase the interconnection reliability of PCB, is particularly suitable for the system of FPC It makes.In addition, chemical bronze plating liquid of the present invention also has many advantages, such as that stability is good, plating speed is high.

(2) chemical bronze plating liquid of the present invention is free of cyanide, and environmental pollution is small.

Specific embodiment

The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright , the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.