JP2001107289A - Electrocalvanizing bath and plating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkaline electrogalvanizing bath giving a high plating deposition rate and excellent leveling properties and to provide a plating method. SOLUTION: This plating bath contains zinc of 1 to 65 g/L, potassium of 20 to 300 g/L, >=2C aliphatic amine and/or polyalkylene polyamine of 0.01 to 35 g/L.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a galvanizing bath widely used in the automobile industry and the home appliance industry.

[0002]

2. Description of the Related Art In general, zinc plating is most widely and generally used as a method for preventing rust on iron-based materials and parts. There are various zinc plating methods, but relatively affordable parts and screws used in the automobile and home appliance industries are three types of electroplating: weak acid bath, cyan bath, and cyanic alkali zincate bath. Most are plated by the bath. The characteristics of these bath types include the following. Alkaline zincate bath and cyan bath have lower current efficiency at practical current density than weak acid bath (weak acid bath has 8 current efficiency).
(Although it is 5% or more, the alkaline bath is about 50-70%.) Compared with the weakly acidic bath, the alkali zincate bath and the cyan bath are inferior in gloss and leveling property. Alkaline zincate bath and cyan bath have better uniform electrodeposition than weak acid bath. Alkaline zincate baths are easier to treat wastewater than other baths. Alkaline zincate bath and cyan bath have longer equipment life than weak acid bath. An acidic bath has less detergency than an alkaline bath (particularly a cyan bath), so it is necessary to completely perform pretreatment. The cyanide bath uses highly toxic cyanide. And the like.

The alkaline zincate bath is a plating bath having a simple structure composed of zinc and sodium hydroxide, and its composition is, for example, that of a technician certified by the Ministry of Labor, which is compiled by the Employment Promotion Agency of Japan. Textbook (second-level technician training process electroplating course <textbook>) contains zinc (zinc oxide) 10 (13) g / L, sodium hydroxide 120 g / L, and a plating technology guidebook issued by Tokyo Plating Materials Cooperative. (Edited by the Tokyo Plating Materials Cooperative Technical Committee) states that zinc oxide is 8 to 13 g / L and caustic soda (sodium hydroxide) is 90 to 150 g / L.
An appropriate amount of brightener (additive) is added to this and used. Zincate plating was developed as a substitute for cyanide bath plating as pollution problems increased, but in the early stages it was not possible to overcome technical problems, and complexing of zinc in fine cyanide baths and amines containing trace amounts of cyanide was not possible. There were times when baths containing chemicals were considered, but of course these were ad hoc and could not solve the original problem of environmental countermeasures. Does not contain harmful substances such as chelating agents,
It is not a zincate plating bath that satisfies the development of a low pollution plating bath). A plating bath using potassium hydroxide, which was announced overseas at the same time, is not an original zincate for the same reason. Plating baths using potassium hydroxide were also studied in Japan, but potassium hydroxide is not only more expensive than sodium hydroxide, but it does not provide particularly good results compared to sodium hydroxide. There was no reason to use potassium hydroxide, for example, the gloss was rather poor. In addition, the bath using potassium hydroxide has a narrower practically usable current density region than the bath using sodium hydroxide, and particularly in the high current density portion, the appearance defect called burn (koge) is likely to occur. Therefore, the bath using potassium hydroxide was inferior to the bath using sodium hydroxide.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a better plating bath by making use of the characteristics of each plating bath in the prior art. Specifically, in addition to obtaining a good uniform electrodeposition property that is not easily affected by the current density, which is a characteristic of zincate baths, and obtaining excellent luster, while maintaining easy drainage, a weak acid bath can be used. It is an object of the present invention to provide a plating bath having a high metal deposition rate and excellent leveling properties.

[0005]

As a result of intensive studies made by the present inventors, it has been found that the above-mentioned problems in the prior art can be solved by combining a specific amount of zinc and potassium with a specific amine polymer. Thus, one of the subjects of the present invention is that 1-65 g / L of zinc, 20-25
0 g / L potassium and 0.01 to 35 g / L carbon number 2
An alkaline electrogalvanizing bath characterized by containing the above aliphatic amine and / or polyalkylene polyamine.

Further, another object of the present invention is to provide a method using an electrogalvanizing bath according to the present invention, wherein plating is carried out prior to plating with an oxygen acid of phosphorus, an oxygen acid compound of phosphorus, a silicic acid, a silicic acid compound, borax, a chelating agent, Surfactants, inhibitors, metal ions, metal compound ions, metal oxoacid ions, organic acids, hydrogen peroxide, hydrochloric acid, sulfuric acid, persulfuric acid, hydrofluoric acid, nitric acid, amines, ammonia, caustic alkalis, alcohols, ethers One or more times, a plating solution is brought into contact with a treatment solution containing one or more kinds of treatment liquids, and after plating using an electrogalvanizing method and an electrogalvanizing bath according to the present invention, a plating film formed. Monovalent to hexavalent metal ion or metal compound ion, metal oxoacid ion, metal complex, for example, titanium, aluminum, iron, cobalt, molybdenum, calcium, magnesium Beam, nickel, copper, silver, barium, strontium, tungsten, vanadium,
Ions such as tin, zirconium, cesium, tantalum, niobium, zinc, chromium, compound ions, oxoacid ions, and chelating ligands such as dicarboxylic acids, tricarboxylic acids, hydroxyl carboxylic acids, especially succinic acid, glutaric acid, adipine Acid, oxalic acid, maleic acid, phthalic acid, terephthalic acid, malonic acid, tartaric acid, citric acid, malic acid,
Ascorbic acid, other chelating ligands such as acetylacetone, urea, urea derivatives, complexing ligands whose complexing functional groups contain nitrogen, phosphorus, or sulfur, phosphinates, phosphinate derivatives, inorganic anions H2O
Mixed complexes and anions, such as halide ions, sulfur-containing ions, phosphorus-containing ions, nitrate ions,
Carboxylate ions, silicon-containing ions, hydrogen peroxide ions, especially chloride ions, sulfate ions, oxyacid ions of phosphorus, oligophosphate ions, cyclic polyphosphate ions, silicate ions and organic acids, especially monocarboxylic acids , Amino acids, uric acid, uric acid compounds, polymers, resins, corrosion inhibitors, silicic acid, especially colloidal or dispersed silicic acid, diols, triols, polyols, amines, other nitrogen-containing compounds, pigments, pigments, desiccants, dispersants A rust preventive film is formed by treating with a treating solution containing one or more of the group consisting of agents, and if necessary, further contacting with an organic or inorganic treating solution to form a stronger rust preventing film. Consisting of forming
This is an electrogalvanizing method.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the alkaline electrogalvanizing bath of the present invention, the desired effects are expected, that is, good throwing power, which is hardly affected by current density, and excellent peeling resistance.
In order to obtain a high metal deposition rate and excellent leveling properties, the combination of zinc and potassium contents and a specific amine is important. Thus, the plating bath according to the present invention comprises:
1 to 65 g / L, preferably 8 to 50 g / L zinc and 2 g
0-300 g / L, preferably 45-200 g / L potassium and 0.01-35 g / L, preferably 0.1-
It contains 25 g / L of an aliphatic amine having 2 or more carbon atoms and / or a polyalkylene polyamine.

If the zinc concentration is less than the above range, the plating deposition rate is abnormally slow, and it takes a long time to obtain an industrially required film thickness, which is commercially disadvantageous. Further, when the concentration is higher than the above range, a defect called burnt (burn) tends to occur in the high current density portion, and at the same time, the economic loss due to pumping out of the liquid and the like increases.

If the potassium concentration is less than the above numerical range, the conductivity and current efficiency of the plating solution are reduced, and uniform plating is difficult to be generated. If the potassium concentration is high, discoloration (deterioration) of the surface of the treated material is liable to occur. At the same time, the economic loss due to the pumping of the liquid and the like also increases.

If the aliphatic amine having 2 or more carbon atoms and / or the polyalkylene polyamine is less than the above range, the effect of the present invention is difficult to obtain, and at the same time, the ability to suppress the deposition of plating metal is reduced. If the amount is too large, the suppressing power becomes excessive, so that the metal deposition rate is reduced, and the stress of the deposited film is increased.

As the polyalkylene polyamine used in the plating bath of the present invention, a polyalkylene polyamine having an aliphatic amine as a monomer as described below can be used.
Particularly preferred examples include a reaction product with a glycidyl compound, particularly a reaction product of an aliphatic polyamine having 5 to 15 carbon atoms with a glycidyl compound, a reaction product with an ether compound, particularly an aliphatic polyamine having 8 to 25 carbon atoms and a carbon number. Reactant of 4 or more ethers, polymer having an ether moiety and a plurality of tertiary or more amines in the structural formula and having 10 to 20 carbon atoms of a monomer, reactant with a carbonyl compound, particularly a plurality of quaternary A polymer having an amine, a secondary amine, a carbonyl group and a monomer having 7 to 26 carbon atoms, a reactant of an organic compound having a hydroxyl group and / or a methyl group, particularly a polymer of an aliphatic amine having 4 to 10 carbon atoms A polymer partially having a hydroxyl group and / or a methyl group, and having an average molecular weight of 100 to 4000
0 is selected from any one or more of the group consisting of polyethyleneimine.

As the aliphatic amine, triethanolamine, ethylenediamine, pentaethylenehexamine,
Diaminopropane, diethylenetriamine, ethylaminoethanol, aminopropylethylenediamine, bisaminopropylpiperazine, hexamethylenetetramine, isopropanolamine, aminoalcohol, imidazole, picoline, piperazine, methylpiperazine,
Morpholine, hydroxyethylaminopropylamine,
Tetramethylpropylenediamine, dimethylaminopropylamine, hexamethylenetetramine, etc., or their reactants or nicotinic acid, uric acid, urea, thiourea, and their methylated or ethylated products Reactants and the like.

The glycidyl compounds include epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, glycidol,
Examples include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycerol diglycidyl ether, ethylene glycol diglycidyl ether, secondary butylphenol diglycidyl ether, and glycidyl methacrylate.

The plating bath of the present invention further comprises dichlorobenzaldehyde, ethylhydroxylaldehyde, octylaldehyde, o-chlorobenzaldehyde, p-chlorobenzaldehyde, p-hydroxybenzaldehyde, and acetaldehyde in order to improve the gloss and the luster. And aldehydes such as anisaldehyde, ethyl vanillin, cinnamaldehyde, salicylaldehyde, vanillin, veratraldehyde, heliotropin and benzaldehyde.

In addition to the same effect, the plating bath of the present invention further includes a structural formula (1) in order to improve uniform electrodeposition property and appearance.

Embedded image Wherein R 1 and R 2 are hydrogen or alkyl having 10 or less carbon atoms, X is a residue of an organic or inorganic anion, preferably halogen, and n is 1 or more. Or structural formula (2)

Embedded image (Wherein, R1 and R2 are hydrogen, methyl, ethyl, butyl or isobutyl, R3 is CH _2, C ₂ H ₄ or C ₃ H ₆
X is a residue of an organic or inorganic anion, preferably halogen, and n is 1 or more), or a structural formula (3)

Embedded image (Where R1, R2, R3 and R4 are each hydrogen or alkyl having 5 or less carbon atoms, Y is S or O,
X is a residue of an organic or inorganic anion, preferably halogen, and n is 1 or more), or a structural formula (4)

Embedded image (Where R1, R2, R3 and R4 are each hydrogen or alkyl having 5 or less carbon atoms, Y is S or O,
X is a residue of an organic or inorganic anion, preferably a halogen, and n is 1 or more), or benzylpyridinium carboxylate, polyamide, thioacetamide, thioacetamide derivative, thiourea, thiourea Urea derivatives, urea, urea derivatives, amino acids,
It can contain one or more members of the group consisting of uric acid, uric acid derivatives, polyethylene imine, polyamine sulfone, polyallylamine, aliphatic amines and aliphatic amine polymers.

These suitable amounts are generally 0.0005 to 2
0 g / L, often 0.005-5 g / L
L is often an appropriate amount.

Since the plating bath according to the present invention has a higher plating deposition rate than the conventional zincate bath, the zinc supply method same as the conventional method may not catch up with the consumption of zinc. If the zinc anode can be sufficiently arranged and there is no problem in supply, that method may be used, but if it is insufficient, other than the method of supplying zinc to the conventional anode or the method of separately immersing zinc in the plating tank, a separate tank It is possible to dissolve the insufficient zinc (or zinc compound) and supply it, or to use a part or all of the anode as an insoluble anode such as iron and rely on the dissolution in a separate tank for most of the zinc supply. . Although a method of directly dissolving the zinc compound in the plating bath may be possible, it is not recommended because a defect called zara occurs easily.

Suitable conditions for carrying out the plating in the plating bath according to the present invention are that the temperature of the plating bath is 20 to 70 ° C., preferably 2 to 70 ° C.
5 to 50 ° C., and the cathode average current density is 0.1 to 40 A
/ Dm ² , preferably 1 to 20 A / dm ² . If the temperature is lower than this, the metal deposition rate decreases and the film properties deteriorate, and if the temperature is higher than this, there are problems such as abnormal consumption of polyalkylene polyamines, increased danger of working environment, and waste of heating energy. If the current density is lower than this, the metal deposition rate is low, and if the current density is higher, the current efficiency involved in the deposition is poor and electric energy is wasted.

Before plating in the plating bath according to the present invention, oxygen plating of phosphorus, oxyacid compound of phosphoric acid, carbonic acid, silicic acid, silicate compound, in order to improve adhesion and appearance of the obtained plating film. Borax, chelating agent, surfactant, inhibitor, metal ion, metal compound ion, metal oxo acid ion, organic acid, hydrogen peroxide, hydrochloric acid, sulfuric acid, persulfuric acid, hydrofluoric acid, nitric acid, amine, ammonia, alkaline ,
It is effective to bring the object to be plated into contact with a treatment solution containing one or more of alcohol, ether, emulsifier, wetting agent, dispersant, and soap. For example, sodium hydroxide, potassium hydroxide, sodium triphosphate, sodium phosphate, sodium metasilicate, sodium orthosilicate, sodium carbonate, rosin acid soap, oleic acid soap, anionic surfactant, cationic surfactant Agents, nonionic surfactants, amphoteric surfactants, EDTA, sodium gluconate tartaric acid, potassium permanganate, sulfamic acid, aliphatic amines, dicarboxylic acids, tricarboxylic acids, diols, and triols are also effective. As these contact methods, in addition to mere immersion in a processing solution containing these, an increase in the effect by electrolysis or ultrasonic waves in the processing solution, or contact by spraying is also possible.

Since the resulting galvanized film is immediately corroded as it is, after plating, a metal ion or metal compound ion of 1 to 6 valences, an oxoacid ion of a metal, a metal complex such as titanium, aluminum, iron, cobalt , Molybdenum, calcium, magnesium, nickel, copper,
Silver, barium, strontium, tungsten, vanadium, tin, zirconium, cesium, tantalum, niobium, zinc, chromium and other ions, compound ions, oxoacid ions, metal complexes, and chelating ligands such as dicarboxylic acid, tricarboxylic acid, Hydroxyl-containing carboxylic acids, especially succinic acid, glutaric acid, adipic acid, oxalic acid, maleic acid, phthalic acid, terephthalic acid, malonic acid, tartaric acid,
Citric acid, malic acid, ascorbic acid, and other chelating ligands such as acetylacetone, urea, urea derivatives, complex ligands in which the complexing functional group contains nitrogen, phosphorus, or sulfur, phosphinates, phosphinates Derivatives, mixed complexes and anions having an inorganic anion and H ₂ O, such as halide ions, sulfur-containing ions, phosphorus-containing ions, nitrate ions, carboxylate ions, silicon-containing ions, hydrogen peroxide ions, especially chloride ions , Sulfate ion, phosphorus oxyacid ion, oligophosphate ion, cyclic polyphosphate ion, silicate ion and organic acid, especially monocarboxylic acid, amino acid, uric acid, uric acid compound, polymer, resin, corrosion inhibitor, Silicic acid, especially colloidal or dispersed silicic acid, diols, triols, polyols, amines and other nitrogen-containing Compounds, dyes, pigments, drying agents, treated to thereby form a protective coating in the processing solution containing one or two or more of the group consisting of dispersing agents.

Of these combinations, 0.01 to 70
g / L (as ion) of titanium, aluminum, iron,
One or more of the group consisting of cobalt, molybdenum, calcium, magnesium, nickel, silicon, copper, silver, barium, strontium, tungsten, vanadium, tin, zirconium, cesium, tantalum, niobium, zinc, chromium and 0.01 Hydrochloric acid, sulfuric acid, nitric acid, hydrogen peroxide, oxygen acid of phosphorus,
Protective coatings formed by treatment solutions containing one or more of the group consisting of carboxylic acids, amino acids, uric acid, uric acid compounds, urea, urea compounds, and other nitrogen-containing compounds show relatively good corrosion resistance, especially 0.5 to 20 g / L of titanium, aluminum, iron, cobalt, calcium, magnesium, nickel, silicon, tin, zinc, chromium
A treatment solution combining 0.5 to 50 g / L of hydrochloric acid, sulfuric acid, nitric acid, phosphorus oxyacid, carboxylic acid, one or more of amino acids and 0.1 to 50 g / L of titanium, aluminum, cobalt, 1 to 250 g / L with at least one of silicon, barium, strontium, zirconium, zinc and chromium
A combination of at least one of the group consisting of nitric acid, hydrochloric acid, sulfuric acid, acetic acid, formic acid, glycolic acid, hydrogen peroxide, dicarboxylic acid, tricarboxylic acid, amino acid, uric acid, uric acid compound, urea, urea compound and other nitrogen-containing compounds Treated solutions often exhibit good corrosion resistance. There is no particular limitation on the source of these substances, and titanium sulfate, titanium chloride, aluminum sulfate, iron sulfate, Mohr salt, cobalt nitrate, cobalt sulfate, magnesium nitrate, nickel sulfate, chromium chloride, chromium sulfate, chromium acetate, etc. are used. It is possible to satisfy two components at the same time. Malonic acid, malic acid,
As organic acids such as gluconic acid, glutamic acid, ascorbic acid, inosinic acid and maleic acid, salts such as sodium tartrate, Rochelle salt, sodium citrate, sodium succinate, sodium lactate and sodium hydrogen phosphate can be used. Of these, a treatment solution that does not use hexavalent chromium is more desirable from the viewpoint of pollution and the effect on the human body.

In the case where the corrosion resistance is insufficient with only these rust-preventive films, it is possible to further increase the corrosion resistance or control the friction coefficient by contacting with an inorganic or organic treatment solution. In the case of an inorganic treatment liquid, a treatment liquid mainly composed of a silicon compound is relatively effective, and in the case of an organic treatment liquid, an acrylic or wax treatment liquid or a treatment liquid in which a silicon compound is blended with an organic treatment is effective. It is.

Conventionally, when the treatment with these inorganic or organic treatment liquids is performed, after the above-mentioned protective film is formed after plating, the film and the treated material are once dried, and then the inorganic or organic treatment is performed. In general, treatment with a liquid is performed, but in the present invention, treatment with these inorganic or organic treatment liquids is possible immediately (without drying) immediately after the formation of the protective film after plating. .

In addition, there is no problem in that the components of the above-mentioned treatment solution for forming a protective film after plating are contained in the inorganic or organic treatment solution and the rust preventive film, and the corrosion resistance is increased by the inclusion. There is.

[0025]

The present invention will be described below with reference to examples. The test piece used was a 50 × 100 × 2 mm iron plate or a normal Hull cell plate. The film thickness was measured with a fluorescent X-ray micropart thickness meter (SFT-8000 manufactured by Seiko Denshi Co., Ltd.).

Example 1 Zinc concentration 7.2 g / L, potassium hydroxide 120 g / L,
1 g / L of a reactant of ethylenediamine and urea and a reactant of epihalohydrin, a compound of structural formula (3) (R1, R2,
R3 and R4 are methyl, Y is O, X is chlorine, n is about 15
Hull cell plating was performed in a 0.2 g / L bath (0 to 200, average molecular weight: about 28,000). For comparison, zinc concentration 7.
Hull cell plating was performed in a bath of 3 g / L, sodium hydroxide 119 g / L, a conventional zincate plating bath brightener (3J065, manufactured by Nippon Surface Chemical Co., Ltd.) A agent 20 mL / L, and B agent 1 mL / L, and each was subjected to chromic acid plating. After treatment with a treatment solution of 2 g / L, sodium sulfate 3 g / L, phosphoric acid 0.5 g / L, pH 1.7, the plating film thickness was measured. Measurement part current density 10 2.5 0.5 0.1 (A / dm ² ) Example 1 (μm) 6.7 4.9 2.7 1.7 Comparative example 1 (μm) 4.0 2.6 1.9 1.3

Example 2 A zinc concentration of 7 g / L, potassium hydroxide of 118 g / L, a reaction product of iminodiethanol trimethylenediamine and allyl glucidyl ether of 1.5 g / L, a compound of the structural formula (2) (R1 and R2 Is methyl, R3 is CH2, X is chlorine, n is 150 to 500, and the average molecular weight is about 50,000)
0.2 g / L, thiourea 0.005 g / L, anisaldehyde 0.02 g / L, ethyl vanillin 0.02 g / L
Hull cell plating was performed in the bath. For comparison, zinc concentration 7
g / L, sodium hydroxide 121 g / L, conventional zincate plating bath brightener (3J065, manufactured by Nippon Surface Chemical Co., Ltd.) A agent 20 mL / L, B agent 1 mL / L, Hull cell plating was performed, and titanium sulfate was used. After treatment with a treatment solution of 2 g / L, aluminum sulfate 7 g / L, hydrogen peroxide 3 g / L, sodium silicate 18 g / L, pH 2.3, the plating film thickness was measured. Measurement part current density 10 2.5 0.5 0.1 (A / dm ² ) Example 2 (μm) 6.4 4.6 2.5 1.6 Comparative example 2 (μm) 4.0 2.4 1.7 1.1

Example 3 A zinc concentration of 9 g / L, potassium hydroxide of 119 g / L, a polymer of structural formula (5) 2 g / L, a compound of structural formula (1) 0.2 g / L, and an acetamide compound 0.5 g / L L, veratraldehyde 0.01 g / L, vanillin 0.02 g
/ L bath was used to perform Hull cell plating. As a comparison, Hull cell plating was performed in a bath having zinc concentration of 8.9 g / L, sodium hydroxide 117 g / L, conventional zincate plating bath brightener (3J065 manufactured by Nippon Surface Chemical Co., Ltd.) A agent 20 mL / L and B agent 1 mL / L. And 8 g of chromium chloride /
L, nitric acid 0.5 g / L, titanium sulfate 1 g / L, cobalt sulfate 1 g / L, phosphoric acid 25 g / L, and a plating solution were measured for 45 seconds after treatment with pH 2.1 for 45 seconds. Measurement part current density 10 2.5 0.5 0.1 (A / dm ² ) Example 3 (μm) 6.7 3.9 2.8 1.9 Comparative example 3 (μm) 4.7 2.9 2.2 1.3 Structural formula (5)

Embedded image (Wherein, R1, R2, R3 and R4 are each methyl, R5 is _{(CH 2) 2 -O- (CH} 2) 2, X is the residue of an organic or inorganic ion, n represents 1 That's all)

Example 4 A zinc concentration of 11 g / L, potassium hydroxide of 139 g / L, a polymer of structural formula (6) 0.8 g / L, a compound of structural formula (4) (R1, R2, R3 and R4 are methyl, Y is O, X
Is chlorine, m is 30,000 to 50,000, n is 10,000
~ 30000, molecular weight 3,000,000 ~ 6,000,000) 0.5g /
L, benzylpyridinium carboxylate 0.03 g
/ L, veratolualdehyde 0.03 g / L, Hull cell plating was performed. For comparison, a zinc concentration of 11.5 g /
L, sodium hydroxide 137 g / L, conventional brightener for zincate plating bath (3J065 Nippon Surface Chemical Co., Ltd.)
Hull cell plating was performed in a bath of Agent A 20 mL / L and Agent B 1 mL / L, and chromium nitrate 10 g / L, cobalt sulfate 5 g / L, succinic acid 8 g / L, and ascorbic acid 8 g, respectively.
/ L, treatment with a treatment solution of pH 2.1 for 45 seconds, and then the plating film thickness was measured. Measurement part current density 10 2.5 0.5 0.1 (A / dm ² ) Example 4 (μm) 7.2 4.9 2.7 1.7 Comparative example 4 (μm) 5.1 3.2 2.1 1.3 Structural formula (6)

Embedded image (Wherein, R1, R2, R3 and R4 are each methyl, R5 is _{(CH 2) 2 -O- (CH} 2) 2, n is 1 or more)

Example 5 Zinc concentration 10 g / L, potassium hydroxide 109 g / L, polymer 2.2 which is a reaction product of laurylpyridinium chloride, triethanolamine and monochlorohydrin
g / L, 0.8 g / L of the compound of structural formula (2) (used in Example 2), 0.3 g / L of polyethyleneimine,
1 g of reaction product of ethylenediamine and epichlorohydrin /
Hull cell plating was performed in a bath of L and 0.06 g / L of ethyl vanillin. As a comparison, Hull cell plating in a bath having a zinc concentration of 10.1 g / L, sodium hydroxide 111 g / L, a conventional zincate plating bath brightener (3J065 manufactured by Nippon Surface Chemical Co., Ltd.) A agent 20 mL / L, and B agent 1 mL / L And 5 g / L of chromium sulfate and 3 g /
L, tartaric acid 5 g / L, inosinic acid 3 g / L, glycine 3
The plating film thickness was measured after processing for 45 seconds with a processing solution of g / L and pH 2.1. Measurement part current density 10 2.5 0.5 0.1 (A / dm ² ) Example 5 (μm) 7.0 4.5 2.3 1.5 Comparative example 5 (μm) 5.0 3.0 1.8 1.1

Example 6 Zinc concentration: 6 g / L, potassium hydroxide: 90 g / L, polymer: 2 g / L, which is a reaction product of diethylaminobutylamine, thiourea, and chlorine adduct of diethyl ether; compound of structural formula (3) Same as used in Example 1)
8 g / L, benzylpyridinium carboxylate 0.
7 g / L, reaction product of diethylenetriamine and epichlorohydrin 0.5 g / L, ethyl vanillin 0.05 g / L
Hull cell plating was performed in a bath of L, heliotropin 0.01 g / L. For comparison, zinc concentration 6 g / L, sodium hydroxide 92 g / L, conventional zincate plating bath brightener (3J065 manufactured by Nippon Surface Chemical Co., Ltd.) A agent 20 mL /
Hull cell plating was carried out in baths of L and B agents 1 mL / L, and chromium chloride 7 g / L, sodium nitrate 6 g / L, glycolic acid 10 g / L, citric acid 1 g / L, glycine 5 g / L, respectively.
The plating film thickness was measured after the treatment with L, pH 2.2 treatment solution for 45 seconds. Measurement part current density 10 2.5 0.5 0.1 (A / dm ² ) Example 6 (μm) 4.0 2.0 1.5 1.0 Comparative example 6 (μm) 3.0 1.5 1.0 0.7

Example 7 Zinc concentration 9 g / L, potassium hydroxide 120 g / L, reaction product of dimethylaminoethylamine, thiourea and epihalohydrin 1.2 g / L, compound of structural formula (1) (used in Example 3) An iron plate was plated in a bath of 0.4 g / L, benzyl pyridinium carboxylate 0.04 g / L ethyl vanillin 0.05 g / L, and thioacetamide 0.03 g / L. For comparison, a zinc concentration of 9.1 was used.
g / L, sodium hydroxide 121 g / L, conventional zincate plating bath brightener (3J065, manufactured by Nippon Surface Chemical Co., Ltd.) A agent 20 mL / L, and B agent 1 mL / L. 0.5 g / L, sodium sulfate 2.5 g / L, nitric acid 0.5 g / L, phosphoric acid 0.3
After treatment with a treatment solution having a pH of 1.8 and a plating solution of g / L, the plating film thickness was measured. Each plating time was 20 minutes, and the current density was 3 A / dm ² . Example 7 6.1 μm Comparative Example 7 4.4 μm

Example 8 Zinc concentration 6.5 g / L, potassium hydroxide 110 g / L,
2.2 g / L of a reaction product of aminoethylaminopropylamine, urea and chlorine adduct of diethyl ether, structural formula (2)
Of the compound (same as that used in Example 2) 0.5 g /
L, polyethyleneimine 0.5 g / L, vanillin 0.0
Plating was performed in a 2 g / L bath. For comparison, plating was carried out in a bath having a zinc concentration of 6.5 g / L, sodium hydroxide of 111 g / L, a conventional zincate plating bath brightener (3J065, manufactured by Nippon Surface Chemical Co., Ltd.) A agent 20 mL / L and B agent 1 mL / L. 4 g / L of chromium sulfate, 2 g / L of titanium sulfate, 5 g / L of aluminum sulfate, 7 g of sodium nitrate
/ L, 18 g / L of sodium silicate, pH 2.3, and then the plating film thickness was measured. Each plating time was 30 minutes, and the current density was 2 A / dm ² . Example 8 9.5 μm Comparative Example 8 6.8 μm

Example 9 Zinc concentration 5.5 g / L, potassium hydroxide 95 g / L, reaction product of dimethylaminopropylamine, urea and epihalohydrin 1.0 g / L, compound of structural formula (2) (Example 2) 0.7 g / L, vanillin 0.1 g / L.
The iron plate was plated in a bath of 02 g / L, veratolualdehyde 0.01 g / L, and thioacetamide 0.15 g / L. For comparison, a zinc concentration of 5.5 g / L, sodium hydroxide of 94 g / L, and a conventional brightener for zincate plating bath (3
J065 Nippon Surface Chemical Co., Ltd.) Agent A 20 mL / L,
Plating is also carried out in a bath of 1 mL / L of the B agent, using a processing solution of chromic acid 2.5 g / L, sodium sulfate 2.5 g / L, nitric acid 0.5 g / L, phosphoric acid 0.3 g / L, pH 1.8, respectively. After the treatment, the plating film thickness was measured. The bath temperature was 25 ° C., the plating time was 30 minutes, and the current density was 2.5 A / d.
m ² . Example 9 7.2 μm Comparative Example 9 5.5 μm

Example 10 Zinc concentration 9.5 g / L, potassium hydroxide 122 g / L,
2.7 g / L of a reaction product of dimethylaminopropylamine, urea and a chlorine adduct of diethyl ether, 0.4 g / L of the compound of the structural formula (3) (same as that used in Example 1),
Plating was performed in a bath of polyethylene imine 0.3 g / L, polyallylamine 0.1 g / L, ethyl vanillin 0.01 g / L, and anisaldehyde 0.01 g / L. For comparison, a zinc concentration of 9.5 g / L and sodium hydroxide 123 were used.
g / L, conventional brightener for zincate plating bath (3J06
5 Nippon Surface Chemical Co., Ltd.) Agent A 20 mL / L, Agent B 1
Plating in a bath of mL / L, each 3g of chromium sulfate
/ L, 2 g / L of titanium sulfate, 5 g / L of aluminum sulfate, 2 g / L of cobalt nitrate, 6.5 g / L of sodium nitrate, 18 g / L of sodium silicate, pH 2.3,
The plating film thickness was measured. The bath temperature was 30 ° C., the plating time was 30 minutes, and the current density was 2 A / dm ² . Example 10 9.7 μm Comparative Example 10 6.9 μm

Example 11 Zinc concentration 25 g / L, potassium hydroxide 180 g / L, polymer of structural formula (6) (same as that used in Example 4) 1.5 g / L, compound of structural formula (4) Bath temperature 35 ° C. in a bath of 0.8 g / L, benzylpyridinium carboxylate 0.05 g / L, anisaldehyde 0.03 g / L (same as used in Example 4), cathode current density 15
Plating was performed at A / dm ² . Structural formula (6) for comparison
Instead of the polymer of formula (4), benzylpyridinium carboxylate and anisaldehyde,
A conventional zincate plating bath brightener (8500, manufactured by Nippon Surface Chemical Co., Ltd.) was added at 6 mL / L to perform plating.
Chromium nitrate 10g / L, cobalt sulfate 5g /
L, 8 g / L of oxalic acid, 8 g / L of ascorbic acid, 1 g / L of sodium nitrate, and a plating film thickness was measured after treatment for 45 seconds with a pH of 2.2. Example 11 24 μm Comparative Example 11 9 μm (poor appearance: kogation (burn) occurs around the test piece)

Example 12 Zinc concentration 45 g / L, potassium hydroxide 230 g / L, reaction product of dimethylaminoethylamine, thiourea and epihalohydrin 1.2 g / L, compound 0.7 of the structural formula (7)
g / L, benzylpyridinium carboxylate 0.0
The iron plate was plated in a bath of 4 g / L, ethyl vanillin 0.05 g / L, and thioacetamide 0.03 g / L. For comparison, a brightener for zincate plating bath (8500) was used instead of the reaction product of dimethylaminoethylamine, thiourea and epihalohydrin, the compound of structural formula (7), benzylpyridinium carboxylate and ethylvanillin.
Plating was performed by adding 8 mL / L of Nippon Surface Chemical Co., Ltd., and chromate 2.5 g / L, sodium sulfate 2.5 g / L, nitric acid 0.5 g / L, phosphoric acid 0.3 g / L,
After the treatment with the treatment solution of pH 1.8, the plating film thickness was measured.
The bath temperature was 45 ° C., the plating time was 10 minutes, and the current density was 20 A / dm ² . The results are shown. Example 12 28 μm Comparative Example 12 12 μm (poor appearance: kogation (burn) occurs around the test piece) Structural formula (7)

Embedded image (Wherein, R1, R2, R3 and R4 are each methyl, R5 is _{(CH 2) 2 -O- (CH} 2) 2, X is the residue of an inorganic or organic anion, n represents 1 or more)

Example 13 Polymer having a zinc concentration of 50 g / L, potassium hydroxide of 275 g / L, a reaction product of laurylpyridinium chloride, triethanolamine and monochlorohydrin 1.2
g / L, 0.8 g / L of the compound of structural formula (2) (same as used in Example 2), 0.7 g / L of the compound of structural formula (7) (same as used in Example 12) L, 0.2 g / L of polyethyleneimine, 0.6 g / L of a reaction product of ethylenediamine and epichlorohydrin, 0.1 g of ethylvanillin.
Plating was performed in a bath of 06 g / L at 50 ° C. for 10 minutes.
The current density was 20 A / dm ² . One of the two test pieces was immersed in an alkaline aqueous solution containing sodium hydroxide, a surfactant, and EDTA at 50 ° C. for 10 minutes, then immersed in 15% hydrochloric acid for 1 minute, and further containing a solution containing sodium hydroxide and sodium gluconate. And subjected to electrolysis for 3 minutes at a liquid temperature of 30 ° C. and a current density of 8 A / dm ² , followed by plating. The other was plated without doing anything. 200 ° C-
As a result of heating for 2 hours, no problems were observed in the test pieces that were brought into contact with various liquids, but the test pieces that did not do anything confirmed that the film had fallen off.

Example 14 Zinc concentration 30 g / L, potassium hydroxide 200 g / L,
Benzylpyridinium carboxylate 0.3 g / L,
0.8 g / L of the compound of structural formula (1) (same as used in Example 3), 0.8 g / L of the compound of structural formula (6) (same as used in Example 4), polyethyleneimine 0.3 g / L, 0.1 g / L of a reaction product of pentaethylenehexamine and epichlorohydrin, 0.06 g of vanillin
/ L in a bath at 40 ° C. for 15 minutes. The current density was 20 A / dm ² . One of the two test pieces is immersed in an alkaline aqueous solution containing sodium hydroxide, a surfactant, and sodium carbonate at 50 ° C. for 10 minutes, immersed in 20% sulfuric acid for 1 minute, and further contains sodium hydroxide and triethanolamine. After being immersed in the solution and subjected to electrolysis for 3 minutes at a solution temperature of 40 ° C. and a current density of 15 A / dm ² , plating was performed. The other was plated without doing anything. 200 ° C plating test piece
As a result of heating for -2 hours, no problems were observed in the test pieces that were brought into contact with various liquids, but the test pieces that did not do anything confirmed that the film had fallen off.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K023 AA15 BA23 BA29 DA04 DA07 DA08 4K024 AA05 AB01 BA02 BB02 BB18 CA03 CB01 DA06 DA07 GA02

Claims (6)

[Claims] 1 to 65 g / L of zinc and 20 to 300 g / L
An alkaline electrogalvanizing bath containing g / L of potassium and 0.01 to 35 g / L of an aliphatic amine having 2 or more carbon atoms and / or a polyalkylene polyamine. 2. A reaction product of a polyalkylene polyamine with a glycidyl compound, particularly a reaction product of an aliphatic polyamine having 5 to 15 carbon atoms with a glycidyl compound, a reaction product of an ether compound, particularly an aliphatic compound having 8 to 25 carbon atoms. A reaction product of a polyamine and an ether having 4 or more carbon atoms, which has an ether portion and a plurality of tertiary or higher amines in the structural formula and has 10 carbon atoms in the monomer.
-20, a reactant with a carbonyl compound,
In particular, a polymer having a plurality of quaternary amines, secondary amines, and carbonyl groups and having 7 to 26 carbon atoms in the monomer, a hydroxyl group and / or
Or a reaction product of an organic compound having a methyl group, particularly a polymer of an aliphatic amine having 4 to 10 carbon atoms, which partially has a hydroxyl group and / or a methyl group, and has an average molecular weight of 1
The galvanizing bath according to claim 1, which is at least one member selected from the group consisting of polyethyleneimine having a molecular weight of from 00 to 40,000. 3. Further, the compound represented by the structural formula (1) (Where R1 and R2 are each hydrogen or carbon 10
Wherein X is a residue of an organic or inorganic ion, and n is 1 or more), or a structural formula (2): (Wherein, R1 and R2 are each hydrogen, methyl, ethyl, butyl or isobutyl, R3 is CH _2, C ₂ H ₄
Or C ₃ H ₆ , X is a residue of an organic or inorganic ion, and n is 1 or more), or a structural formula (3): (Where R1, R2, R3 and R4 are each hydrogen or alkyl having 5 or less carbon atoms, Y is S or O,
X is a residue of an organic or inorganic ion, and n is 1 or more), or a structural formula (4): (Where R1, R2, R3 and R4 are hydrogen or carbon atoms having 5
The following alkyl, Y is S or O, X is a residue of an organic or inorganic ion, and n is 1 or more), or benzylpyridinium carboxylate, polyamide, thioacetamide Thioacetamide derivatives, thiourea, thiourea derivatives, urea, urea derivatives, amino acids, uric acid, uric acid derivatives, polyethyleneimine, polyamine sulfone, polyallylamine, aliphatic amines and aliphatic amine polymers, and at least one of the group consisting of aldehydes The zinc plating bath according to claim 1, wherein the zinc plating bath contains: 4. Oxygen acid of phosphorus, oxygen acid compound of phosphorus, carbonic acid, silicic acid, silicate compound, borax, chelating agent, surfactant, inhibitor, metal ion, metal compound ion, metal oxo acid ion, organic acid, A treatment liquid containing one or more of hydrogen peroxide, hydrochloric acid, sulfuric acid, persulfuric acid, hydrofluoric acid, nitric acid, amine, ammonia, caustic alkali, alcohol, ether, emulsifier, wetting agent, dispersant and soap. An electrogalvanizing method, comprising: forming a plating film in the galvanizing bath according to any one of claims 1 to 3 after contacting the plated product. 5. A film formed after plating using the zinc plating bath according to claim 1 or 4.
A film formed by the method described in 1 above, a metal ion or metal compound ion of 1 to 6 valent, oxo acid ion of metal, metal complex such as titanium, aluminum, iron, cobalt, molybdenum, calcium, magnesium, nickel, copper ,
Silver, barium, strontium, tungsten, vanadium, tin, zirconium, cesium, tantalum, niobium, zinc, chromium and other ions, compound ions, oxoacid ions, metal complexes, and chelating ligands such as dicarboxylic acid, tricarboxylic acid, Hydroxyl-containing carboxylic acids, especially succinic acid, glutaric acid, adipic acid, oxalic acid, maleic acid, phthalic acid, terephthalic acid, malonic acid, tartaric acid,
Citric acid, malic acid, ascorbic acid, and other chelating ligands such as acetylacetone, urea, urea derivatives, complex ligands in which the complexing functional group contains nitrogen, phosphorus, or sulfur, phosphinates, phosphinates Derivatives, mixed complexes and anions having an inorganic anion and H ₂ O, such as halide ions, sulfur-containing ions, phosphorus-containing ions, nitrate ions, carboxylate ions, silicon-containing ions, hydrogen peroxide ions, especially chloride ions , Sulfate ion, phosphorus oxyacid ion, oligophosphate ion, cyclic polyphosphate ion, silicate ion and organic acid, especially monocarboxylic acid, amino acid, uric acid, uric acid compound, polymer, resin, corrosion inhibitor, Silicic acid, especially colloidal or dispersed silicic acid, diols, triols, polyols, amines and other nitrogen-containing Compound, a pigment, a pigment, a desiccant, a treatment liquid containing one or more of the group consisting of a dispersant to form a protective film, and if necessary, further to an organic or inorganic treatment liquid. An electrogalvanizing method characterized by forming a stronger rust preventive film upon contact. 6. The temperature of a plating bath is 20 to 70 ° C.,
The plating method using a zinc plating bath according to claim 4, wherein the cathode has an average current density of 0.1 to 40 A / dm ² .