阅读说明：本技术 一种镀镍液添加剂、镀镍液及电镀工艺 (Nickel plating solution additive, nickel plating solution and electroplating process ) 是由 梁国柱 梁彪 于 2020-08-12 设计创作，主要内容包括：一种镀镍液添加剂,包括主光剂、柔软剂和配位导电盐。所述镀镍液添加剂中的组分在高、中、低电流密度区各具特性,通过各组分的协同作用,主光剂可提高镍镀层的光亮度,柔软剂可提高镍镀层的光亮和整平度并调节镀层的应力,配位导电盐可细化镍层结晶,提高镀液的均镀能力和抗金属离子杂质污染能力,得到全光亮且整平的镍镀层。(A nickel plating solution additive comprises a main polishing agent, a softening agent and coordination conductive salt. The components in the nickel plating solution additive have characteristics in high, medium and low current density regions, through the synergistic effect of the components, the main light agent can improve the brightness of a nickel plating layer, the softening agent can improve the brightness and flatness of the nickel plating layer and adjust the stress of the plating layer, the coordination conductive salt can refine the crystallization of the nickel layer, the uniform plating capacity and the metal ion impurity pollution resistance of the plating solution are improved, and the full-bright and leveled nickel plating layer is obtained.)

1. A nickel plating solution additive, comprising:

a primary light agent, the primary light agent comprising:

a main light agent first component, wherein the main light agent first component comprises one to three of benzene sulfonyl imide salt, alkyne compound and alkyl sulfo pyridine salt;

a main polishing agent second component, wherein the main polishing agent second component comprises one to three of alkyne alkyl ether, alkyne sulfonate and alkene alkyl sulfonate;

the third component of the main polishing agent comprises one or two of alkynylamine and azathiocycle;

the fourth component of the main polishing agent, the fourth component of the main polishing agent comprises one to three of aryl sulfonate, alkene alkyl sulfonate and aldehyde;

the light stabilizer comprises a light stabilizer first component, a light stabilizer second component and a light stabilizer second component, wherein the light stabilizer second component comprises one to three of aryl sulfonate, alkynyl alkyl ether and aldehyde;

the light stabilizer comprises a light stabilizer sixth component, wherein the light stabilizer sixth component comprises one to four of acetylene salt, butyl ether salt, acetylene amine compounds and sulfur-nitrogen heterocyclic compounds;

a gloss reducing agent third component, the gloss reducing agent third component comprising a surfactant;

the light stabilizer comprises a light stabilizer component A and a light stabilizer component B, wherein the light stabilizer component A comprises a light stabilizer component A and a light stabilizer component B, and the light stabilizer component B comprises a light stabilizer component B and a light stabilizer component B;

also includes a softening agent, the softening agent includes:

a softener first component comprising one to three of arylsulfonylimide salts, acetylenic alkyl ethers, alkylaminopropyls;

a softener second component, wherein the softener second component comprises one to three of acetylene sulfonate, alkene alkyl sulfonate and acetylene alkyl ether;

a third component of a softening agent, wherein the third component of the softening agent comprises one or two of alkynylamine compounds and sulfur-nitrogen heterocyclic compounds;

a fourth component of a softening agent, wherein the fourth component of the softening agent comprises one to three of aryl sulfonate, alkene alkyl sulfonate and aldehyde;

a softening agent fifth component, wherein the softening agent fifth component comprises one to three of aryl sulfonate, alkynyl alkyl ether and aldehyde;

the softening agent sixth component comprises one to four of acetylene salt, butyl ether salt, acetylene amine compounds and sulfur and nitrogen heterocyclic compounds;

a softening agent seventh component, wherein the softening agent seventh component comprises one to four of acetylene salt, aldehyde, alkyl amino propyne and benzyl-alkyl alkynol pyridine inner salt;

also includes coordination conductive salt.

2. The nickel plating solution additive according to claim 1, wherein:

the main light agent first component comprises six to eight of saccharin, propargyl alcohol propoxy ether, propargyl alcohol ethoxy ether, diethylaminopropyne, pyridinium propanesulfonate, propargyl alcohol, pyridinium hydroxypropanesulfonate and dimethylaminopropyne;

the second component of the main light agent comprises three to four of butynediol diethoxy ether, butynediol monopropoxy ether, sodium propiolate, sodium allylsulfonate and sodium vinylsulfonate;

the main light agent third component comprises two to three of sodium allylsulfonate, diethylamino propyne, sodium propyne sulfonate and s-hydroxyethyl isothiouronium salt;

the fourth component of the main light agent comprises two to five of sodium benzene sulfinate, sodium propiolate, butynediol diethoxy ether, butynediol monopropoxy ether, sodium allyl sulfonate, sodium vinyl sulfonate and alkylsulfopyridine salt;

the fifth component of the main light agent comprises one or two of formaldehyde, chloral hydrate and sodium benzene sulfinate;

the sixth component of the main light agent comprises two to three of diethylamino propyne, butyl ether type humate, propane type humate and s-carboxyethyl isothiourea humate;

the gloss reducing agent a seventh component comprising an anionic or nonionic surfactant;

the eighth component of the main light agent comprises three to four of benzyl-methyl alkynol pyridine inner salt, propiolic salt, butyl ether salt, formaldehyde, dimethylamino propine and diethylamino propine.

3. The nickel plating solution additive according to claim 2, wherein:

the first component of the softening agent comprises six to seven of saccharin, bisbenzenesulfonylimine, propargyl alcohol propoxy ether, propargyl alcohol ethoxy ether, diethylaminopropyne, pyridinium hydroxypropanesulfonate and dimethylaminopropyne;

the second component of the softening agent comprises three to four of butynediol diethoxy ether, sodium propiolate, sodium allylsulfonate and sodium vinylsulfonate;

the third component of the softening agent comprises three to four of sodium allylsulfonate, diethylamino propyne, sodium propyne sulfonate, s-carboxyethyl isothiourea salt and diethylenetriamine;

the fourth component of the softening agent comprises four to five of sodium benzene sulfinate, sodium propiolate, butynediol diethoxy ether, sodium allyl sulfonate and sodium vinyl sulfonate;

the fifth component of the softening agent comprises one or two of formaldehyde, sodium benzene sulfinate and chloral hydrate;

the sixth component of the softening agent comprises three to four of diethylamino propyne, butyl ether humate, propane sulfonic acid humate, formaldehyde and s-carboxyethyl isothiourea humate;

the seventh component of the softening agent comprises four to five of diethylamino propine, propane salt, butyl ether salt, benzyl-methyl alkynol pyridine inner salt, formaldehyde and dimethylamino propine.

4. The nickel plating solution additive according to claim 3, wherein:

the main optical agent comprises 35-60g of phenylsulfonyl imine compounds, 5-15g of aryl sulfonate, 50-150g of alkenyl alkyl sulfonate, 78-89g of ether compounds, 0-2g of alcohol compounds, 40-60g of alkynyl sulfonate, 4-8g of alkyne compounds, 1-2g of aldehyde compounds, 10-15.1g of surfactant, 250g of pyridinium alkyl sulfonate, 2-4g of pyridinium alkyl ether sulfonate and 2-3g of sulfur nitrogen heterocyclic compounds per liter.

Each liter of softening agent comprises 90-110g of benzene sulfonyl imide compounds, 3-6g of aryl sulfonate, 150g of alkenyl alkyl sulfonate, 5-7g of ether compounds, 4-8g of alkynyl sulfonate, 0.3-0.6g of alkyne compounds, 1-3g of aldehyde compounds, 30-50g of pyridinium alkyl sulfonate, 0.05-0.3g of sulfur nitrogen heterocyclic compounds and 0.02-0.15g of polyethylene polyamine compounds.

5. The nickel plating solution additive according to claim 4, wherein:

the main optical agent per liter comprises 20-50g of saccharin, 0-20g of dibenzenesulfonylimide, 5-15g of sodium benzene sulfinate, 60-100g of sodium allylsulfonate, 5-10g of butynediol diethoxy ether, 30-60g of propiolic alcohol ethoxy ether, 20-40g of propiolic alcohol propoxy ether, 0-2g of propiolic alcohol, 30-60g of sodium propiolic sulfonate, 4-8g of diethylaminopropiolic acid, 1-2g of formaldehyde, 10-15g of sodium isethionate, 0-0.1g of sodium dodecyl sulfate, 0-20g of pyridinium propane sulfonate, 200 g of pyridinium hydroxypropanesulfonate, 250g of butylate sulfonate and 2-3g of s-carboxyethylisothiouronium sulfonate.

6. The nickel plating solution additive according to claim 5, wherein:

each liter of softener comprises 40-50g of saccharin, 40-60g of dibenzenesulfonyl imide, 3-6g of sodium benzene sulfinate, 250g of sodium allylsulfonate, 2-3g of butynediol diethoxy ether, 1-2g of propiolic ethoxy ether, 1-2g of propiolic propoxy ether, 4-8g of sodium propiolate, 0.3-0.6g of diethylaminopropiolic acid, 1-3g of formaldehyde, 0-10g of pyridinium propanesulfonate, 0-50g of pyridinium carboxypropanesulfonate, 0.05-0.3g of s-carboxyethylisothiouronium salt and 0.02-0.15g of diethylenetriamine.

7. The nickel plating solution additive according to claim 6, wherein:

the coordination conductive salt comprises one or more of citrate, gluconate and magnesium salt.

8. The nickel plating solution additive according to claim 7, wherein:

the coordination conductive salt comprises one or more of sodium citrate, potassium citrate, sodium gluconate, potassium gluconate and magnesium sulfate.

9. A nickel plating solution is characterized in that:

prepared by nickel plating solution additive and neutral solution containing nickel salt; the nickel plating solution additive is the nickel plating solution additive according to any one of claims 1 to 8;

the nickel plating solution comprises 0.1-0.2ml/L of main light agent, 8-10ml/L of softening agent and 180g/L of coordination conductive salt 130-;

the nickel salt includes nickel sulfate heptahydrate and nickel chloride hexahydrate.

10. An electroplating process, comprising:

pre-treating a part to be plated; washing the parts with water, and then activating with weak acid; barrel plating nickel plating is carried out under the neutral condition; carrying out post-treatment; wherein the nickel plating solution used for barrel nickel plating is the nickel plating solution according to claim 9.

Technical Field

The invention belongs to the field of electroplating, and particularly relates to a nickel plating solution additive, a nickel plating solution and an electroplating process.

Background

The electroplating process mainly comprises a rack plating type and a barrel plating type. Rack plating is commonly used to plate expensive or large plated parts. Barrel plating is commonly used to plate small plated parts.

The nickel plating is an important plating species which is widely applied at present, and the existing nickel plating process is divided into acid nickel plating solution, alkaline nickel plating solution and neutral nickel plating solution from the acid-base part of the plating solution.

(1) Acid nickel plating solution: in the acidic nickel plating solution, nickel exists in the form of positively charged nickel hydrate ions. In the acidic nickel plating solution, nickel ions are easy to discharge and deposit on the cathode, the allowed cathode current density range is wide, a full bright and highly leveled nickel plating layer is easy to obtain, and the nickel plating layer can bear 8A/dm under strong air stirring²Of a cathodeThe excellent performances of high brightness and flatness and high deposition speed of the plating layer are particularly outstanding.

(2) Alkaline nickel plating solution: in the alkaline nickel plating solution, nickel and a complexing agent generate complex ions with stronger electronegativity. Under the alkaline environment, nickel complex ions have larger polarization in a cathode region and need graded discharge electrodeposition, and hydrogen can be separated out under higher current density, so that the coating is brittle. Therefore, the cathode current density of bright nickel plating under alkaline environment is not more than 2A/dm². When the plating solution is weakly alkaline, nickel hydroxide is easily generated on the anode during electroplating, and the dissolution of the anode is influenced.

(3) Neutral nickel plating solution: in the neutral nickel plating solution, nickel ions and a complexing agent generate complex ions with electronegativity and medium strength. Under the neutral environment, the nickel complex ions have small polarization in the cathode region. At the current density of barrel plating, the nickel deposit has excellent brightness and leveling.

In the bright barrel plating nickel plating process, metal ions such as zinc ions are easily dissolved into a plating solution from a plated part under an acidic environment, so that a nickel plating layer becomes dark and black. In the neutral nickel solution, nickel ions and a complexing agent generate complex ions with medium electronegativity, and the nickel solution is suitable for barrel nickel plating production of zinc-aluminum alloy or steel; the neutral plating solution has wider tolerance to zinc impurities, so the method is particularly suitable for the electroplating processing of zinc-aluminum alloy.

During the electroplating process, various compounds adsorbed on the cathode or anode are continuously consumed, and the reduction or oxidation speed of various compounds on the electrode is different, so that the composition of the additive of the electroplating solution is a more complex system. In barrel plating, the components in the additive of the plating solution can form a synergistic effect and act on different current density areas, so that a bright and smooth plating layer can be obtained.

At present, the prior art can only obtain a semi-bright nickel plating layer by electroplating in a weak alkaline or neutral nickel plating process, and how to obtain a full-bright nickel plating layer with high leveling property by electroplating in a neutral solution is a hot problem in current research.

Disclosure of Invention

The invention aims to overcome the defects and shortcomings in the prior art and provide a nickel plating solution additive, wherein the nickel plating solution additive is used for electroplating nickel under a neutral condition, so that a nickel plating layer with full brightness and high leveling property can be obtained on a plated part.

The invention is realized by the following technical scheme: a nickel plating solution additive comprises a main light agent, wherein the main light agent comprises a first main light agent component, and the first main light agent component comprises one to three of benzenesulfonylimide salt, acetylenic compounds and alkylsulfopyridine humate salt; a main polishing agent second component, wherein the main polishing agent second component comprises one to three of alkyne alkyl ether, alkyne sulfonate and alkene alkyl sulfonate; the third component of the main polishing agent comprises one or two of alkynylamine and azathiocycle; the fourth component of the main polishing agent, the fourth component of the main polishing agent comprises one to three of aryl sulfonate, alkene alkyl sulfonate and aldehyde; the light stabilizer comprises a light stabilizer first component, a light stabilizer second component and a light stabilizer second component, wherein the light stabilizer second component comprises one to three of aryl sulfonate, alkynyl alkyl ether and aldehyde; the light stabilizer comprises a light stabilizer sixth component, wherein the light stabilizer sixth component comprises one to four of acetylene salt, butyl ether salt, acetylene amine compounds and sulfur-nitrogen heterocyclic compounds; a gloss reducing agent third component, the gloss reducing agent third component comprising a surfactant; the light stabilizer comprises a light stabilizer component A and a light stabilizer component B, wherein the light stabilizer component A comprises a light stabilizer component A and a light stabilizer component B, and the light stabilizer component B comprises a light stabilizer component B and a light stabilizer component B;

also includes a softening agent, the softening agent includes: a softener first component comprising one to three of arylsulfonylimide salts, acetylenic alkyl ethers, alkylaminopropyls; a softener second component, wherein the softener second component comprises one to three of acetylene sulfonate, alkene alkyl sulfonate and acetylene alkyl ether; a third component of a softening agent, wherein the third component of the softening agent comprises one or two of alkynylamine compounds and sulfur-nitrogen heterocyclic compounds; a fourth component of a softening agent, wherein the fourth component of the softening agent comprises one to three of aryl sulfonate, alkene alkyl sulfonate and aldehyde; a softening agent fifth component, wherein the softening agent fifth component comprises one to three of aryl sulfonate, alkynyl alkyl ether and aldehyde; the softening agent sixth component comprises one to four of acetylene salt, butyl ether salt, acetylene amine compounds and sulfur and nitrogen heterocyclic compounds; a softening agent seventh component, wherein the softening agent seventh component comprises one to four of acetylene salt, aldehyde, alkyl amino propyne and benzyl-alkyl alkynol pyridine inner salt;

also includes coordination conductive salt.

Compared with the prior art, the nickel plating solution additive is applied to a barrel plating process under a neutral environment, the components in the nickel plating solution additive have characteristics in a high current density area, a medium current density area and a low current density area respectively, the first component of the main brightener is easy to adsorb in the high current density area, the second component of the main brightener is easy to adsorb in the medium current density area, the third component of the main brightener is easy to adsorb in the low current density area, the fourth component of the main brightener can adsorb in the low current density area and the high current density area, the fifth component of the main brightener is easy to generate oxidation or reduction reaction on an electrode, the sixth component of the main brightener can improve the microscopic leveling performance of a plating layer, and the eighth component of the main brightener can adjust a desorption potential and coordinate competitive adsorption and induced adsorption of certain components of the additive; the first component of the softening agent is easy to adsorb in a high current density area, the second component of the softening agent is easy to adsorb in a medium current density area, the third component of the softening agent is easy to adsorb in a low current density area, the fourth component of the softening agent can adsorb in both the low current density area and the high current density area, the fifth component of the softening agent is easy to generate oxidation or reduction reaction on an electrode, the sixth component of the softening agent can improve the micro-leveling property of a plating layer, and the seventh component of the softening agent can adjust desorption potential and coordinate competitive adsorption and induced adsorption of certain components of additives. Through the synergistic effect of the components, the nickel plating solution additive can be used for barrel plating and nickel plating in a neutral environment to obtain a nickel plating layer with full brightness and high leveling property.

Further, the main brightening agent first component comprises six to eight of saccharin, propargyl alcohol propoxy ether, propargyl alcohol ethoxy ether, diethylaminopropyne, pyridinium propanesulfonate, propargyl alcohol, pyridinium hydroxypropanesulfonate and dimethylaminopropyne; the second component of the main light agent comprises three to four of butynediol diethoxy ether, butynediol monopropoxy ether, sodium propiolate, sodium allylsulfonate and sodium vinylsulfonate; the main light agent third component comprises two to three of sodium allylsulfonate, diethylamino propyne, sodium propyne sulfonate and s-hydroxyethyl isothiouronium salt; the fourth component of the main light agent comprises two to five of sodium benzene sulfinate, sodium propiolate, butynediol diethoxy ether, butynediol monopropoxy ether, sodium allyl sulfonate, sodium vinyl sulfonate and alkylsulfopyridine salt; the fifth component of the main light agent comprises one or two of formaldehyde, chloral hydrate and sodium benzene sulfinate; the sixth component of the main light agent comprises two to three of diethylamino propyne, butyl ether type humate, propane type humate and s-carboxyethyl isothiourea humate; the gloss reducing agent a seventh component comprising an anionic or nonionic surfactant; the eighth component of the main light agent comprises three to four of benzyl-methyl alkynol pyridine inner salt, propiolic salt, butyl ether salt, formaldehyde, dimethylamino propine and diethylamino propine. The main light agent is used for improving the brightness of the nickel coating.

Further, the first component of the softening agent comprises six to seven of saccharin, dibenzenesulfonyl imine, propargyl alcohol propoxy ether, propargyl alcohol ethoxy ether, diethylaminopropyne, pyridinium hydroxypropanesulfonate and dimethylamino propyne; the second component of the softening agent comprises three to four of butynediol diethoxy ether, sodium propiolate, sodium allylsulfonate and sodium vinylsulfonate; the third component of the softening agent comprises three to four of sodium allylsulfonate, diethylamino propyne, sodium propyne sulfonate, s-carboxyethyl isothiourea salt and diethylenetriamine; the fourth component of the softening agent comprises four to five of sodium benzene sulfinate, sodium propiolate, butynediol diethoxy ether, sodium allyl sulfonate and sodium vinyl sulfonate; the fifth component of the softening agent comprises one or two of formaldehyde, sodium benzene sulfinate and chloral hydrate; the sixth component of the softening agent comprises three to four of diethylamino propyne, butyl ether humate, propane sulfonic acid humate, formaldehyde and s-carboxyethyl isothiourea humate; the seventh component of the softening agent comprises four to five of diethylamino propine, propane salt, butyl ether salt, benzyl-methyl alkynol pyridine inner salt, formaldehyde and dimethylamino propine. The softening agent is used for improving the brightness and the flatness of the nickel coating and adjusting the stress of the coating.

Furthermore, each liter of the main light agent comprises 35-60g of phenylsulfonyl imide compounds, 5-15g of aryl sulfonate, 50-150g of alkenyl alkyl sulfonate, 78-89g of ether compounds, 0-2g of alcohol compounds, 40-60g of alkynyl sulfonate, 4-8g of alkyne compounds, 1-2g of aldehyde compounds, 10-15.1g of surfactant, 250g of pyridinium alkyl sulfonate, 2-4g of phosphonium alkyl ether and 2-3g of sulfur nitrogen heterocyclic compounds. The main polishing agent is used for optimizing the component concentration for improving the brightness of the nickel coating.

Each liter of softening agent comprises 90-110g of benzene sulfonyl imide compounds, 3-6g of aryl sulfonate, 150g of alkenyl alkyl sulfonate, 5-7g of ether compounds, 4-8g of alkynyl sulfonate, 0.3-0.6g of alkyne compounds, 1-3g of aldehyde compounds, 30-50g of pyridinium alkyl sulfonate, 0.05-0.3g of sulfur nitrogen heterocyclic compounds and 0.02-0.15g of polyethylene polyamine compounds. The softening agent is used for improving the brightness and the flatness of the nickel coating and adjusting the stress of the coating to optimize the component concentration.

Furthermore, each liter of the main light agent comprises 20-50g of saccharin, 0-20g of dibenzenesulfonylimide, 5-15g of sodium benzene sulfinate, 60-100g of sodium allylsulfonate, 5-10g of butynediol diethoxy ether, 30-60g of propiolic alcohol ethoxy ether, 20-40g of propiolic alcohol propoxy ether, 0-2g of propiolic alcohol, 30-60g of sodium propiolic sulfonate, 4-8g of diethylaminopropyne, 1-2g of formaldehyde, 10-15g of sodium isethionate, 0-0.1g of sodium dodecyl sulfate, 0-20g of pyridinium propane sulfonate, 250g of pyridinium hydroxy propane sulfonate, 2-4g of butylcellosolve salt and 2-3g of s-carboxyethylisothiouronium sulfonate. The main light agent is used for enabling the nickel coating to achieve better brightness.

Furthermore, each liter of softener comprises 40-50g of saccharin, 40-60g of dibenzenesulfonyl imide, 3-6g of sodium benzene sulfinate, 180g of sodium allyl sulfonate, 2-3g of butynediol diethoxy ether, 1-2g of propiolic alcohol ethoxy ether, 1-2g of propiolic alcohol propoxy ether, 4-8g of sodium propiolate, 0.3-0.6g of diethylaminopropyne, 1-3g of formaldehyde, 0-10g of pyridinium propanesulfonate, 0-50g of pyridinium carboxypropanesulfonate, 0.05-0.3g of s-carboxyethylisothiouronium salt and 0.02-0.15g of diethylenetriamine. The softening agent enables the nickel plating layer to be bright and have better flatness, and further adjusts the stress of the plating layer.

Further, the coordination conductive salt comprises one or more of citrate, gluconate and magnesium salt, and is used for improving the stability and the conductive capability of the plating solution.

Further, the coordination conductive salt comprises one or more of sodium citrate, potassium citrate, sodium gluconate, potassium gluconate and magnesium sulfate. The coordination conductive salt can refine the crystallization of the nickel coating, and improve the uniform plating capacity of the plating solution and the capacity of resisting metal ion impurity pollution.

Meanwhile, the invention also provides a nickel plating solution which is prepared by a nickel plating solution additive and a neutral solution containing nickel salt; the nickel plating solution additive is the nickel plating solution additive; the nickel plating solution comprises 0.1-0.2ml/L of main light agent, 8-10ml/L of softening agent and 180g/L of coordination conductive salt 130-; the nickel salt includes nickel sulfate heptahydrate and nickel chloride hexahydrate.

Compared with the prior art, the nickel plating solution of the invention is added with the nickel plating solution additive, so that a bright nickel plating layer with strong leveling property can be obtained.

Meanwhile, the invention also provides an electroplating process.

An electroplating process comprising the steps of: pre-treating a part to be plated; washing the parts with water, and then activating with weak acid; barrel plating nickel plating is carried out under the neutral condition; carrying out post-treatment; wherein the nickel plating solution used for barrel plating nickel plating is the nickel plating solution of the invention.

Compared with the prior art, the electroplating process provided by the invention adopts the nickel plating solution containing the nickel plating solution additive, so that a bright nickel plated product with strong leveling property can be obtained.

For a better understanding and practice, the present invention is described in detail below with reference to the following examples.

Detailed Description

The invention obtains the nickel plating solution additive applied to barrel plating nickel plating under the neutral condition and the electroplating process by researching the components and the proportion of the nickel plating solution additive, and obtains the nickel plating product with bright nickel plating layer and high leveling property. The following examples are intended to illustrate the details.