阅读说明：本技术 一种化学镀铜液及其制备方法 (A kind of chemical bronze plating liquid and preparation method thereof ) 是由 邵永存 于 2019-09-26 设计创作，主要内容包括：本发明提供了一种化学镀铜液及其制备方法,所述化学镀铜液按质量浓度计,包括水溶性二价铜盐1-10g/L、第一络合剂10-100g/L、第二络合剂3-20g/L、还原剂2-50g/L和稳定剂0.001-100mg/L。本发明所述化学镀铜液选用了特定的第二络合剂,并且通过两种络合剂之间的相互配合,协同增效,使得到的化学镀铜液不仅在施镀过程中稳定无分解,而且其镀速也得到了大幅提升。另外,本发明所述化学镀铜液施镀后得到的镀铜膜平整均匀,能够满足功能性化学镀铜的要求。(The present invention provides a kind of chemical bronze plating liquids and preparation method thereof, the chemical bronze plating liquid is based on mass concentration, including water soluble bivalent nantokite 1-10g/L, the first complexing agent 10-100g/L, the second complexing agent 3-20g/L, reducing agent 2-50g/L and stabilizer 0.001-100mg/L.Chemical bronze plating liquid of the present invention has selected specific second complexing agent, and by the mutual cooperation between two kinds of complexing agents, synergistic, the chemical bronze plating liquid made is not only stablized during plating without decomposition, but also its plating speed is also significantly enhanced.In addition, the copper plating film even uniform obtained after chemical bronze plating liquid plating of the present invention, can satisfy the copper-plated requirement of functional chemical.)

1. a kind of chemical bronze plating liquid, which is characterized in that the chemical bronze plating liquid is based on mass concentration, including following component:

First complexing agent is selected from tartaric acid, tartrate, citric acid, citrate, N-hydroxyethyl-ethylenediamine triacetic acid, N- In hydroxyethylethylene diamine tri-acetic acid salt, triethanolamine, nitrilotriacetic acid or nitrilotriacetic acid salt any one or at least two group It closes；

Second complexing agent in tetrasodium ethylenediamine tetraacetate, succinic acid, sodium succinate or ethylenediamine any one or At least two combination.

2. chemical bronze plating liquid according to claim 1, which is characterized in that first complexing agent is sodium potassium tartrate tetrahydrate；

Preferably, second complexing agent is tetrasodium ethylenediamine tetraacetate；

Preferably, the mass concentration ratio of first complexing agent and the second complexing agent is (1-20): 1.

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

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

4. chemical bronze plating liquid according to claim 1 to 3, which is characterized in that in the chemical bronze plating liquid, bivalent cupric ion Mass concentration be 0.1-5g/L；

Preferably, the water soluble bivalent nantokite is in copper chloride, cupric sulfate pentahydrate, copper nitrate, cupric tartrate or copper acetate Any one or at least two combination, preferably cupric sulfate pentahydrate.

5. chemical bronze plating liquid described in -4 according to claim 1, which is characterized in that the reducing agent be formaldehyde, sodium hypophosphite or In glyoxylic acid any one or at least two combination, preferably formaldehyde.

6. chemical bronze plating liquid described in -5 according to claim 1, which is characterized in that the stabilizer be selected from bipyridyl, Cymag, The sour potassium hydrate of potassium cyanide, four cyano nickel (II), potassium ferrocyanide, thiocarbamide, thiourea derivative, persulfate or thiosulfate In any one or at least two combination, preferably potassium ferrocyanide.

7. a kind of preparation method of chemical bronze plating liquid, which is characterized in that the preparation method includes will be as any such as claim 1-6 Each component in the item chemical bronze plating liquid is added to the water mixing.

8. preparation method according to claim 7, which is characterized in that the preparation method includes: first by watersoluble divalent Mantoquita is mixed with water progress first time, then is successively carried out second with the first complexing agent, the second complexing agent, stabilizer and reducing agent Mixing, obtains the chemical bronze plating liquid.

9. preparation method according to claim 8, which is characterized in that the preparation method further include: mixed at second PH to 12-13 is adjusted using sodium hydroxide and/or potassium hydroxide afterwards.

10. preparation method according to claim 8 or claim 9, which is characterized in that the preparation method further include: at second Water constant volume is utilized after mixing.

Technical field

The present invention relates to wiring board production technical fields, and in particular to a kind of chemical bronze plating liquid and preparation method thereof.

Background technique

From in the 1950s, electroless copper realizes industrialization.By the effort of over half a century, this technology is in state The every field of people's economy is applied.Electroless copper occupies highly important status in chemical plating, extensive at present The various aspects such as the electro-magnetic screen layer applied to the bottom of non-metal electroplating, the hole metallization of printed board and electronic instrument.And it is close Over 30 years, the research about electroless copper has achieved a large amount of achievements, but remains many problems at present, for example, how It coordinates the stability of chemical bronze plating liquid and plates this fast contradiction, obtain the electroless copper with certain plating speed and high stability Liquid is always the important topic of this field.For electroless copper, plating speed is higher, and the stability of plating solution is more difficult to control；And The stability of plating solution is better, and plating speed is just difficult to improve.

CN104018140B discloses a kind of chemical bronze plating liquid and preparation method thereof, contains copper in the chemical bronze plating liquid Salt, complexing agent, stabilizer, reducing agent and surfactant also contain imazaquin in the chemical bronze plating liquid.The invention mentions The chemical bronze plating liquid of confession, by common chemical bronze plating liquid increase newly imazaquin, can effectively improve plating solution activity and Stability is particularly suitable for LDS copper-plating technique, and it is fast to plate speed.But it, which plates speed, only up to reach 4 μm/h, not be able to satisfy material The functional requirements of material.

CN104141120B discloses a kind of monovalence copper chemical bronze plating liquid, and the monovalence copper chemical bronze plating liquid of the invention can be More metallic coppers are deposited in the case where consumption equivalent formaldehyde, the plating speed of electroless copper not only can be improved, but also can be with The usage amount for saving formaldehyde, is conducive to the raising of production efficiency and the control of production cost.But monovalence copper is in electroless copper It is unstable in liquid, it is also necessary to which that additional addition antioxidant maintains the stabilization of cuprous ion, complicated component, and technique is cumbersome.

Therefore, the relationship for coordinating chemical bronze plating liquid stability and plating speed obtains the stable chemical plating fluid of high speed, being always The research direction for learning copper facing field, develops that a kind of high stability, plating speed is high and can obtain the electroless copper of good quality of coating Liquid has very real meaning.

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 and preparation method thereof, institutes The plating speed for stating chemical bronze plating liquid can reach 10 μm/h or more, and bath stability, and the copper plating film even uniform obtained after plating can Meet the copper-plated requirement of functional chemical.

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, which is characterized in that the chemical bronze plating liquid presses mass concentration Meter, including following component:

First complexing agent is selected from tartaric acid, tartrate, citric acid, citrate, three second of N-hydroxyethyl-ethylenediamine Any one in acid, N-hydroxyethyl-ethylenediamine triacetate, triethanolamine, nitrilotriacetic acid or nitrilotriacetic acid salt or at least two Combination；

Second complexing agent is any one in tetrasodium ethylenediamine tetraacetate, succinic acid, sodium succinate or ethylenediamine Kind or at least two combination.

Chemical bronze plating liquid of the present invention has selected specific second complexing agent, and passes through the first complexing agent and the second network Mutual cooperation between mixture, it is synergistic, the stability of plating solution can not only be improved, moreover it is possible to the plating speed of plating solution is effectively improved, In addition, the copper plating film even uniform obtained after chemical bronze plating liquid plating of the present invention, it is copper-plated to can satisfy functional chemical It is required that.

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..

First complexing agent 10-100g/L, for example, can be 10g/L, 12g/L, 15g/L, 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..

Second complexing agent 3-20g/L, for example, can be 3g/L, 3.5g/L, 4g/L, 4.5g/L, 5g/L, 5.5g/L, 6g/L, 6.5g/L、7g/L、7.5g/L、8g/L、8.5g/L、9g/L、9.5g/L、10g/L、11g/L、12g/L、13g/L、14g/L、15g/ L, 16g/L, 17g/L, 18g/L, 19g/L or 20g/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..

Stabilizer 0.001-100mg/L, such as 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, first complexing agent is sodium potassium tartrate tetrahydrate.

Preferably, second complexing agent is tetrasodium ethylenediamine tetraacetate.

Preferably, the mass concentration ratio of first complexing agent and the second complexing agent is (1-20): 1, such as can be 1: 1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1、10:1、11:1、12:1、13:1、14:1、15:1、16:1、17:1、18: 1,19:1 or 20:1 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 adjusts the pH of the chemical bronze plating liquid using sodium hydroxide and/or potassium hydroxide Value, dosage are subject to being adjusted to the pH of the chemical bronze plating liquid in the range of 12-13.

Preferably, in the chemical bronze plating liquid, the mass concentration of bivalent cupric ion is 0.1-5g/L, such as be can be 0.1g/L、0.2g/L、0.5g/L、0.8g/L、0.9g/L、1g/L、1.2g/L、1.5g/L、2g/L、2.5g/L、3g/L、3.5g/ L, 4g/L, 4.5g/L or 5g/L etc..

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 stabilizer is selected from the sour potassium hydrate of bipyridyl, Cymag, potassium cyanide, four cyano nickel (II), ferrous iron In potassium cyanide, thiocarbamide, thiourea derivative, persulfate or thiosulfate any one or at least two combination, preferably For potassium ferrocyanide.

Second aspect, the present invention also provides a kind of preparation method of chemical bronze plating liquid, the preparation method includes will be as Each component in chemical bronze plating liquid described in first aspect is added to the water mixing.

Preferably, the preparation method includes: and water soluble bivalent nantokite and water is first carried out first time to mix, then successively with First complexing agent, the second complexing agent, stabilizer and reducing agent carry out second and mix, and obtain the chemical bronze plating liquid.

Preferably, the preparation method further include: adjusted after being mixed at second using sodium hydroxide and/or potassium hydroxide PH to 12-13.

Preferably, the preparation method further include: utilize water constant volume after mixing at second.

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

(1) chemical bronze plating liquid of the present invention has selected specific second complexing agent, and passes through the first complexing agent and the Mutual cooperation between two complexing agents, it is synergistic, the stability of plating solution can not only be improved, guarantees that it stablizes during plating Without decomposition, moreover it is possible to effectively improve the plating speed of plating solution.The plating speed of chemical bronze plating liquid of the present invention can reach 10 μm/h or more；

(2) the copper plating film even uniform obtained after chemical bronze plating liquid plating of the present invention, can satisfy functional chemical Copper-plated requirement.

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.