WO2022186183A1 - Additif pour bain de placage d'alliage de zinc acide, bain de placage d'alliage de zinc acide et film de placage d'alliage de zinc - Google Patents

Additif pour bain de placage d'alliage de zinc acide, bain de placage d'alliage de zinc acide et film de placage d'alliage de zinc Download PDF

Info

Publication number
WO2022186183A1
WO2022186183A1 PCT/JP2022/008540 JP2022008540W WO2022186183A1 WO 2022186183 A1 WO2022186183 A1 WO 2022186183A1 JP 2022008540 W JP2022008540 W JP 2022008540W WO 2022186183 A1 WO2022186183 A1 WO 2022186183A1
Authority
WO
WIPO (PCT)
Prior art keywords
alloy plating
zinc alloy
nickel
zinc
plating bath
Prior art date
Application number
PCT/JP2022/008540
Other languages
English (en)
Japanese (ja)
Inventor
奨悟 西原
司 丹羽
寿裕 杉浦
泰紀 青木
Original Assignee
ユケン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ユケン工業株式会社 filed Critical ユケン工業株式会社
Priority to JP2023503852A priority Critical patent/JPWO2022186183A1/ja
Publication of WO2022186183A1 publication Critical patent/WO2022186183A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel

Definitions

  • the present invention relates to an additive for an acidic zinc alloy plating bath, an acidic zinc alloy plating bath, and a zinc alloy plating film.
  • zinc alloy plating refers to plating consisting of zinc, alloy components, and unavoidable impurities.
  • the concentration (% by mass) of zinc in the plating may be higher than the concentration (% by mass) of any other alloying element, or the concentration (% by mass) of the alloying element is higher than the concentration (% by mass) of zinc. may be included.
  • Zinc-nickel alloy, zinc-iron alloy, tin-zinc alloy and other zinc alloy plating films are steel materials such as steel sheets for automobiles and bolts and nuts. It is widely used for the purpose of improving functionality such as corrosion resistance and heat resistance for members around us, including machine parts made of.
  • the zinc alloy plating film is formed by electroplating in which electrolysis is performed while the member to be plated is immersed in a plating bath (also referred to as a “zinc alloy plating bath” in this specification) for forming the zinc alloy plating film.
  • a plating bath also referred to as a “zinc alloy plating bath” in this specification
  • This zinc alloy plating bath is roughly divided into an alkaline bath (for example, Patent Document 1, etc.) and an acid bath (eg, Patent Document 2, etc.).
  • An appropriate bath is selected from these zinc alloy plating baths in consideration of various conditions such as the desired hardness and gloss of the zinc alloy plating film, the shape and size of the member to be plated, and the working environment.
  • a substrate made of cast iron or steel is coated with an acetate selected from the group consisting of sodium acetate, potassium acetate, ammonium acetate, and mixtures thereof, a zinc ion source, a nickel ion source, and contacting an electrolytic composition comprising an aminoacetic acid and applying an electric current to form a zinc-nickel alloy layer on the substrate having a nickel codeposition rate of 10 to 18% by weight and substantially free of internal stress; wherein the acetate and aminoacetate are in a molar ratio of from about 0.35:1 to about 0.91:1 acetate:aminoacetate
  • a method is disclosed that ranges from
  • JP-A-1-298192 Japanese Patent No. 4307810 U.S. Pat. No. 8,435,398
  • the acidic zinc alloy plating bath has the advantage of high current efficiency and excellent productivity.
  • the current density dependence of the film thickness and appearance tends to increase, when the member to be plated has a complicated shape, there is a tendency that the throwing power tends to decrease and appearance defects tend to occur.
  • the input amount in barrel plating and increase the applied voltage in rack plating there is a tendency to increase the input amount in barrel plating and increase the applied voltage in rack plating. Such a tendency tends to cause a local increase in current density, and as a result, local appearance defects tend to occur.
  • An object of the present invention is to provide an additive used to obtain an acidic zinc alloy plating bath capable of obtaining a zinc alloy plating film with a good appearance.
  • the present invention also provides an acidic zinc alloy plating bath capable of obtaining a zinc alloy plating film with a good appearance, and a zinc alloy plating film with a good appearance formed using the above acidic zinc alloy plating bath. intended to provide
  • a zinc alloy-plated member refers to a member comprising a member to be plated and a zinc alloy plating film formed on the surface of the member to be plated.
  • good appearance with respect to the zinc alloy plating film means that the lower limit of the current density at which abnormal deposition is likely to occur in the zinc alloy plating film is increased compared to the conventional one, and that the zinc alloy plating film is not glossy at a certain current density. It means that the zinc alloy plating film satisfies at least one of bright or semi-bright even at the same current density.
  • One aspect of the present invention provided for solving the above problems is an additive for an acidic zinc alloy plating bath, characterized by containing a glycine-containing water-soluble substance and an aliphatic polyamine having 12 or less carbon atoms as active ingredients. be.
  • the aliphatic polyamine contained in the acidic zinc alloy plating bath additive may contain one or more selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
  • the glycine/polyamine ratio which is the ratio of the glycine-equivalent molar concentration of the glycine-containing water-soluble substance contained in the acidic zinc alloy plating bath additive to the molar concentration of the aliphatic polyamine, is preferably 0.1 or more and 40 or less. 1 or more and 35 or less may be more preferable, and 4 or more and 34 or less may be particularly preferable.
  • Another aspect of the present invention is an acidic zinc alloy plating bath characterized by containing a bath-soluble zinc-containing substance, a bath-soluble metal-containing substance, and the active ingredient of the above additive.
  • the acidic zinc alloy plating bath may have a pH of 4 or more and 6 or less.
  • the above acidic zinc alloy plating bath may be preferably free of boric acid.
  • the acidic zinc alloy plating bath described above may preferably be ammonia-free.
  • the acidic zinc alloy plating bath described above may preferably contain an acetic acid-containing substance.
  • the above acidic zinc alloy plating bath may contain a bath-soluble nickel-containing substance as a bath-soluble metal-containing substance.
  • the sedimentation rate may be 5% by mass or more and 20% by mass or less.
  • the acidic zinc alloy plating bath contains a bath-soluble nickel-containing substance, and has a glycine/nickel ratio of 0.1, which is the ratio of the glycine-equivalent molar concentration of the glycine-containing water-soluble substance to the nickel-equivalent molar concentration of the bath-soluble nickel-containing substance.
  • a glycine/nickel ratio of 0.1 which is the ratio of the glycine-equivalent molar concentration of the glycine-containing water-soluble substance to the nickel-equivalent molar concentration of the bath-soluble nickel-containing substance.
  • the above acidic zinc alloy plating bath may contain at least one of a primary brightener and a secondary brightener.
  • Another aspect of the present invention is that when measuring the depth profile of a zinc alloy plated member in which a zinc alloy plating film is formed on a member to be plated made of an iron-based material,
  • the zinc alloy plating film is characterized in that it does not have an alloying element-concentrated region having a relatively high alloying element concentration on the other side.
  • the zinc alloy plating film described above is a zinc alloy plating film containing nickel as an alloying element, and is preferably formed from a plating bath containing glycine and an aliphatic polyamine having 12 or less carbon atoms.
  • the zinc concentration is 60 mass% or more and the position closest to the outermost surface is the surface side end of the zinc alloy plating film, and the iron concentration derived from the member to be plated. is defined as the end of the zinc alloy plating film on the side of the member to be plated, and the length of the region from the end on the surface side to the end on the side of the member to be plated is defined as the thickness of the zinc alloy plating film,
  • the average nickel concentration [Ni1] in the intermediate region from 40% to 60% of the zinc alloy plating thickness from the surface side end, and 30% of the zinc alloy plating thickness from the plated member side end The maximum value of nickel concentration [Ni2] in the initial region consisting of the position moved to the surface side and the end portion of the member to be plated, and the maximum value of nickel concentration [Ni2] in between are calculated by the following formula ( It may be preferable to satisfy 1). [Ni1] ⁇ [Ni2] (1)
  • a zinc alloy plating film with a good appearance can be obtained. Further, according to the present invention, a zinc alloy plated member having a zinc alloy plated film with a good appearance can be obtained.
  • FIG. 2 is a depth profile of the zinc-nickel alloy plating film of Example 2 at a current density of 11 A/dm 2 .
  • 1 is a depth profile of nickel concentration at a current density of 11 A/dm 2 in zinc-nickel alloy plating films of Example 1 and Comparative Example 1.
  • FIG. 2 is a depth profile relating to nickel concentration at a current density of 11 A/dm 2 in the zinc-nickel alloy plating films of Example 2 and Comparative Example 2.
  • FIG. 2 is a depth profile relating to the nickel concentration at a current density of 11 A/dm 2 in the zinc-nickel alloy plating films of Example 3 and Comparative Example 3.
  • FIG. 10 is a depth profile related to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 4 at a current density of 11 A/dm 2 ;
  • FIG. FIG. 10 is a depth profile related to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 5 at a current density of 11 A/dm 2 ;
  • FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 6 at a current density of 11 A/dm 2 ;
  • FIG. 10 is a depth profile of nickel concentration at a current density of 11 A/dm 2 in the zinc-nickel alloy plating film of Example 7.
  • FIG. FIG. 10 is a depth profile related to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 4 at a current density of 11 A/dm 2 ;
  • FIG. 10 is a depth profile related to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 5 at
  • FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 8 at a current density of 11 A/dm 2 ;
  • FIG. 10 is a depth profile of nickel concentration at a current density of 11 A/dm 2 in the zinc-nickel alloy plating film of Example 9.
  • FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 10 at a current density of 11 A/dm 2 ;
  • FIG. FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 11 at a current density of 11 A/dm 2 ;
  • FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 12 at a current density of 11 A/dm 2 ;
  • FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 13 at a current density of 11 A/dm 2 ;
  • FIG. 4 is a depth profile related to nickel concentration at a portion of the zinc-nickel alloy plating film of Comparative Example 4 at a current density of 11 A/dm 2 .
  • 10 is a depth profile related to the nickel concentration in the zinc-nickel alloy plating film of Comparative Example 6 at a current density of 11 A/dm 2 .
  • FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 12 at a current density of 11 A/dm 2 .
  • FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film
  • FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Comparative Example 7 at a current density of 11 A/dm 2 ;
  • FIG. FIG. 10 is a depth profile related to nickel concentration at a portion of the zinc-nickel alloy plating film of Comparative Example 8 at a current density of 11 A/dm 2 ;
  • FIG. 10 is a depth profile related to nickel concentration at a current density of 11 A/dm 2 in the zinc-nickel alloy plating film of Example 16.
  • FIG. FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 17 at a current density of 11 A/dm 2 ;
  • FIG. 10 is a depth profile related to nickel concentration at a current density of 11 A/dm 2 in the zinc-nickel alloy plating film of Example 18.
  • FIG. 10 is a depth profile relating to nickel concentration at a current density of 11 A/dm 2 in the zinc-nickel alloy plating film of Example 19.
  • FIG. 10 is a depth profile relating to nickel concentration at a portion of the zinc-nickel alloy plating film of Example 20 at a current density of 11 A/dm 2 ;
  • additive for an acidic zinc alloy plating bath comprises, as active ingredients, a glycine-containing water-soluble substance and a fat having 12 or less carbon atoms and having a plurality of amino groups.
  • group polyamine which may be abbreviated as "polyamine (A)" in this specification).
  • a glycine-containing water-soluble substance is a glycine-based water-soluble substance produced in a plating bath from a glycine source, which is a substance capable of giving glycine in the plating bath, such as glycine and glycine hydrochloride. Since the plating bath according to this embodiment is acidic, glycinium ions are a specific example of the glycine-containing water-soluble substance. Specific examples of glycine sources also include glycine derivatives such as the methyl ester of glycine.
  • the polyamine (A) is aliphatic with 12 or less carbon atoms and has no other structure as long as it has a plurality of amino groups.
  • Polyamine (A) may be any of primary amine, secondary amine and tertiary amine.
  • the polyamine (A) may be ionized by being given one or more protons (H + ). Specific examples of the polyamine (A) will be described later.
  • a zinc alloy plating film having a glossy appearance can be easily obtained from an acidic zinc alloy plating bath containing a glycine-containing water-soluble substance and polyamine (A).
  • a zinc alloy plating film having a glossy appearance can be easily obtained from an acidic zinc alloy plating bath containing a glycine-containing water-soluble substance and polyamine (A).
  • the resulting zinc alloy plated film is unlikely to have poor appearance due to abnormal deposition.
  • the plating of the region proximal to the end of the plated member side of the plating film that is, the initial stage of the plating process (immediately after the start of energization)
  • the nickel concentration of the plating formed in the area tends to be specifically higher than in other areas.
  • the abnormal deposition of the plating film is related to the phenomenon that nickel is preferentially deposited at the beginning of plating (immediately after the start of current application) to form a nickel-enriched region (details will be described later).
  • the present additive may contain amino acids other than glycine, even if the present additive contains other amino acids (eg, alanine, glutamine, glutamic acid, etc.), the same effect as glycine can be obtained. is not obtained. That is, other amino acids are not active ingredients of the additive.
  • a nickel-enriched region is less likely to be formed, so that a zinc alloy plating film with a glossy appearance can be stably formed. easy to obtain.
  • high current density plating is intermittently repeated, so the appearance of the zinc alloy plating film formed by barrel plating is easily affected by the plating that is formed at the beginning of plating (immediately after the start of energization). .
  • the plating bath according to the prior art in which the nickel-enriched region is likely to be formed, is used, the appearance of the obtained plating film is likely to be poor.
  • the nickel-enriched region is less likely to be formed in the plating bath according to the present embodiment, poor appearance is less likely to occur even in barrel plating.
  • the glycine/polyamine ratio which is the ratio of the molar concentration of the glycine-containing water-soluble substance in terms of glycic acid to the molar concentration of the polyamine (A), stably realizes that nickel-enriched regions are less likely to occur in the zinc alloy plating film. From the viewpoint, it is preferably 0.1 or more and 40 or less, more preferably 1 or more and 35 or less, and particularly preferably 4 or more and 35 or less.
  • the glycine-containing water-soluble substance and polyamine (A) function as primary brighteners, the content of surfactants normally used as primary brighteners can be reduced. By reducing the content of the surfactant in the plating bath, the problem of foaming that reduces the workability of zinc alloy plating can be alleviated.
  • the zinc alloy plating bath is a zinc-nickel alloy plating bath
  • the zinc alloy plating bath contains the glycine-containing water-soluble substance and the polyamine (A), so that the nickel eutectoid ratio is 10% by mass or more and 20% by mass.
  • a zinc-nickel alloy plating film having a content of preferably 12% by mass or more and 18% by mass or less, more preferably 14% by mass or more and 16% by mass or less may be easily obtained.
  • primary amine polyamine (A) include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis-(3-aminopropyl) ether, 1,2 -bis-(3-aminopropoxy)ethane, 1,3-bis-(3-aminopropoxy)-2,2'-dimethylpropane, aminoethylethanolamine, 1,2-bisaminocyclohexane, 1,3-bis Aminocyclohexane, 1,4-bisaminocyclohexan
  • secondary amine polyamine (A) include N,N'-dimethylethylenediamine, N,N'-dimethyl-1,2-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N , N′-dimethyl-1,2-diaminobutane, N,N′-dimethyl-1,3-diaminobutane, N,N′-dimethyl-1,4-diaminobutane, N,N′-dimethyl-1, 5-diaminopentane, N,N'-dimethyl-1,6-diaminohexane, N,N'-dimethyl-1,7-diaminoheptane, N,N'-diethylethylenediamine, N,N'-diethyl-1, 2-diaminopropane, N,N'-diethyl-1,3-diaminopropane, N,N'-
  • tertiary amine polyamine (A) examples include tetramethylethylenediamine, N,N'-dimethylpiperazine, N,N'-bis((2-hydroxy)propyl)piperazine, hexamethylenetetramine, N,N,N ',N'-tetramethyl-1,3-butanamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N,N,N-tris(3-dimethylaminopropyl)amine, 2,4,6-tris (N,N-dimethylaminomethyl)phenol, heptamethylisobiguanide and the like.
  • the polyamine (A) may have two or more of primary amino groups, secondary amino groups and tertiary amino groups. Examples of such compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and biguanides. Among these, the polyamine (A) preferably contains diethylenetriamine, more preferably composed of diethylenetriamine, from the viewpoint of high stability of the effect, high availability, and the like.
  • the polyamine (A) may be composed of one type of compound, or may be composed of multiple types of compounds.
  • the content ratio of those compounds is not limited. It is appropriately set according to the desired characteristics.
  • the number of carbon atoms in the polyamine (A) may be preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less.
  • Examples of preferred polyamines (A) include ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and among these, ethylenediamine, diethylenetriamine and triethylenetetramine are more preferred polyamines (A).
  • the polyamine (A) preferably has neither a carbonyl group nor a group containing a carbonyl group.
  • the additive may contain components other than polyamine (A).
  • components other than polyamine (A) include primary brighteners, secondary brighteners, antioxidants, defoamers, sequestering agents, and the like.
  • the polyamine (A) contained in the additive according to one embodiment of the present invention functions as a primary brightener and a secondary brightener. At least one may not be contained.
  • a zinc alloy plating bath according to one embodiment of the present invention contains a bath-soluble zinc-containing substance, a bath-soluble metal-containing substance, the above water-soluble glycine-containing substance, and polyamine (A). Therefore, the silver-white zinc alloy plating film formed from the zinc alloy plating bath according to the present embodiment tends to have a good appearance.
  • the zinc alloy plating bath according to the present embodiment contains a bath-soluble zinc-containing substance.
  • the bath-soluble zinc-containing substance is a source of zinc deposited as a zinc alloy plating film, and is one or two selected from the group consisting of zinc cations and bath-soluble substances containing the same.
  • the above ingredients Since the zinc alloy plating bath according to this embodiment is acidic, an example of bath-soluble zinc-containing substances is zinc ions (Zn 2+ ).
  • Zinc chloride, zinc sulfate, zinc oxide and the like are exemplified as raw materials for supplying bath-soluble zinc-containing substances to the plating bath (also referred to as "zinc source" in the present invention).
  • the content of the soluble zinc-containing substance in terms of zinc (the content of the soluble zinc-containing substance in the bath in terms of zinc) in the zinc alloy plating bath according to the present embodiment is not limited. If the content is excessively small, the zinc alloy plating film may be difficult to deposit, so the content in terms of zinc is preferably 5 g / L or more, more preferably 10 g / L or more. It is preferably 15 g/L or more, and particularly preferably 15 g/L or more. If the zinc conversion content of the soluble zinc-containing substance is excessively large, poor appearance and decreased throwing power may occur, so the above zinc conversion content is preferably 100 g / L or less. It is more preferably 80 g/L or less, particularly preferably 60 g/L or less.
  • the zinc alloy plating bath according to one embodiment of the present invention contains a bath-soluble metal-containing substance.
  • the bath-soluble metal-containing substance is a source of metal other than zinc contained in the zinc alloy plating film, and is selected from the group consisting of cations of metal elements and bath-soluble substances containing the same. Refers to one or more components.
  • metal elements contained in the bath-soluble metal-containing substance include iron, nickel, and tin.
  • the metal element contained in the metal-containing substance is selected from the group consisting of iron, nickel, and tin.
  • the raw material for supplying the bath-soluble metal-containing substance to the plating bath may be appropriately selected according to the type of metal element contained in the bath-soluble metal-containing substance.
  • the metal element contained in the bath-soluble metal-containing substance is iron
  • 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.
  • NiSO 4 .6H 2 O, NiCl 2 .6H 2 O, Ni(OH) 2 and the like are exemplified as nickel sources.
  • metal element contained in the bath-soluble metal-containing substance is tin, that is, when the zinc alloy plating bath contains the bath-soluble tin-containing substance, SnSO 4 , SnCl 2 , SnCl 2 .2H 2 O, etc. Exemplified as a tin source.
  • the metal equivalent content of the bath-soluble metal-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is appropriately set according to the composition of the target zinc alloy plating.
  • the content of the bath-soluble iron-containing substance in terms of iron is exemplified to be about 1 g/L or more and 100 g/L or less.
  • the content of the bath-soluble nickel-containing substance in terms of nickel is exemplified to be about 0.1 g/L or more and 60 g/L or less.
  • the tin-equivalent content of the bath-soluble tin-containing substance is exemplified to be about 1 g/L or more and 100 g/L or less.
  • the alloying element content (eutectoid ratio) in the zinc alloy plating film is set according to the properties of the plating bath, the type of alloying elements, the application, and the like.
  • the alloying element contained in the zinc alloy plating bath according to one embodiment of the present invention is nickel
  • the eutectoid ratio of nickel in the zinc-nickel alloy plating film obtained from the zinc alloy plating bath is from the viewpoint of enhancing corrosion resistance. Therefore, it is preferably 5% by mass or more and 20% by mass or less.
  • a zinc-nickel alloy with a nickel content of 10% by mass or more is particularly excellent in corrosion resistance. Therefore, when particularly excellent corrosion resistance is required, the nickel eutectoid ratio in the zinc-nickel alloy plating film should be 10% by mass or more.
  • the eutectoid ratio of nickel is preferably 20% by mass or less, and more preferably 12% by mass or more and 18% by mass or less from the viewpoint of enhancing corrosion resistance and uniformity of the composition of the coating. If the application does not require particularly high corrosion resistance, the eutectoid ratio of nickel in the zinc-nickel alloy plating film should be 5% by mass or more and less than 10% by mass in consideration of the balance between corrosion resistance and productivity (production cost). It may be preferable to The eutectoid rate of nickel can be adjusted by changing the bath composition and current density.
  • Additive component A zinc alloy plating bath according to one embodiment of the present invention contains the aforementioned glycine-containing water-soluble substance and polyamine (A) as active components. It may contain other additive components.
  • a zinc alloy plating bath according to an embodiment of the present invention contains the above-described glycine-containing water-soluble substance.
  • the content of the glycine-containing water-soluble substance depends on the type and content of components other than the glycine-containing water-soluble substance contained in the zinc alloy plating bath, the composition of the zinc alloy plating film formed from the zinc alloy plating bath, etc. Appropriately set.
  • a non-limiting example of the glycine-equivalent content of the glycine-containing water-soluble substance in the zinc alloy plating bath according to one embodiment of the present invention is 0.1 g/L or more and 100 g/L or less.
  • the glycine-containing water-soluble substance When the glycine-containing water-soluble substance is 0.1 g/L or more, the effect of containing the glycine-containing water-soluble substance can be easily obtained. Also, if the glycine-containing water-soluble substance is 100 g/L or less, the substance can be sufficiently dissolved in the plating bath. In setting the composition of the plating bath, it is sometimes preferable that the content of the glycine-containing water-soluble substance is 70 g/L or less from the viewpoint of reducing the influence on the adjustment range of the contents of other components.
  • the glycine-containing water-soluble substance and the polyamine (A) suppress the preferential deposition of nickel at the initial stage of plating (immediately after the start of energization). can be done.
  • the glycine-containing water-soluble substance in the zinc alloy plating bath may be preferably 1 g/L or more, and more preferably 10 g/L or more.
  • the glycine/nickel ratio which is the ratio of the glycine-equivalent molar concentration of the glycine-containing water-soluble substance to the nickel-equivalent molar concentration of the bath-soluble nickel-containing substance, is 0. .1 or greater may be preferred, 0.5 or greater may be more preferred, 1.2 or greater may be particularly preferred, and 1.4 or greater is highly preferred. Sometimes.
  • the upper limit of the glycine/nickel ratio is not set from the viewpoint of improving the appearance of the plating film.
  • the content of the glycine-containing water-soluble substance is excessively large, it may be necessary to adjust the content of other components (for example, potassium-containing components), so the glycine/nickel ratio is 3 or less. is sometimes preferable, and sometimes it is more preferable to be 2 or less.
  • the glycine/nickel ratio has little effect on the eutectoid ratio of nickel in the zinc alloy plating film.
  • a zinc alloy plating bath according to one embodiment of the present invention contains the polyamine (A) described above.
  • the content of polyamine (A) depends on the type of polyamine (A), the type and content of components other than polyamine (A) contained in the zinc alloy plating bath, and the zinc alloy plating film formed from the zinc alloy plating bath. It is appropriately set according to the composition and the like.
  • a non-limiting example of the content of the polyamine (A) in the zinc alloy plating bath according to one embodiment of the present invention is 0.1 g/L or more and 100 g/L or less. When the polyamine (A) is 0.1 g/L or more, the effect of containing the polyamine (A) can be easily obtained. In addition, when the polyamine (A) is 100 g/L or less, the possibility of generating insoluble substances in the bath is reduced.
  • the appearance of the zinc alloy plating film formed from the zinc alloy plating bath can be more stably improved by setting the polyamine (A) in the zinc alloy plating bath to a predetermined content or less. It may be possible to do so.
  • the content of the polyamine (A) is 30 g/L or less, so that the appearance of the zinc-nickel alloy plating film formed from the zinc-nickel alloy plating bath is It may become easier to stably produce good results.
  • the content of the polyamine (A) is preferably 20 g/L or less from the viewpoint of more stably improving the appearance of the zinc-nickel alloy plating film.
  • the zinc alloy plating bath according to one embodiment of the present invention may contain additive components other than the polyamine (A) described above.
  • additive components or materials that provide additive components in zinc alloy plating baths include the following.
  • the zinc alloy plating bath according to one embodiment of the present invention may contain a primary brightener as one of additive components.
  • a primary brightener examples include anionic surfactants, nonionic surfactants and water-soluble organic compounds such as water-soluble cationic polymer compounds used in various zinc plating baths.
  • the primary brightener may have both a structure contained in anionic surfactants such as sulfonic acid groups and a structure contained in nonionic surfactants such as polyethers.
  • anionic surfactants such as sulfonic acid groups
  • nonionic surfactants such as polyethers.
  • Such compounds include alkali metal salts of aromatic or aliphatic polyether sulfates.
  • the primary brightener may preferably be a nitrogen-free surfactant.
  • surfactants include the above aromatic or aliphatic polyether sulfate ester alkali metal salts and polyether compounds of acetylenic dialcohols.
  • the content of the primary brightener in the zinc alloy plating bath is not limited. It is appropriately set according to the type of primary brightener, the type and content of components other than the primary brightener contained in the zinc alloy plating bath, the composition of the zinc alloy plating film formed from the zinc alloy plating bath, and the like.
  • the content of the primary brightener is preferably 0.1 g/L or more and 100 g/L or less, more preferably 0.5 g/L or more and 20 g/L or less.
  • the polyamine (A) functions as a primary brightener, it is possible to reduce the content of the primary brightener composed of a surfactant. By reducing the content of the surfactant in the plating bath, the problem of foaming that reduces the workability of zinc alloy plating can be alleviated.
  • the zinc alloy plating bath according to one embodiment of the present invention may contain a secondary brightener as one of additive components.
  • a secondary brightener as one of additive components.
  • an aromatic compound having a carbonyl group may be contained as a secondary brightener.
  • aromatic aldehydes such as anisaldehyde, veratraldehyde, o-chlorobenzaldehyde (OCAD), salicylaldehyde, vanillin, piperonal and p-hydroxybenzaldehyde; acetone having an aromatic ring such as benzylideneacetone; be done.
  • the content of the secondary brightener in the zinc alloy plating bath is not limited. It is appropriately set according to the type of secondary brightener, the type and content of components other than the secondary brightener contained in the zinc alloy plating bath, the composition of the zinc alloy plating film formed from the zinc-based plating bath, etc. .
  • the content of the secondary brightener is preferably 0.001 g/L or more and 10 g/L or less, more preferably 0.005 g/L or more and 1 g/L or less.
  • the zinc alloy plating bath according to one embodiment of the present invention may contain additive components other than the above components.
  • additive components include antioxidants, antifoaming agents, sequestering agents, and the like.
  • antioxidants examples include phenol, catechol, resorcinol, hydroquinone, hydroxyphenyl compounds such as pyrogallol, L-ascorbic acid, sorbitol, and the like.
  • antifoaming agents examples include silicone antifoaming agents and organic antifoaming agents such as surfactants, polyethers, and higher alcohols.
  • sequestering agents examples include silicates (specific examples include sodium silicate), silica (specific examples include colloidal silica), and the like.
  • the content of the sequestering agent in the zinc alloy plating bath is not limited. It may be appropriately set in consideration of the type of sequestering agent, the composition of the solvent, and the like.
  • the content of the sequestering agent is preferably 0.1 g/L or more and 100 g/L or less, more preferably 0.5 g/L or more and 20 g/L or less.
  • the zinc alloy plating bath according to one embodiment of the present invention may contain a substance having a buffering action as a buffering agent.
  • a buffering agent By containing the buffering agent, excessive increase in the pH in the vicinity of the surface of the member to be plated is suppressed. As a result, the deposition form of metal such as zinc on the member to be plated is stabilized, and abnormal deposition is less likely to occur.
  • the type of buffering agent is not limited.
  • Specific examples of buffering agents include acetate-containing substances that contain at least one of acetate and acetate ions, ammonia-containing substances that contain at least one of ammonia and ammonium ions, and at least one of boric acid and borate ions.
  • boric acid-containing substances which are substances containing
  • the zinc alloy plating applied to the zinc alloy plating bath is a zinc alloy plating
  • the inclusion of an acetic acid-containing substance as a buffer may stabilize the deposition of the zinc alloy plating.
  • the alloying element in the zinc alloy plating is preferably nickel. Potassium acetate is preferred as an acetic acid source for supplying the acetic acid-containing substance to the plating bath.
  • the content of the acetic acid-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is preferably 200 g/L or less, and 100 g/L or less in terms of acetic acid. is more preferable, and 50 g/L or less is even more preferable.
  • the content of the acetic acid-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is preferably 1 g/L or more in terms of acetic acid. /L or more, and particularly preferably 10 g/L or more.
  • the content of the ammonia-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is preferably 100 g/L or less, and 50 g/L or less in terms of ammonia. is more preferably 10 g/L or less, and it is particularly preferable that the zinc alloy plating bath according to one embodiment of the present invention does not substantially contain an ammonia-containing substance (ammonia-free).
  • ammonia-free means not containing ammonia and ammonium ions to the extent that they function as a buffer in the plating bath.
  • the content of the boric acid-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is preferably 5 g / L or less, and 1 g / L or less in terms of boric acid. more preferably 0.1 g/L or less, and the zinc alloy plating bath according to one embodiment of the present invention contains substantially no boric acid-containing substance (boric acid free).
  • boric acid-free means not containing boric acid and borate ions to the extent that it functions as a buffer in the plating bath.
  • acetic acid-containing substance can serve as a buffer for the plating bath.
  • acetic acid-containing substances include substances (acetic acid, acetate ion) based on acetic acid sources such as potassium acetate and sodium acetate.
  • the compounding amount of potassium acetate is preferably 100 g/L or less. There are cases where it is more preferable to make it 70/L or less.
  • the zinc alloy plating bath according to an embodiment of the present invention has a low content of ammonia-containing substances and boric acid-containing substances, and the zinc alloy plating bath has a low environmental load, This means that the zinc alloy plating bath has excellent wastewater treatment properties.
  • a zinc alloy plating bath according to one embodiment of the present invention may contain an inorganic electrolyte.
  • inorganic electrolytes include chloride ions, sulfate ions, nitrate ions, phosphate ions, sodium ions, potassium ions, magnesium ions, and aluminum ions. may be blended in.
  • a potassium salt such as potassium chloride may be preferred from the viewpoint of ease of dissolution.
  • the total content of the inorganic electrolyte contained in the zinc alloy plating bath according to one embodiment of the present invention is not limited.
  • the total content of the inorganic electrolyte contained in the zinc alloy plating bath is preferably 10 g/L or more and 1000 g/L or less, more preferably 50 g/L or more and 500 g/L or less.
  • the concentration of chloride ions in the bath is 100 g/L or more and 400 g from the viewpoint of ensuring the stability of the bath. /L or less may be preferable, and 120 g/L or more and 280 g/L or less may be more preferable.
  • the solvent of the zinc alloy plating bath according to one embodiment of the present invention has water as its main component.
  • a solvent other than water an organic solvent having high solubility in water such as alcohol, ether, ketone, etc. may be mixed.
  • the ratio is preferably 10% by volume or less with respect to the total solvent.
  • the zinc alloy plating bath according to one embodiment of the present invention is acidic, and its pH is preferably 4 or more and 6 or less, more preferably 5.0 or more and 5.8 or less.
  • the type of material used for adjusting the pH of the plating bath is not particularly limited. Known materials such as hydrochloric acid, sulfuric acid, nitric acid, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide may be used.
  • the preparation method of the zinc alloy plating bath according to the present embodiment is not particularly limited.
  • the zinc alloy plating bath contains a zinc source, a metal source, a glycine source, a polyamine (A) source which is a substance capable of producing polyamine (A) in the plating bath, and optionally the other additive components described above as optional additive components. , a buffering agent, an inorganic electrolyte, etc., in a solvent.
  • the glycine source contains glycine
  • the polyamine (A) source contains polyamine (A).
  • a zinc alloy plated member can be obtained by bringing the zinc alloy plating bath according to the present embodiment into contact with a member to be plated, and performing electrolysis using the member to be plated as a cathode.
  • the contact method between the zinc alloy plating bath and the member to be plated is not limited.
  • the member to be plated is brought into contact with the zinc alloy plating bath, and the contact may be performed by spraying the plating solution that constitutes the zinc alloy plating bath onto the member to be plated.
  • the material of the member to be plated is not particularly limited as long as it has conductivity.
  • Metal materials such as iron materials, and non-conductive materials such as resin materials and ceramic materials having a layer made of a conductive material formed by electroless plating on the surface are exemplified.
  • the shape of the member to be plated is also not particularly limited. Primary processed products such as plates, rods, and wires; cut and ground products such as screws, bolts, and molds (which may be further polished); press processing such as vehicle body frames and equipment housings products, and secondary products such as castings such as brake calipers and engine blocks. If the member to be plated is a casting made of an iron-based material, a zinc alloy plating film cannot be formed from an alkaline zinc alloy plating bath due to the influence of the components contained to improve castability. Sometimes.
  • the material that constitutes the anode is not particularly limited.
  • a metallic material containing zinc or an alloying element may be used as the soluble anode.
  • As soluble anodes an anode made of a zinc-based material and an anode made of a material containing an alloy element may be separately prepared. Then, these anodes may be connected to different power sources and voltage application to each anode may be independently controlled.
  • the current density in electrolysis is not particularly limited. If the current density is too low, the deposition rate of the resulting zinc alloy plating film may be low and productivity may be poor. Considering that there is a possibility that the electrodepositability, throwing power, etc. may be deteriorated, it may be appropriately set. From the viewpoint of improving productivity and improving the quality of the plating film, it is preferably 0.1 A/dm 2 or more and 15 A/dm 2 or less, and 0.5 A/dm 2 or more and 13 A/dm 2 or less. is more preferable.
  • the acidic zinc alloy plating bath containing the glycine-containing water-soluble substance and polyamine (A) can Since nickel-enriched regions are less likely to be formed in the plated film, the obtained plated film is less likely to have poor appearance.
  • the temperature of the plating bath (plating bath temperature) in electrolysis may be in the range of about 15°C to about 50°C, and may be performed at about room temperature (about 25°C).
  • the electrolysis time (plating time) is appropriately set from the deposition rate of the plating film determined by the composition of the zinc alloy plating bath, the above-mentioned current density, plating bath temperature, etc., and the desired thickness of the plating film.
  • the configuration of the plating equipment is not particularly limited.
  • a member to be plated as a cathode is placed in a zinc alloy plating bath so as to face a plate-shaped or rod-shaped anode, and electrolysis is performed while appropriately stirring the liquid in the zinc alloy plating bath to form a zinc alloy plating film on the member to be plated. may be formed.
  • the liquid may be stirred by using a liquid circulation pump, by aeration, or by moving the member to be plated or the like in the plating bath.
  • a barrel containing a member to be plated such as a bolt is immersed in a zinc alloy plating bath, and electrolysis is performed while rotating the barrel to form a zinc alloy plating film on the member to be plated.
  • a barrel plating facility that forms a Specific examples of members to be plated using barrel plating equipment include bolts, nuts, and screws.
  • Zinc alloy plated film In the zinc-nickel alloy plated film formed using this additive, when the depth profile of the zinc alloy plated member formed on the member to be plated made of iron-based material is measured, A nickel-enriched region having a relatively high nickel concentration is less likely to be formed on the proximal side.
  • the nickel-enriched region can be confirmed by a graph (depth profile) showing changes in the thickness direction of the plating film in the component concentration of the plating member.
  • a graph depth profile showing changes in the thickness direction of the plating film in the component concentration of the plating member.
  • the zinc concentration is 60% by mass or more and the position closest to the outermost surface is the zinc alloy It is defined as the surface side edge of the plating film.
  • the position where the concentration of zinc is equal to the concentration of iron derived from the member to be plated is defined as the side end portion of the member to be plated for zinc alloy plating.
  • the length of the region from the surface-side end to the plated-side end is defined as the thickness of the zinc alloy plating film.
  • the initial region consisting of the position shifted from the end of the zinc alloy plating film on the side of the member to be plated to the surface side by 30% of the thickness of the zinc alloy plating and the end on the side of the member to be plated.
  • a partial region with a nickel concentration in the case where the alloying element in the alloying element concentration is nickel
  • that partial region is treated with nickel It is called an enriched region (when the alloying element in the alloying element enriched region is nickel).
  • the presence of nickel-enriched regions should be judged from the overall shape of the depth profile, but the following evaluation method also helps to confirm the presence of nickel-enriched regions. That is, when the range of 40% to 60% of the thickness of the zinc alloy plating from the surface side edge is defined as the intermediate region, the zinc nickel alloy plating film having the nickel enriched region has an average nickel concentration in this intermediate region value (this average value is also referred to as “intermediate region average value”) [Ni1], and the maximum value of nickel concentration in the initial region (this maximum value is also referred to as “initial region maximum value”) [Ni2]. , satisfies the following formula (2), there is a high possibility that a nickel-enriched region occurs in the initial region. [Ni1] ⁇ [Ni2] (2)
  • the zinc alloy plating film (zinc-nickel alloy plating film) is formed from a plating bath containing a glycine-containing water-soluble substance and polyamine (A). is less likely to occur, and the following formula (1) is likely to be satisfied. [Ni1] ⁇ [Ni2] (1)
  • the zinc alloy plating film (zinc-nickel alloy plating film) according to the present embodiment has a high current density, specifically, even at a portion formed under conditions exceeding 10 A / dm is less likely to occur.
  • a chemical conversion treatment may be applied to the zinc alloy plating film of the zinc alloy plated member.
  • the zinc-nickel alloy plating film formed from the zinc-nickel plating bath according to this example containing glycine, which is a glycine-containing water-soluble substance, and diethylenetriamine, which is a polyamine (A), has a current density of 11A. No particular poor appearance was observed in the /dm 2 portion.
  • FIG. 1 shows a depth profile of concentrations of zinc and nickel contained in the zinc-nickel alloy plating film and iron contained in the cathode plate.
  • the position closest to the outermost surface where the concentration of zinc was 60% by mass or more was defined as the edge on the surface side of the zinc alloy plating film.
  • the length of the range from the end on the surface side to the end on the side of the member to be plated (indicated by the white arrow in FIG. 1) was defined as the thickness of the zinc alloy plating film. Based on the depth profile shown in FIG. 1, the thickness of the zinc alloy plating film was 275 nm. The length between the edge on the surface side and the outermost surface was about 1 nm, which was almost negligible considering the measurement accuracy of the depth profile of GD-OES.
  • FIGS. 2 to 4 Depth profiles were obtained for the nickel concentration at the current density of 11 A/dm 2 in each of the zinc-nickel alloy plating films produced by the examples and the comparative examples. The results are shown in FIGS. 2 to 4.
  • the maximum value [Ni2] in the initial region tends to be larger than the average value [Ni1] in the intermediate region ([Ni1] ⁇ [Ni2]). observed, confirming the presence of a nickel-enriched region.
  • the average value [Ni1] in the intermediate region tends to be greater than or equal to the maximum value [Ni2] in the initial region ([Ni1] ⁇ [Ni2]), and the nickel enriched region was not confirmed.
  • Examples 4 to 13 and 20 Using the composition of the plating solution of Example 1 as a base, as shown in Table 3, a plurality of types of plating solutions having different nickel equivalent molar concentrations of the bath-soluble nickel-containing substances and different glycine molar concentrations were prepared.
  • Table 4 the numbers in the columns “Ni”, “Gly” and “DETA” are the molar concentrations of nickel (unit: mol/L), the molar concentrations of glycine (unit: mol/L) and the molar concentrations of diethylenetriamine, respectively. (Unit: mmol/L).
  • the numbers in the "Gly/Ni” column are the calculation results (glycine/nickel ratio) of (molar concentration of glycine)/(molar concentration of nickel), and the numbers in the "Gly/PA” column are (molar concentration of glycine). It is a calculation result (glycine/polyamine ratio) of (molar concentration)/(molar concentration of diethylenetriamine).
  • Electrolysis was performed for each of the prepared plating solutions under the same conditions as in Example 1, and the appearance of the zinc-nickel alloy plating film formed on the cathode plate at a current density of 11 A/dm 2 was observed.
  • the films according to any of the examples were glossy (appearance of silvery white color, and the observer's eyes could clearly see them when facing the cathode plate). .
  • the depth profile was measured by glow discharge optical emission spectroscopy (GD-OES) for the portion of the obtained zinc-nickel alloy plating film with a current density of 11 A/dm 2 .
  • the results are shown in FIGS. 5 to 14.
  • FIG. As shown in these figures, no nickel-enriched region was observed in the initial region in the depth profiles of any of the plating films. Comparing the average value [Ni1] in the intermediate region and the maximum value [Ni2] in the initial region, as shown in Table 3, basically the average value [Ni1] in the intermediate region is the maximum value [Ni2] in the initial region. Ni2] or more ([Ni1] ⁇ [Ni2]), and no result was obtained in which [Ni2] clearly exceeded [Ni1]. That is, even in the portion where the current density exceeds 10 A/dm 2 , an appropriate A zinc-nickel alloy plating film having a good appearance was obtained.
  • Example 14 to 19 and Comparative Examples 4 to 8 Plating baths shown in Table 4 were prepared.
  • the plating bath of Comparative Example 4 is included in the scope of the electrolytic composition shown as Example 1 of Patent Document 3.
  • diethylenetriamine which is a kind of polyamine according to the present invention, was added to the plating bath of Comparative Example 4 so that the glycine/polyamine ratio was the same as in Example 1 (6.0). It is a thing.
  • the plating bath of Example 15 has almost the same composition as the plating bath of Example 1.
  • the plating bath of Comparative Example 5 was obtained by removing diethylenetriamine from the plating bath of Example 15 and containing the same amount of boric acid as in the plating bath of Comparative Example 4.
  • the plating bath of Comparative Example 5 is the plating bath of Comparative Example 4 with the same nickel concentration and chlorine concentration as in Example 15.
  • the plating bath of Comparative Example 6 is the same as the plating bath of Comparative Example 4 except that it does not contain boric acid. This composition differs from the plating bath of Comparative Example 1 shown for reference in nickel concentration and chlorine concentration.
  • Plating baths shown in Table 5 were prepared.
  • the plating bath of Comparative Example 7 does not contain glycine from the plating bath of Comparative Example 4 included in the range of the electrolytic composition shown as Example 1 of Patent Document 3, and contains the same amount of diethylenetriamine as that of Example 14. It is what I let you do.
  • the plating bath of Comparative Example 8 was obtained by adding the same amount of boric acid as in Comparative Example 4 to the plating bath of Comparative Example 1.
  • the plating bath of Example 16 has the same composition as the plating bath of Example 15.
  • the plating bath of Example 18 was obtained by adding 100 g/L (1.9 mol/L) of ammonium chloride to the plating bath of Example 16 and lowering the concentration of potassium chloride to 120 g/L (1.6 mol/L). and a chlorine concentration of 180 g/L (5.1 mol/L).
  • the chlorine concentration (152 g/L) of Example 16 is 4.3 mol/L.
  • the cathode plate on which the zinc-nickel alloy plating film was formed was equally divided into 20 regions with different current densities. Arithmetic mean value of the current density of and the current density of the end on the low current density side was obtained. The calculated arithmetic average value was taken as the average current density in that region. The numerical value (unit: A/dm 2 ) in the second row of Table 6 indicates this average current density.
  • the numbers in bold in the rows of each example and comparative example are the results of classifying the appearance evaluation results of each region as follows. 1: Glossy (It has a silvery white appearance, and the observer's eyes can be clearly seen when facing the cathode plate and looking into it.) 2: Semi-gloss (Appearance is silvery white, but the observer's eyes are blurred, or reflection can be confirmed) 3: Black (appearance is black instead of silvery white) 4: Burnt (plated surface is rough)
  • Nickel measured by glow discharge optical emission spectroscopy (GD-OES) for portions of the zinc-nickel alloy plating films according to Comparative Example 4, Comparative Examples 6 to 8, and Examples 16 to 20 at a current density of 11 A/dm 2 were measured (Figs. 15 to 22).
  • the horizontal axis indicating the depth is standardized by the thickness of each plating film (the depth at which the zinc concentration and the iron concentration are equal).
  • the standardized depth was about 0.8 to about 0.85. The existence of a nickel-enriched region where the concentration of is specifically increased was confirmed. In contrast, as shown in FIGS.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

La présente invention concerne un additif destiné à un bain de placage d'alliage de zinc acide, l'additif étant utilisé pour obtenir un bain de placage d'alliage de zinc acide pouvant offrir un film de placage d'alliage de zinc présentant un aspect satisfaisant, et contenant comme constituants actifs une substance soluble dans l'eau contenant de la glycine, et une polyamine aliphatique comportant 12 atomes de carbone au maximum. Le rapport glycine/polyamine, c'est-à-dire un rapport de la concentration molaire en termes de glycine de la substance soluble dans l'eau contenant de la glycine, à la concentration molaire de la polyamine aliphatique, peut être compris de préférence entre 0,1 et 40 inclus. La présente invention concerne également un bain de placage d'alliage de zinc acide comprenant l'additif, et un film de placage d'alliage de zinc formé à l'aide du bain de placage d'alliage de zinc acide.
PCT/JP2022/008540 2021-03-05 2022-03-01 Additif pour bain de placage d'alliage de zinc acide, bain de placage d'alliage de zinc acide et film de placage d'alliage de zinc WO2022186183A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023503852A JPWO2022186183A1 (fr) 2021-03-05 2022-03-01

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-035404 2021-03-05
JP2021035404 2021-03-05

Publications (1)

Publication Number Publication Date
WO2022186183A1 true WO2022186183A1 (fr) 2022-09-09

Family

ID=83154763

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/008540 WO2022186183A1 (fr) 2021-03-05 2022-03-01 Additif pour bain de placage d'alliage de zinc acide, bain de placage d'alliage de zinc acide et film de placage d'alliage de zinc

Country Status (2)

Country Link
JP (1) JPWO2022186183A1 (fr)
WO (1) WO2022186183A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60106996A (ja) * 1983-11-16 1985-06-12 Kawasaki Steel Corp 耐食性Ζｎ−アルミナ複合めっき鋼板の製造方法
JPS60114587A (ja) * 1983-11-28 1985-06-21 C Uyemura & Co Ltd 酸性亜鉛めっき方法
JPS60116794A (ja) * 1983-11-28 1985-06-24 C Uyemura & Co Ltd 酸性亜鉛めっき方法
JPS61163289A (ja) * 1985-01-14 1986-07-23 Nippon Kagaku Sangyo Kk ニツケル及びニツケル合金による黒色電気めつき浴
JPS61204387A (ja) * 1985-03-07 1986-09-10 C Uyemura & Co Ltd 酸性亜鉛めつき方法
JPS61204390A (ja) * 1985-03-07 1986-09-10 C Uyemura & Co Ltd 酸性亜鉛めつき方法
JPH0874089A (ja) * 1994-09-09 1996-03-19 Nkk Corp 白色度に優れる電気亜鉛めっき鋼板及びその製造方法
JP2016065295A (ja) * 2014-09-25 2016-04-28 ユケン工業株式会社 酸性亜鉛合金めっき浴用添加剤、酸性亜鉛合金めっき浴および亜鉛合金めっき部材の製造方法
JP2018523017A (ja) * 2015-08-11 2018-08-16 ポスコＰｏｓｃｏ 表面外観に優れた電気亜鉛めっき鋼板用の亜鉛フラッシュめっき溶液、それを用いた電気亜鉛めっき鋼板の製造方法、及び電気亜鉛めっき鋼板

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60106996A (ja) * 1983-11-16 1985-06-12 Kawasaki Steel Corp 耐食性Ζｎ−アルミナ複合めっき鋼板の製造方法
JPS60114587A (ja) * 1983-11-28 1985-06-21 C Uyemura & Co Ltd 酸性亜鉛めっき方法
JPS60116794A (ja) * 1983-11-28 1985-06-24 C Uyemura & Co Ltd 酸性亜鉛めっき方法
JPS61163289A (ja) * 1985-01-14 1986-07-23 Nippon Kagaku Sangyo Kk ニツケル及びニツケル合金による黒色電気めつき浴
JPS61204387A (ja) * 1985-03-07 1986-09-10 C Uyemura & Co Ltd 酸性亜鉛めつき方法
JPS61204390A (ja) * 1985-03-07 1986-09-10 C Uyemura & Co Ltd 酸性亜鉛めつき方法
JPH0874089A (ja) * 1994-09-09 1996-03-19 Nkk Corp 白色度に優れる電気亜鉛めっき鋼板及びその製造方法
JP2016065295A (ja) * 2014-09-25 2016-04-28 ユケン工業株式会社 酸性亜鉛合金めっき浴用添加剤、酸性亜鉛合金めっき浴および亜鉛合金めっき部材の製造方法
JP2018523017A (ja) * 2015-08-11 2018-08-16 ポスコＰｏｓｃｏ 表面外観に優れた電気亜鉛めっき鋼板用の亜鉛フラッシュめっき溶液、それを用いた電気亜鉛めっき鋼板の製造方法、及び電気亜鉛めっき鋼板

Also Published As

Publication number Publication date
JPWO2022186183A1 (fr) 2022-09-09

Similar Documents

Publication Publication Date Title
CN1922343B (zh) 用于电镀锌-镍三元的和更高的合金的电镀液，系统和方法及其电镀产品
KR101502804B1 (ko) Ｐｄ 및 Ｐｄ-Ｎｉ 전해질 욕조
EP2350355B1 (fr) Bains et procédés d'électroplacage d'alliage de zinc
CN104911648A (zh) 无氰化物的酸性亚光银电镀组合物及方法
US3730853A (en) Electroplating bath for depositing tin-lead alloy plates
WO2007025606A1 (fr) Additif polymère azoté utilisé pour le dépôt électrolytique de zinc et d’alliages de zinc et procédé servant à le préparer et à l’utiliser
JP5419021B2 (ja) ジンケート型亜鉛めっき浴
WO2022186183A1 (fr) Additif pour bain de placage d'alliage de zinc acide, bain de placage d'alliage de zinc acide et film de placage d'alliage de zinc
JP3261676B2 (ja) 電気ニッケルめっき浴。
JP2007308801A (ja) ニッケル・コバルト・リン電気メッキの組成物及びその用途
JP2016069725A (ja) 酸性亜鉛合金めっき浴用添加剤、酸性亜鉛合金めっき浴および亜鉛合金めっき部材の製造方法
CN114164466B (zh) 一种碱性电镀锌铁合金添加剂及电镀液
JP5740616B1 (ja) 酸性亜鉛合金めっき浴用添加剤、酸性亜鉛合金めっき浴および亜鉛合金めっき部材の製造方法
KR101173879B1 (ko) 니켈플래시 도금용 다기능성 과포화 슬러리 도금용액
JP5861176B2 (ja) 亜鉛−ニッケル合金めっき液並びにめっき方法
JP2014088608A (ja) ジンケート型亜鉛系めっき浴、ジンケート型亜鉛系めっき浴用添加剤および亜鉛系めっき部材の製造方法
JP5747359B2 (ja) ジンケート型亜鉛系めっき浴、ジンケート型亜鉛系めっき浴用添加剤および亜鉛系めっき部材の製造方法
JPH1060683A (ja) 電気めっき三元系亜鉛合金とその方法
JP2020117803A (ja) インジウム電気めっき組成物及びインジウムをニッケル上に電気めっきするための方法
JP5728711B2 (ja) ジンケート型亜鉛系めっき浴用添加剤、ジンケート型亜鉛系めっき浴および亜鉛系めっき部材の製造方法
JP2014037621A (ja) ジンケート型亜鉛系めっき浴、ジンケート型亜鉛系めっき浴用添加剤および亜鉛系めっき部材の製造方法
US11643742B2 (en) Silver/tin electroplating bath and method of using the same
JPH05222568A (ja) メッキ液組成物
KR20130070235A (ko) 아연도금강판용 황산욕 Ｆｅ계 전해액
WO2010101212A1 (fr) Bain d'électro-placage d'alliage de cuivre et de zinc et procédé de placage au moyen de celui-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22763238

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023503852

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22763238

Country of ref document: EP

Kind code of ref document: A1