JP5747359B2 - Zincate-type zinc-based plating bath, additive for zincate-type zinc-based plating bath, and method for producing zinc-based plated member - Google Patents

Description

  The present invention relates to a so-called zincate type zinc plating bath which is alkaline and does not contain cyanide.

  In this specification, the zinc-based plating is a general term for zinc plating composed of zinc and inevitable impurities and zinc alloy plating composed of zinc and alloy components and inevitable impurities. Here, in zinc alloy plating, the content (mass%) of zinc in plating may be higher than any of the contents (mass%) of other alloy elements, or may be higher than the content (mass%) of zinc. An alloy element having a high content may be included.

  Films made of zinc-based plating (also referred to as “zinc-based plated film” in this specification) apply to parts around us, including machine parts made of steel such as automotive steel plates and bolts and nuts. It is widely used for the purpose of improving corrosion resistance. Zinc alloy plating films such as zinc-nickel alloy, zinc-iron alloy, and tin-zinc alloy are also widely used when improvement in heat resistance and salt water resistance is required in addition to corrosion resistance.

  The zinc-based plating film is formed by electroplating in which a member to be plated is immersed in a plating bath for forming the zinc-based plating film (also referred to as “zinc-based plating bath” in this specification). The This zinc-based plating bath is roughly classified into an alkaline bath and an acidic bath. The alkaline bath includes a cyanide bath and a zincate-type zinc-based plating bath, and the acidic bath includes a zinc chloride bath and a zinc sulfate bath. An appropriate bath is selected from these zinc-based plating baths in consideration of various conditions such as the required hardness and gloss of the zinc-based plating film, the shape and size of the member to be plated, and the working environment.

  Among these zinc-based plating baths, zincate-type zinc-based plating baths do not use cyanide, which has a large burden on wastewater treatment, and the bath composition is relatively simple and easy to manage. For zinc presses, bolts, nuts, etc. Due to the advantages that can be applied, it is preferred and industrially practiced. Many improved baths have been developed from the viewpoint of improving the properties of the plating film and improving the stability of the bath.

  For example, in Patent Document 1, a water-soluble reactivity between nicotinic acid and a specific compound is provided for the purpose of providing a stable alkaline zinc and zinc alloy plating bath in which a smooth and bright plating film of zinc metal is obtained. Techniques have been disclosed for using the product as a brightener for alkaline zinc and zinc alloy plating baths.

JP2011-84821A

  However, the brightener disclosed in Patent Document 1 does not necessarily have high stability in the zincate-type zinc-based plating bath, and the insoluble material formed in the plating bath as the usage time of the plating bath increases. In some cases, the amount increases, which adheres to the member to be plated and causes a poor appearance of the plating film.

The present invention relates to a zincate type zinc-based plating bath in which insoluble substances are hardly formed in the plating bath even when the usage time of the plating bath is increased, and a zincate type in which insoluble substances are hardly formed in the bath when added to the plating bath. An object of the present invention is to provide an additive for a zinc-based plating bath and a method for producing a zinc-based plated member formed using the zinc-based plating bath.
In addition, a zinc-type plating member means the member provided with the to-be-plated member and the zinc-type plating film laminated | stacked on the to-be-plated surface of this to-be-plated member.

The present invention provided to solve the above problems is as follows.
(1) At least one of chain alkyl halide and alicyclic alkyl halide, and hydrogen in the alkyl halide is an amino group, a hydroxy group, an oxyalkylene ether group, an alkylcarboxyalkyl group, an arylcarboxyalkyl group, a carboxyalkyl group, Reaction of reaction product (a) of nicotinic acid amide with one or more compounds selected from the group consisting of phosphonic acid group or aryl group, and alkanesartone, and glycidyltrimethylammonium halide A zincate-type zinc-based plating bath characterized by containing a reaction product (A) obtained by heating and a bath-soluble zinc-containing substance.

(2) The plating bath according to (1), wherein the reaction product (A) is contained in an amount of 0.1 g / L to 15 g / L.

(3) The plating bath according to (1) or (2), which does not contain cyanide.

(4) The plating bath according to any one of (1) to (3) above, wherein the bath-soluble zinc-containing substance is contained in an amount of 2 g / L or more and 60 g / L in terms of zinc.

(5) From the above (1), further comprising a bath-soluble metal-containing substance, wherein the metal element contained in the bath-soluble metal-containing substance is one or more selected from the group consisting of iron, nickel, cobalt and manganese The plating bath according to any one of (4).

(6) Additive for zincate-type zinc-based plating bath containing the reaction product (A) described in (1) above.

(7) A method for producing a zinc-based plating member comprising a member to be plated and a zinc-based plating film laminated on a surface to be plated of the member to be plated, which is any one of (1) to (5) above Using the zincate zinc-based plating bath described above, plating is performed while the content of the reaction product (A) contained in the plating bath is controlled in the range of 0.1 g / L to 15 g / L. The manufacturing method of the zinc-type plating member characterized by the above-mentioned.

(8) A method for producing a zinc alloy plating member comprising a member to be plated and a zinc alloy plating film laminated on the surface to be plated of the member to be plated, the zincate type described in (5) above Using a zincate-type zinc alloy plating bath which is a zinc-based plating bath containing a bath-soluble nickel-containing substance, the eutectoid rate of nickel in the zinc alloy plating film obtained from the zincate-type zinc alloy plating bath is 12% by mass or more. The manufacturing method of the zinc alloy plating member made into 20 mass% or less.

  The zincate-type zinc-based plating bath according to the above invention can form a zinc-based plating film having an excellent appearance.

It is a graph which shows the relationship between the position from the high current density side edge part of the plating surface of the member which has a plating film concerning Examples 1 to 3 and Comparative Examples 1 to 3, and the thickness of the plating film.

The present invention will be described in detail below.
1. Zincate-type zinc-based plating bath Since the zinc-based plating bath according to one embodiment of the present invention is a zincate-type plating bath, the liquidity is alkaline. In addition, the zinc-based plating bath according to a preferred example of the present embodiment does not contain cyanide and does not generate harmful cyanide gas. Therefore, the zinc plating bath is excellent in workability and environmentally friendly.

(1) Metal component (1-1) Bath-soluble zinc-containing material The zinc-based plating bath according to the present embodiment contains a bath-soluble zinc-containing material. In this specification, the bath-soluble zinc-containing substance is a source of zinc deposited as a zinc-based plating film, and is one or more selected from the group consisting of zinc cations and bath-soluble substances containing the same. Refers to the ingredients. Since the zinc-based plating bath according to this embodiment is a zincate type bath, the plating bath is alkaline. Thus, an example of a bath-soluble zinc-containing material is a zincate ion ([Zn (OH) ₄ ] ²⁻ ).
Zinc oxide is exemplified as a source material (also referred to as “zinc source” in the present invention) for supplying the bath-soluble zinc-containing material to the plating bath.

  The zinc equivalent content of the soluble zinc-containing substance in the zinc-based plating bath according to this embodiment is not limited. When this content is excessively small, the zinc-based plating film is difficult to deposit. Therefore, the content in terms of zinc is preferably 2 g / L or more, more preferably 4 g / L or more, It is particularly preferably 8 g / L or more. When the zinc equivalent content of the soluble zinc-containing substance is excessively large, there is a concern that the appearance defect and the throwing power decrease may occur. Therefore, the zinc equivalent content is preferably 60 g / L or less, It is more preferably 40 g / L or less, and particularly preferably 20 g / L or less.

(1-2) Bath-soluble metal-containing substance The zinc-based plating bath according to an embodiment of the present invention contains a bath-soluble metal-containing substance when the plating bath is a zinc alloy plating bath. In this specification, the bath-soluble metal-containing material is a source of a metal other than zinc contained in the zinc alloy plating film, and is selected from the group consisting of a cation of a metal element and a bath-soluble material containing the metal element. It refers to one or more components. Examples of the metal element contained in the bath-soluble metal-containing material include iron, nickel, cobalt, and manganese. In a preferred example, the metal element contained in the metal-containing material is selected from the group consisting of iron, nickel, cobalt, and manganese.

The source material (also referred to as “metal source” in the present invention) for supplying the bath-soluble metal-containing material to the plating bath may be appropriately selected according to the type of metal element contained in the bath-soluble metal-containing material. For example, when the metal element contained in the bath-soluble metal-containing material is iron, that is, when the zinc alloy plating bath contains a bath-soluble iron-containing material, Fe ₂ (SO ₄ ) ₃ · 7H ₂ O, FeSO ₄ · 7H ₂ O, Fe (OH) ₃ , FeCl ₃ · 6H ₂ O, FeCl ₂ · 4H ₂ O and the like are exemplified as iron sources. When the metal element contained in the bath-soluble metal-containing material is nickel, that is, when the zinc alloy plating bath contains the bath-soluble nickel-containing material, NiSO ₄ .6H ₂ O, NiCl ₂ .6H ₂ O, Ni (OH) ₂ or the like is exemplified as the nickel source. When the metal element contained in the bath-soluble metal-containing material is manganese, that is, when the zinc alloy plating bath contains a bath-soluble manganese-containing material, MnSO ₄ , MnSO ₄ .H ₂ O, MnCl ₂ .4H ₂ O etc. are illustrated as a manganese source.

  The metal equivalent content of the soluble metal-containing substance in the zinc-based plating bath according to this embodiment is appropriately set according to the composition of the intended zinc alloy plating. When the zinc-based plating bath contains a bath-soluble iron-containing substance, the iron equivalent content of the soluble iron-containing substance is exemplified as about 5 mg / L or more and 300 mg / L or less, and is 10 mg / L or more and 150 mg / L. In some cases, it may be preferable to be about 20 mg / L or more and 70 mg / L or less. When the zinc-based plating bath contains a bath-soluble nickel-containing substance, it is exemplified that the nickel equivalent content of the soluble nickel-containing substance is about 50 mg / L or more and 10,000 mg / L or less, and is 100 mg / L or more and 4000 mg / L. In some cases, it may be preferable to be about 200 mg / L or more and 2000 mg / L or less. When the zinc-based plating bath contains a bath-soluble manganese-containing substance, it is exemplified that the manganese equivalent content of the soluble manganese-containing substance is about 2 g / L or more and 80 g / L or less, and is 5 g / L or more and 50 g / L. In some cases, it is preferable to be about 10 g / L or more and about 20 g / L or less.

(2) Additive component The plating bath according to the present embodiment contains a reaction product (A) described below as an additive component, and further contains other additive components as necessary.

(2-1) Reaction product (A)
The plating bath according to the present embodiment includes a chain alkyl halide and an alicyclic alkyl halide, and at least one of hydrogens in the alkyl halide is an amino group, a hydroxy group, an oxyalkylene ether group, an alkylcarboxyalkyl group, an arylcarboxyalkyl group. A compound substituted with a group, a carboxyalkyl group, a phosphonic acid group or an aryl group, and one or more selected from the group consisting of alkanesultone (in the present specification, these compounds are collectively referred to as “addition compounds”) The reaction product (A) obtained by reacting the reaction product (a) of nicotinic acid amide with a halide of glycidyltrimethylammonium is contained as one of the additive components.

  The specific types of the halogen contained in the reaction product (a) and the halogen contained in the halide of glycidyltrimethylammonium are not particularly limited. From the viewpoint of not reducing workability and reducing the burden of waste liquid treatment, it is preferable not to use fluorine as the halogen, and from the viewpoint of ease of handling, the halogen is preferably chlorine.

  The method for producing the reaction product (a) is not particularly limited. The addition compound and nicotinamide may be reacted under appropriate conditions. The reaction conditions will be described below by taking the case where the addition compound is ethylene halohydrin as a specific example. That is, nicotinic acid amide and ethylene halohydrin are charged into an aqueous solvent at a molar ratio of these (nicotinic acid amide / ethylene halohydrin) of about 0.5 to 2, and the liquid obtained is about 100 ° C. Stir at temperature for about 2-6 hours. Then, the liquid containing the reaction product (a) can be obtained by cooling to about 20 to 40 ° C. while maintaining stirring of the liquid. The reaction product (a) may be taken out of the liquid containing the reaction product (a) by an operation such as crystallization. However, from the viewpoint of improving productivity, the liquid containing the reaction product (a). May be used as a starting material for obtaining the next reaction product (A).

The reaction product (a) obtained by the above production method is considered to contain a pyridinium amide compound obtained by reacting nicotinamide with an addition compound using nitrogen in the pyridine ring as a reaction site. Specific examples of such a pyridinium amide compound include 1-propanol-pyridinium-3-carboxamide (hereinafter also referred to as “PPCA”) as a pyridinium amide compound when the addition compound is composed of ethylene halohydrin.
The relationship between the specific example of the addition compound and the group bonded to nitrogen of the pyridine ring in the pyridinium amide compound contained in the above reaction product (a) is as follows.
Addition compound: ethylene chlorohydrin → group obtained: hydroxyethyl group Addition compound: methyl iodide → group obtained: methyl group Addition compound: ethyl iodide → group obtained: ethyl group Addition compound: propyl bromide → obtained Group: Propyl group Addition compound: Bromomethylcyclohexane → Resulting group: Cyclohexylmethyl group Addition compound: Methyl chloroacetate → Resulting group: Methylcarboxymethyl group Addition compound: Chloroacetic acid → Resulting group: Carboxymethyl group Addition compound: Propane Sultone → Group obtained: Sulfopropyl group Addition compound: Benzyl chloride → Group obtained: Benzyl group

  The method for producing the reaction product (A) is not particularly limited. The reaction product (a) and the glycidyltrimethylammonium halide may be reacted under appropriate conditions. As an example, the case where the liquid containing the reaction product (a) is used as a starting material for obtaining the next reaction product (A) as described above is as follows. That is, the nicotinic acid amide used to obtain the liquid containing the reaction product (a) by using a halide of glycidyltrimethylammonium in the liquid containing the reaction product (a) cooled to about 20 to 40 ° C. And a glycidyltrimethylammonium halide molar ratio (nicotinamide / glycidyltrimethylammonium halide) in an amount of about 0.5 to 2. If necessary, a small amount of water as a solvent is further added, and the obtained liquid is refluxed for about 2 to 4 hours. Although the temperature at the time of this reflux is not specifically limited, As a specific example, about 50 to 80 degreeC is mentioned. By cooling the liquid after this reflux to room temperature, a liquid containing the reaction product (A) is obtained.

The reaction product (A) obtained by the above production method is a compound obtained by reacting a pyridinium amide compound considered to be contained in the reaction product (a) with a glycidyltrimethylammonium halide using the amide group as a reaction site. It is thought to contain (α). As a specific example of the compound (α) when the above addition compound is ethylene chlorohydrin, the compound (α1) (1- (2-hydroxyethyl-3- [N- (1- Trimethylammonio 2-hydroxypropyl) carbamoyl] -pyridinium ion).

  Further, the reaction product (A) obtained by the above production method may contain a compound (β) obtained by reacting with the halide of glycidyltrimethylammonium with the amide group and hydroxyl group as reaction sites. is there. A specific example of the compound (β) in the case where the above addition compound is ethylene chlorohydrin includes a compound (β1) represented by the following formula (II).

  This reaction product (A) can function as an excellent additive in both a zinc plating bath and a zinc alloy plating bath. Hereinafter, the function of the reaction product (A) will be described using the compound (α1) represented by the formula (I) considered to be contained in the reaction product (A) as a specific example.

  Even if the compound (α1) is hydrolyzed in an alkaline zinc-based plating bath or electrolyzed by electrolysis for plating deposition, a decomposition product of the compound (α1) or a polymer thereof (this specification) "Degradation products etc.") can maintain solubility. For example, even if the amide bond in the compound (α1) is hydrolyzed, the decomposition product formed in the alkaline plating bath becomes a cation compound having a quaternary amino group and a carboxylate ion having a nicotinic acid skeleton. . For this reason, as the electrolysis time increases, problems arise due to accumulation of insoluble substances (oily substances or resinous substances) based on decomposition products of additives in the plating bath. Hateful. When such an insoluble material is generated, the oily substance exists so as to float on the surface of the plating bath, and the resinous substance floats in the plating bath, both of which are on the surface of the member to be plated. Adsorption causes deterioration of the plating appearance and corrosion resistance. In addition, since the compound (α1) hardly generates insoluble substances, the concentration of addition in the plating bath can be increased, and as a result, a zinc-based plating film having an excellent appearance (such as gloss) is easily obtained under a wide range of plating conditions. Become. In addition, even if it is a case where a reaction product (A) contains a compound ((beta)), it is anticipated that said function will be acquired.

  When the galvanizing bath contains the reaction product (A) that is considered to contain the compound (α1), the reaction product (A) functions as a brightener, and the resulting galvanized film has gloss. In this case, the reaction product (A) can ease the dependence of the deposition rate of the obtained galvanized film on the current density, and can improve the throwing power and throwing power of the galvanized film. . Furthermore, these functions are less dependent on the content of the reaction product (A) in the galvanizing bath, and range from a low content of about 0.1 g / L to a high content of about 15 g / L. A galvanized film having gloss at current density is obtained.

  Therefore, when the galvanizing bath contains the reaction product (A), it was obtained even when the surface to be plated of the member to be plated had irregularities and it was difficult to make the current density uniform. The galvanized film has high throwing power and throwing power, and the glossiness of the plated film is also high. In addition, it is easy to manage the composition of the galvanizing bath, especially the additive concentration. Therefore, by using the reaction product (A) as an additive component, a zinc-based plated member having an excellent quality galvanized film can be obtained with high productivity.

  Even when the zinc alloy plating bath contains the reaction product (A), the reaction product (A) functions as a brightener, and a zinc alloy plating film having excellent gloss in a wide current density range is obtained. In addition, normal brighteners can be classified into primary brighteners and secondary brighteners. Since reaction product (A) plays both roles in the zinc alloy plating bath, primary brighteners and secondary brighteners can be used. Even without additional use, a zinc alloy plating having an excellent appearance can be obtained. Furthermore, the compound (α), which is considered to be contained in the reaction product (A), is unlikely to cause chemical interaction in the plating bath with the metal element (for example, nickel) related to the bath-soluble metal-containing material. There is little change in the liquid property (for example, liquid permeability) of the plating bath due to the change in the content of the product (A). Therefore, the plating bath according to this embodiment is easy to manage the composition of the plating bath and is excellent in productivity.

  And when a zinc alloy plating bath contains the reaction product (A), the zinc alloy plating film obtained from the said plating bath is formed from the zinc alloy plating bath containing the additive which concerns on a prior art. Excellent corrosion resistance compared to zinc alloy plating film. Although the details are shown in the examples, the zinc alloy plating film obtained from the zinc alloy plating bath containing the reaction product (A) according to the present embodiment is represented by an iron-based member (in this specification, “iron-based member”). Means a member having an iron-based metal surface.) When a member (zinc alloy plated member) on the surface was subjected to a corrosion resistance test, it was obtained from a zinc alloy plating bath containing a brightener according to the prior art. Compared to a zinc alloy plated member, the degree of red rust generated due to the corrosion of the zinc alloy plated film is small, and the properties (surface roughness, etc.) of the surface made of the zinc alloy plated film are less likely to deteriorate. That is, by using the reaction product (A) as an additive component, a zinc-based plated member having a zinc alloy plating film having excellent corrosion resistance can be obtained with high productivity.

  The content of the reaction product (A) in the zinc plating bath is not particularly limited. When the amount is excessively small, it is difficult to obtain an effect based on the inclusion of the reaction product (A) (such as obtaining a plating having an excellent appearance). When the amount is excessively large, the current density is high. There is a concern that it may be difficult to obtain a glossy plating. Therefore, the content of the reaction product (A) in the zinc-based plating bath is preferably 0.1 g / L or more and 15 g / L or less, and more preferably 0.5 g / L or more and 10 g / L or less. 1 g / L or more and 5 g / L or less is particularly preferable.

  The reaction product (A) emits blue light (emission wavelength: about 450 to 460 nm) when irradiated with i-line (wavelength 365 nm) of a high-pressure mercury lamp. The structure that gives this light emission is not clear, but the interaction between the amide bond part of the compound (α) and the compound (β), in particular the carbonyl group, and the hydroxyl group at the β position relative to the nitrogen of the amide bond. It may be based. Since the zincate-based zinc plating bath according to the prior art does not contain a component exhibiting light emission as described above as an additive, a certain zincate-type zinc-based plating bath is the zinc-based plating bath according to this embodiment. This can be confirmed by the presence or absence of this light emission. That is, as an aspect, the present embodiment has a reaction product in a zincate zinc plating bath depending on whether or not blue light emission is observed when i-line of a high pressure mercury lamp is irradiated on the zincate zinc plating bath. A method for determining whether (A) is included is also provided.

(2-2) Other additive components The zinc-based plating bath according to the present embodiment may contain additive components other than the reaction product (A). Examples of such an additive component or a material that provides the additive component in the plating bath include the following.

i) Primary brightener The zinc-based plating bath according to the present embodiment may contain a primary brightener as a kind of additive component. Examples of such primary brighteners include water-soluble organic compounds such as anionic surfactants, nonionic surfactants, polyamine compounds and water-soluble cationic polymer compounds used in various zinc plating baths. .
Examples of the polyamine compound and the water-soluble cationic polymer compound include polyallylamine, polyepoxypolyamine, polyamide polyamine, and polyalkylene polyamine.

  Specific examples of polyallylamine include a copolymer of diallyldimethylammonium chloride and sulfur dioxide. Specific examples of polyepoxypolyamines include condensation polymers of ethylenediamine and epichlorohydrin, condensation polymers of dimethylaminopropylamine and epichlorohydrin, condensation polymers of imidazole and epichlorohydrin, and imidazoles such as 1-methylimidazole and 2-methylimidazole. Examples thereof include condensation polymers of derivatives and epichlorohydrin, and condensation polymers of heterocyclic amines including triazine derivatives such as acetoguanamine and benzoguanamine, and epichlorohydrin. Specific examples of the polyamide polyamine include polyamine polyurea resins such as a condensation polymer of 3-dimethylaminopropylurea and epichlorohydrin, a condensation polymer of bis (N, N-dimethylaminopropyl) urea and epichlorohydrin, N, N- Examples thereof include water-soluble nylon resins such as a condensation polymer of dimethylaminopropylamine, alkylenedicarboxylic acid and epichlorohydrin. Specific examples of polyalkylene polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenepentamine, a condensation polymer of dimethylaminopropylamine and 2,2′-dichlorodiethyl ether, dimethylaminopropylamine. And 1,3-dichloropropane condensation polymer, N, N, N ′, N′-tetramethyl-1,3-diaminopropane and 2,2′-dichlorodiethyl ether condensation polymer, N , N, N ′, N′-tetramethyl-1,3-diaminopropane and 1,4-dichlorobutane condensation polymer, N, N, N ′, N′-tetramethyl-1,3-diaminopropane and Examples thereof include condensation polymers with 1,3-dichloropropan-2-ol.

  In addition, since said reaction product (A) has a function as a primary brightener, the decomposition product of said primary brightener may deteriorate the external appearance and characteristics (corrosion resistance etc.) of a zinc-type plating film. In this case, a zinc-based plating film having an excellent appearance can be obtained without including the primary brightener in the zinc-based plating bath according to the present embodiment. This tendency is particularly remarkable when the zinc-based plating bath is a zinc alloy plating bath. Usually, it is difficult to obtain a zinc alloy plating film having an excellent appearance from a zinc alloy plating bath not containing a primary brightener, but when the reaction product (A) is contained, it contains a primary brightener. A zinc alloy plating film having an excellent appearance can be stably obtained without any problems. When the zinc-based plating bath according to the present embodiment is a galvanizing bath, a galvanized film having an excellent appearance may be obtained more stably when a primary brightener is contained.

ii) Secondary brightener The zinc-based plating bath according to this embodiment may contain a primary brightener as a kind of additive component. In particular, from the viewpoint of improving glossiness and throwing power, at least one of an aromatic aldehyde and a pyridinium compound may be contained as a secondary brightener.
Aromatic aldehydes that can function as secondary brighteners include anisaldehyde, veratraldehyde, salicylaldehyde, vanillin, piperonal, and p-hydroxybenzaldehyde. Veratraldehyde and vanillin are exemplified as aromatic aldehydes preferably contained as a secondary brightener from the viewpoint of improvement of gloss and stability of compounds contained in the zinc-based plating bath.
Examples of the pyridinium compound that can function as a secondary brightener include benzylpyridinium carboxylate (3-carboxybenzylpyridinium chloride) and 3-carbamoylbenzylpyridinium chloride.

iii) Plating Accelerator “Plating Accelerator” has a function of accelerating the deposition of plating metal, and it is adsorbed on the surface to be plated and causes a reduction reaction of metal ions in the vicinity of the adsorbed region. Presumed to be promoting.
As such a plating accelerator, a thiadiazole compound which is a compound having a thiadiazole skeleton is exemplified. There is a possibility that three sulfur contained in the thiadiazole skeleton are chemisorbed on the surface to be plated and promote the reduction reaction of metal ions in the chemisorbed region. Specific examples of thiadiazole compounds include 2,5-dimercapto-1,3,4-thiadiazole, 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole, 2,5-dithioacetic acid-1,3,4 Thiadiazole, 2-hydroxyethylthio-5-mercapto-1,3,4-thiadiazole, 2,5-dihydroxyethylthio-1,3,4-thiadiazole, epichlorohydrin modified 2,5-dimercapto-1,3 4-thiadiazole, bis (1,3,4-thiadiazole-2,5-diyl) and the like can be mentioned.

iv) Chelating agent When the zinc-based plating bath according to the present embodiment is a zinc alloy plating bath, a chelating agent may be contained.
Specific examples of chelating agents include tartaric acid, citric acid, gluconic acid, ethylenediamine, hexamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, triaminotriethylamine , Methylaminopropylamine, monoethanolamine, diethanolamine, triethanolamine, diethanolaminopropylamine, 2-hydroxyethylaminopropylamine, 1,3-bis- (3-aminopropoxy) ethane, nitrilotriacetic acid (NTA), ethylenediamine Examples include tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and triethylenetetraminehexaacetic acid (TTHA). This chelating agent may be a chelating agent that also functions as a primary brightener, such as polyamine compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. When the chelating agent has an acid partial structure such as carboxylic acid, the chelating agent may be added to the zinc alloy plating bath as a free acid form or as a salt. Alternatively, it may be added to the zinc alloy plating bath in the form of a derivative (for example, ester) that can form an acid ion by hydrolysis in an alkaline zinc alloy plating bath.

v) Antioxidants, antifoaming agents, etc. Antioxidants include hydroxyphenyl compounds such as phenol, catechol, resorcin, hydroquinone, pyrogallol, L-ascorbic acid, sorbitol and the like. In addition, when said chelating agent is a reducing substance, since the chelating agent has the function of antioxidant, it is not necessary to contain antioxidant.
Examples of antifoaming agents include silicone-based antifoaming agents and organic antifoaming agents such as surfactants, polyethers, and higher alcohols.

(3) Solvent, liquidity The solvent of the plating bath which concerns on this embodiment has water as a main component. As a solvent other than water, an organic solvent having high solubility in water, such as alcohol, ether, and ketone, may be mixed. In this case, the ratio is preferably 10% by volume or less with respect to the total solvent from the viewpoint of the stability of the entire plating bath and the relaxation of the load on the waste liquid treatment.

  Since the zinc-based plating bath according to this embodiment is a zincate-type plating bath, it is alkaline. The type of material used to make the plating bath alkaline (also referred to as “alkaline component” in this specification) is not particularly limited. A known material such as an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be used.

  The content of the alkali component contained in the zinc-based plating bath according to this embodiment is not particularly limited. If the amount is excessively small, the liquidity of the zinc-based plating bath cannot be made alkaline, and it is difficult to generate zincate ions in the plating bath. On the other hand, when the content of the alkali component is excessively high, the stability of the zinc-based plating bath may decrease, and the appearance of the resulting zinc-based plating film may decrease or the throwing power may decrease. Is done. Therefore, the content of the alkali component contained in the zinc-based plating bath is preferably 40 g / L or more and 400 g / L or less, more preferably 80 g / L or more and 250 g / L or less in terms of sodium hydroxide, It is particularly preferable that the amount be 100 g / L or more and 200 g / L or less.

(4) Preparation method The preparation method of the zinc-type plating bath which concerns on this embodiment is not specifically limited. In the case of a galvanizing bath, a component containing an alkali component, a zinc source and a reaction product (A) (a liquid containing the aforementioned reaction product is given as a specific example of such a component. It can also be prepared by dissolving the above-mentioned other additive components and the like as optional additional components in a solvent such as water. In the case of a zinc alloy plating bath, it is prepared by dissolving an alkali component, a zinc source, a metal source and a reaction product (A) source, and, if necessary, other additive components as described above in a solvent. can do. Usually, a zinc-based plating bath can be prepared safely and without reducing workability by adding an alkaline component to a solvent and then adding other components.

2. Additive for zincate-type zinc-based plating bath The additive for zincate-type zinc-based plating bath according to the present embodiment contains an additive component contained in the zinc-based plating bath according to the present embodiment. That is, the additive for zincate-type zinc-based plating bath according to the present embodiment contains the reaction product (A), and if necessary, other additives such as a primary brightener, a secondary brightener, and a plating accelerator. Contains ingredients. As mentioned above, since the reaction product (A) emits blue light when irradiated with i-line (wavelength 365 nm) of a high-pressure mercury lamp, an additive contains the reaction product (A). Whether or not blue emission is observed when the additive is irradiated with i-line of a high-pressure mercury lamp can be determined.

The content of the reaction product (A) in the zincate-type zinc plating bath additive according to this embodiment is not particularly limited. Since the reaction product (A) has high solubility, the content can be increased to about 50 g / L.
In the case where the additive for zincate-type zinc plating bath according to the present embodiment contains components other than the reaction product (A), their contents should be appropriately set in relation to the function of the additive. is there.

3. Method for Producing Zinc-Based Plating Member A zinc-based plated member can be obtained by immersing a member to be plated in the zinc-based plating bath according to the present embodiment and performing electrolysis using the member to be plated as a cathode (cathode). The material of the member to be plated is not particularly limited as long as it has conductivity. Examples are those in which a layer made of a conductive material is formed on the surface of a metal-based material such as an iron-based material and a non-conductive material made of a resin-based material or a ceramic-based material by electroless plating or the like . The shape of the member to be plated is not particularly limited. Examples include primary processed products such as plate materials, bar materials, and wire materials, and secondary processed products such as screws, bolts, and pressed products.
In addition, the material which comprises an anode (anode) is not specifically limited. Usually, iron-based materials that are inexpensive and easily available are used.

The current density in electrolysis is not particularly limited. When the current density is excessively low, the deposition rate of the obtained zinc-based plating film is low and the productivity is inferior. When the current density is excessively high, the appearance of the obtained zinc-plating film is deteriorated or the electrodeposition is uniform. Considering that there is a concern that the throwing power may be lowered, it may be set as appropriate. From the viewpoint of improving productivity and improving the quality of the plating film, it is preferably 0.01 A / dm ² or more and 10 A / dm ² or less, and 0.5 A / dm ² or more and 6 A / dm ² or less. And more preferably 0.5 A / dm ² or more and 3 A / dm ² or less.

  The temperature of the plating bath in electrolysis (plating bath temperature) may be about room temperature (about 25 ° C.). When the plating bath temperature is excessively high, there is a concern that the solvent and low molecular weight organic components are likely to volatilize. When this volatilization becomes significant, the liquid composition becomes unstable and it becomes difficult to maintain the quality stability of the plating film. When the plating bath temperature is excessively low, there is a concern that the productivity may be adversely affected, for example, the deposition rate of the plating film may decrease.

  The electrolysis time (plating time) is appropriately set based on the deposition rate of the plating film determined by the composition of the plating bath, the current density, the plating bath temperature, and the like, and the desired thickness of the plating film.

  The configuration of the plating facility is not particularly limited. A member to be plated as a cathode is placed in a zinc-based plating bath so as to face the plate-like or rod-shaped anode, and a zinc-based plating film is applied to the member to be plated by performing electrolysis while appropriately stirring the solution in the zinc-based plating bath. The barrel to be plated such as bolts is immersed in a zinc plating bath, and electrolysis is performed while rotating the barrel. May be formed.

  Hereinafter, although the effect of the present invention is explained based on an example, the present invention is not limited to this.

1. Preparation of a zinc-based plating bath and production of a member having a zinc-based plating film [Example 1]
(1) Production of reaction product (A1) source 97.7 g (0.8 mol) of nicotinamide and 168.6 g of water were placed in a 1000 ml three-necked flask and stirred, and ethylene chlorohydrin was placed in the flask. 70.9 g (0.88 mol) was added. After the addition, the liquid temperature in the flask was maintained at 100 ° C. and stirred for 4 hours, and then the liquid in the flask was allowed to cool while stirring to lower the liquid temperature to 35 ° C., and then glycidyltrimethylammonium in the flask. 166.7 g (0.8 mol) of an aqueous solution containing chloride as a main component (“Kachio Master (registered trademark) G” manufactured by Yokkaichi Synthesis Co., Ltd., 73% pure content) and 76.7 ml of water were added and stirred. Subsequently, a liquid containing a reaction product (hereinafter also referred to as “reaction product (A1)”) obtained by adjusting the liquid temperature in the flask to 65 ° C. and refluxing for 2 hours is a kind of plating bath additive. Using. This liquid is a kind of reaction product (A) source, and is hereinafter also referred to as “reaction product (A1) source”. The obtained reaction product (A1) source was a brown liquid having a yield of 580.6 g and a solid content (that is, the content of the reaction product (A1)) of 50% by weight.

(2) Preparation of zinc plating bath Zinc oxide as a zinc source, an amount in which the zinc equivalent content in a plating bath of a bath-soluble zinc-containing substance derived therefrom is 12 g / L, sodium hydroxide as an alkali component The amount of dissolution of the reaction product (A1) per liter of the plating bath is 120 g, and the amount of the reaction product (A1) in the plating bath is 1.0 g / L. The reaction product (A1) source is 2.0 g / L), and a polymer of N, N′-bis [3- (dimethylamino) propylurea] and 1,1′-oxybis [2-chloroethane] (Rhodia “MIRAPOL WT” (hereinafter referred to as “Polymer 1”) manufactured by Nikka Corporation has a content of 2 g / cation polymer (hereinafter referred to as “cationic polymer 1”) formed in the plating bath based on Polymer 1. An alkaline zincate-type galvanizing bath containing a bath-soluble zinc-containing substance and compound (A1) was prepared by dissolving in an amount of L and a solvent comprising pure water.

(3) Production of zinc-based plating member having galvanized film A liquid circulation type hull cell tester (manufactured by Yamamoto Plating Tester Co., Ltd .: Smart Hull Cell B-53-SM) having a stirrer rotation speed of 1000 rpm was prepared. At predetermined positions in the plating tank of this tester, an iron plate as an anode having a length of 45 mm, a width of 45 mm, and a thickness of 1 mm, and an iron plate as a member to be plated (cathode) having a length of 67 mm, a width of 100 mm, and a thickness of 0.3 mm Arranged. The above-described plating bath was placed in the plating tank until the liquid level reached a predetermined height. The anode and the cathode were connected to a plating power source, and electroplating was performed under the following electrolytic conditions to obtain a zinc-based plated member having a zinc plating film.
Current: 1A
Energizing time: 10 minutes Plating bath temperature: 25 ° C
In the above current, cathode current density ranged from 0.1 A / dm ² of 5A / dm ^2.

[Example 2]
In preparing the plating bath according to Example 1, the content of the reaction product (A1) in the plating bath was changed to 5.0 g / L by changing the blending amount of the reaction product (A1) source. Prepared a plating bath and electroplated by the same operation as in Example 1 to obtain a zinc-based plated member having a galvanized film.

[Example 3]
In preparing the plating bath according to Example 1, the content of the reaction product (A1) in the plating bath was changed to 10 g / L by changing the blending amount of the reaction product (A1) source. A plating bath was prepared and electroplated in the same manner as in Example 1 to obtain a zinc-based plated member having a galvanized film.

[Comparative Example 1]
In preparation of the plating bath according to Example 1, instead of the reaction product (A1) source, a hydrochloride of benzylpyridinium carboxylate (BPC) is blended, and the amount of BPC formed in the plating bath is included. A plating bath was prepared and electroplated in the same manner as in Example 1 except that the amount was 0.24 g / L, and a zinc-based plated member having a galvanized film was obtained.

[Comparative Example 2]
In preparing the plating bath according to Comparative Example 1, the preparation of the plating bath was carried out in the same manner as in Comparative Example 1 except that the amount of BPC hydrochloride was changed and the BPC content was 1.2 g / L. And electroplating was performed to obtain a zinc-based plated member having a galvanized film.

[Comparative Example 3]
In preparation of the plating bath according to Comparative Example 1, the preparation of the plating bath was carried out in the same manner as in Comparative Example 1, except that the amount of BPC hydrochloride was changed and the content of BPC was changed to 2.4 g / L. And electroplating was performed to obtain a zinc-based plated member having a galvanized film.

[Example 4]
(1) Preparation of zinc alloy plating bath Zinc oxide as a zinc source, an amount in which the zinc equivalent content in a plating bath of a bath-soluble zinc-containing substance derived therefrom is 10 g / L, and nickel sulfate as a nickel source , The amount of the bath-soluble nickel-containing substance derived from this in an amount such that the nickel equivalent content in the plating bath is 1.5 g / L, the amount of sodium hydroxide as the alkaline component is 120 g dissolved per 1 L of the plating bath , Tetraethylenepentamine (TEPA) as the chelating agent, the amount of the plating bath content to be 15 g / L, and the reaction product (A1) source, the content of the reaction product (A1) in the plating bath Is dissolved in a solvent consisting of pure water in an amount of 1.0 g / L, and a bath-soluble zinc-containing material, a bath-soluble nickel-containing material, a reaction product (A1), and an alkase containing TEPA A reusable zincate type zinc-nickel alloy plating bath was prepared.

(2) Production of zinc-based plating member having zinc alloy plating film A liquid circulation type hull cell tester (manufactured by Yamamoto Plating Tester Co., Ltd .: Smart Hull Cell B-53-SM) having a stirrer rotation speed of 1000 rpm was prepared. At predetermined positions in the plating tank of this tester, an iron plate as an anode having a length of 45 mm, a width of 45 mm, and a thickness of 1 mm, and an iron plate as a member to be plated (cathode) having a length of 67 mm, a width of 100 mm, and a thickness of 0.3 mm Arranged. The above-described plating bath was placed in the plating tank until the liquid level reached a predetermined height. The anode and the cathode were connected to a plating power source, and electroplating was performed under the following electrolytic conditions to obtain a zinc-based plated member having a zinc-nickel alloy plating film.
Current: 1A
Energizing time: 10 minutes Plating bath temperature: 25 ° C
In the above current, cathode current density ranged from 0.1 A / dm ² of 5A / dm ^2.

[Example 5]
In preparing the plating bath according to Example 4, the content of the reaction product (A1) in the plating bath was changed to 5.0 g / L by changing the blending amount of the reaction product (A1) source. A plating bath was prepared and electroplated in the same manner as in Example 4 to obtain a zinc-based plated member having a zinc-nickel alloy plating film.

[Example 6]
In preparation of the plating bath according to Example 4, the amount of the reaction product (A1) source was changed to change the content of the reaction product (A1) in the plating bath to 10 g / L. A plating bath was prepared and electroplated by the same operation as in No. 4 to obtain a zinc-based plated member having a zinc-nickel alloy plating film.

[Comparative Example 4]
In preparing the plating bath according to Example 4, the benzylpyridinium carboxylate (BPC) hydrochloride was blended in place of the reaction product (A1) source, and the content of BPC formed in the plating bath was 0.00. The preparation of the plating bath was carried out in the same manner as in Example 4 except that the amount of the cationic polymer 1 was 0.001 mol / L and the amount of the polymer 1 was 0.001 mol / L. Electroplating was performed to obtain a zinc-based plated member having a zinc-nickel alloy plating film.

[Comparative Example 5]
In preparing the plating bath according to Comparative Example 4, the preparation of the plating bath was carried out in the same manner as in Comparative Example 4 except that the amount of BPC hydrochloride was changed and the BPC content was 1.2 g / L. And electroplating was performed to obtain a zinc-based plated member having a zinc-nickel alloy plating film.

[Comparative Example 6]
In preparing the plating bath according to Comparative Example 4, the preparation of the plating bath was carried out in the same manner as in Comparative Example 4 except that the amount of BPC hydrochloride was changed and the BPC content was 2.4 g / L. And electroplating was performed to obtain a zinc-based plated member having a zinc-nickel alloy plating film.

[Example 7]
(1) Preparation of zinc alloy plating bath In preparation of the plating bath according to Example 4, the content of the reaction product (A1) in the plating bath was changed to 0 by changing the blending amount of the reaction product (A1) source. A plating bath was prepared in the same manner as in Example 4 except that the amount was changed to 0.5 g / L.
(2) Production of a zinc-based plating member having a zinc alloy plating film A plating tank having a stirrer rotation speed of 450 rpm and a length of 100 mm, a width of 100 mm, and a height of 145 mm was prepared. In a predetermined position in the plating tank, two nickel plates as anodes with a length of 130 mm, a width of 65 mm, and a thickness of 1 mm, and an iron plate as a member to be plated (cathode) with a length of 50 mm, width of 100 mm, and thickness of 1 mm as an anode Arranged between. The plating bath was placed in the plating tank until the liquid level reached 130 mm. The anode and the cathode were connected to a plating power source, and electroplating was performed under the following electrolytic conditions to obtain a zinc-based plated member having a zinc-nickel alloy plating film.
Current density: 2 A / dm ²
Energizing time: 19 minutes Plating bath temperature: 25 ° C
The thickness of the obtained plating film was in the range of 6 to 7 μm.

[Example 8]
Using the plating bath according to Example 4, electroplating was performed on the nickel plate in the same manner as in Example 7 to obtain a zinc-based plated member having a zinc-nickel alloy plating film with a thickness of 6 to 7 μm. It was.

[Example 9]
(1) Production of reaction product (A2) 97.7 g (0.8 mol) of nicotinamide and 222.6 g of water were placed in a three-necked flask having a capacity of 1000 ml and stirred, and methyl iodide 124. 9 g (0.88 mol) was added. After the addition, the liquid temperature in the flask was maintained at 100 ° C. and stirred for 4 hours, and then the liquid in the flask was allowed to cool while stirring to lower the liquid temperature to 35 ° C., and then glycidyltrimethylammonium in the flask. 166.7 g (0.8 mol) of an aqueous solution containing chloride as a main component (“Kachio Master (registered trademark) G” manufactured by Yokkaichi Synthesis Co., Ltd., 73% pure content) and 76.7 ml of water were added and stirred. Subsequently, a liquid containing a reaction product (hereinafter also referred to as “reaction product (A2)”) obtained by adjusting the liquid temperature in the flask to 65 ° C. and refluxing for 2 hours is used as a kind of plating bath additive. Using. This liquid is a kind of source of reaction product (A), and is hereinafter also referred to as “reaction product (A2) source”. The obtained reaction product (A1) source was a brown liquid having a yield of 688.6 g and a solid content (that is, the content of the reaction product (A2)) of 50% by weight.

(2) Preparation of zinc alloy plating bath Zinc oxide as a zinc source is used in such an amount that the zinc equivalent content in the plating bath of the bath-soluble zinc-containing substance derived therefrom is 10 g / L, and nickel sulfate is used as the nickel source. , The amount of the bath-soluble nickel-containing substance derived from this in an amount such that the nickel equivalent content in the plating bath is 1.5 g / L, the amount of sodium hydroxide as the alkaline component is 120 g dissolved per 1 L of the plating bath , Tetraethylenepentamine (TEPA) as the chelating agent, the amount of the plating bath content to be 15 g / L, and the reaction product (A2) source, the content of the reaction product (A2) in the plating bath Is dissolved in a solvent comprising pure water in an amount of 1.0 g / L, and a bath-soluble zinc-containing material, a bath-soluble nickel-containing material, a reaction product (A2), and an alkase containing TEPA A reusable zincate type zinc-nickel alloy plating bath was prepared.

(3) Production of a zinc-based plating member having a zinc alloy plating film Using the above plating bath, electroplating was performed on a nickel plate in the same manner as in Example 7 to obtain a zinc having a thickness of 6 to 7 μm. A zinc-based plating member having a nickel alloy plating film was obtained.

[Comparative Example 7]
In preparing the plating bath according to Comparative Example 4, the plating bath was prepared by the same operation as in Comparative Example 4 except that the blending amount of BPC hydrochloride was changed so that the BPC content was 0.12 g / L. did.
Using the obtained plating bath, electroplating was performed on the nickel plate in the same manner as in Example 7 to obtain a zinc-based plated member having a zinc-nickel alloy plating film with a thickness of 6 to 7 μm.

[Examples 10 to 12]
In preparing the plating bath according to Example 4, the same as Example 4 except that the following amount of each of the cationic polymers 2 to 4 was blended in the plating bath so that the amount of each polymer was 1.5 g / L. A plating bath was prepared and electroplated by operation to obtain a zinc-based plated member having a zinc-nickel alloy plating film.
Cationic polymer 2: 1 mol of urea, 2 mol of N, N-dimethylaminopropylamine and 1 mol of epichlorohydrin Cationic polymer 3: 1 mol of urea and 1.5 mol of N, N-dimethylaminopropylamine and epi Reactive substance of 1 mol of chlorohydrin Cationic polymer 4: Reaction of 1 mol of urea, 1.5 mol of N, N-dimethylaminopropylamine, 0.6 mol of epichlorohydrin, 0.8 mol of dichloroethyl ether

2. Evaluation (1) Appearance Evaluation of Plating Bath The appearances of the plating baths prepared in Examples 4 to 6 and Comparative Examples 4 to 6 were visually observed to evaluate their properties. The evaluation results are shown in Table 1. In addition, the numerical value shown in the column of “content (g / L)” in Table 1 is the content of the reaction product (A1) for Examples 4 to 6, and BPC for Comparative Examples 4 to 6. Content.

(2) Appearance evaluation of plated surface The properties of the plated surface of the member having the plating film prepared according to the examples and comparative examples are the end portions (hereinafter referred to as “high current”) that had a high current density when electroplating was performed. It was visually observed at a position of every 10 mm from the “density side end” and evaluated according to the following criteria.
1: Almost mirror surface high gloss 2: Gloss 3: Semi-gloss 4: Matte 5: Rough surface based on bubble generation Tables 2 to 3 show the evaluation results. In addition, the numerical value shown in the column of “content (g / L)” in Tables 2 and 3 is the content of the reaction product (A1) for Examples 1 to 6 and 10 to 12, and is a comparative example. 1 to 6 are BPC contents.

(3) Plating film thickness distribution The thickness (unit: μm) of the plating film of the member having the plating film prepared according to the example and the comparative example is set at a position of every 10 mm from the end portion on the high current density side. The thickness was measured with a thickness meter (SFT-9200, manufactured by SII).
The measurement results are shown in Tables 4 to 6 and FIG.

(4) Nickel eutectoid rate The nickel eutectoid rate (unit: mass%) in the plating film of the member having the plating film produced in Examples 4 to 6 and 10 to 12 and Comparative Examples 4 to 6 is expressed as high current density. It measured with the fluorescent X-ray film thickness meter (SII company make: SFT-9200) in the position for every 10 mm from a side edge part.
The measurement results are shown in Tables 7 and 8.

(5) Corrosion Resistance Test For the zinc-based plated members according to Examples 7 to 9 and Comparative Example 7, the corrosion resistance test based on CCT (Automobile Parts Appearance Corrosion Test Method) defined in JASO M609 was performed for 5 cycles.

The conditions of the corrosion resistance test are shown below.
(A) Salt spray temperature: 35 ± 1 ° C
Salt water concentration: 5 ± 0.5%
Others conformed to JIS Z2371: 2000 (ISO 9227: 1990).
(B) Drying temperature: 60 ± 1 ° C
Relative humidity: 20-30% RH
(C) Wetting temperature: 50 ± 1 ° C
Relative humidity: 95% RH or more (D) Time and content of 1 cycle Salt spray 2 hours, Dry 4 hours, Wet 2 hours Each time represents the transition time (after the transition to each condition, Time to reach relative humidity).
(E) Transition time Drying to drying: within 30 minutes Drying to wet: within 15 minutes Wet to spraying: within 30 minutes (Normally, this transition time is instantaneous.)
(F) Test piece holding angle As a general rule, the test piece is held so that the evaluation target surface of the test piece is 15 to 20 ° with respect to the vertical.

The surface consisting of the zinc-nickel alloy plating film of the zinc-based plated member after the end of 5 cycles was visually observed, and the number of positions (red rust occurrence points) where red rust was generated was measured. Moreover, the surface roughness of the surface consisting of a zinc-nickel alloy plating film was measured before and after performing the corrosion resistance test (measuring device: manufactured by Tokyo Seimitsu Co., Ltd., Surfcom 1400G). In addition, centerline average roughness Ra ₇₅ , ten-point average roughness Rz, and maximum height Rmax (all based on JIS B0601: 1994) were determined as parameters related to surface roughness. Further, for each parameter, the ratio of the measurement results before and after the corrosion resistance test (after the test / before the test) was calculated.
Table 9 shows the measurement results.

(6) Confirmation of the presence or absence of light emission The reaction product (A1) source and the reaction product (A2) source, and the zincate zinc plating baths according to Examples 1 to 9 and Comparative Examples 1 to 7 were combined with a high-pressure mercury lamp (i-line). ), The reaction product (A1) source and the reaction product (A2) source containing the reaction product (A1) or the reaction product (A2) and the zincate zinc system according to Examples 1 to 9 For the plating bath, blue (450-460 nm) emission was observed. On the other hand, no blue light emission was observed for the zincate-type zinc plating baths according to Comparative Examples 1 to 7.

Claims (8)

A chain alkyl halide and an alicyclic alkyl halide, and at least one of hydrogen in the alkyl halide is an amino group, a hydroxy group, an oxyalkylene ether group, an alkylcarboxyalkyl group, an arylcarboxyalkyl group, a carboxyalkyl group, a phosphonic acid group Or a compound substituted with an aryl group, and a reaction product (a) of nicotinamide with one or more selected from the group consisting of alkanesultone and a halide of glycidyltrimethylammonium. A zincate-type zinc-based plating bath characterized by containing a reaction product (A) obtained and a bath-soluble zinc-containing substance.   The plating bath according to claim 1, wherein the reaction product (A) is contained in an amount of 0.1 g / L or more and 15 g / L or less.   The plating bath according to claim 1 or 2, which does not contain cyanide.   The plating bath according to any one of claims 1 to 3, wherein the bath-soluble zinc-containing material contains 2 g / L or more and 60 g / L in terms of zinc. Further containing a bath-soluble metal-containing substance,
The plating bath according to any one of claims 1 to 4, wherein the metal element contained in the bath-soluble metal-containing substance is one or more selected from the group consisting of iron, nickel, cobalt, and manganese. An additive for a zincate zinc-based plating bath containing the reaction product (A) according to claim 1. A method for producing a zinc-based plating member comprising a member to be plated and a zinc-based plating film laminated on a surface to be plated of the member to be plated,
Using the zincate-type zinc plating bath according to any one of claims 1 to 5, the content of the reaction product (A) contained in the plating bath is 0.0001 mol / L or more and 0.05 mol / L. A method for producing a zinc-based plated member, characterized in that plating is performed while controlling within the following range. A method for producing a zinc alloy plating member comprising a member to be plated and a zinc alloy plating film laminated on a surface to be plated of the member to be plated,
A zincate-type zinc-based plating bath according to claim 5, wherein the zincate-type zinc alloy plating bath contains a bath-soluble nickel-containing substance.
The manufacturing method of the zinc alloy plating member which makes the eutectoid rate of nickel in the zinc alloy plating film obtained from the said zincate type zinc alloy plating bath 12 mass% or more and 20 mass% or less.

Images