JP5728711B2 - Zincate-type zinc-based plating bath additive, zincate-type zinc-based plating bath, and method for producing zinc-based plated member - Google Patents
Zincate-type zinc-based plating bath additive, zincate-type zinc-based plating bath, and method for producing zinc-based plated member Download PDFInfo
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- JP5728711B2 JP5728711B2 JP2013159859A JP2013159859A JP5728711B2 JP 5728711 B2 JP5728711 B2 JP 5728711B2 JP 2013159859 A JP2013159859 A JP 2013159859A JP 2013159859 A JP2013159859 A JP 2013159859A JP 5728711 B2 JP5728711 B2 JP 5728711B2
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- Prior art keywords
- zinc
- plating bath
- bath
- soluble
- water
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- 238000007747 plating Methods 0.000 title claims description 229
- 239000011701 zinc Substances 0.000 title claims description 163
- 229910052725 zinc Inorganic materials 0.000 title claims description 162
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 160
- 239000000654 additive Substances 0.000 title claims description 39
- 230000000996 additive effect Effects 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 71
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 125000005647 linker group Chemical group 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 238000005246 galvanizing Methods 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- -1 zinc cations Chemical class 0.000 description 24
- 239000007788 liquid Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910001297 Zn alloy Inorganic materials 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 230000002159 abnormal effect Effects 0.000 description 13
- 239000002738 chelating agent Substances 0.000 description 13
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- 238000001556 precipitation Methods 0.000 description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000003352 sequestering agent Substances 0.000 description 6
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 5
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- 230000000694 effects Effects 0.000 description 4
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
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- 239000000956 alloy Substances 0.000 description 3
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- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
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- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Description
本発明は、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に関する。 The present invention relates to an additive for zincate-type zinc-based plating bath, a zincate-type zinc-based plating bath, and a method for producing a zinc-based plated member.
本明細書において、亜鉛系めっきとは、亜鉛および不可避的な不純物からなる亜鉛めっきと、亜鉛および合金成分ならびに不可避的な不純物からなる亜鉛合金めっきとの総称である。ここで、亜鉛合金めっきはめっき中の亜鉛の含有量（質量％）が他の合金元素の含有量（質量％）のいずれよりも高くてもよいし、亜鉛の含有量（質量％）よりも含有量が高い合金元素が含まれていてもよい。 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.
亜鉛系めっきからなる皮膜（本明細書において「亜鉛系めっき皮膜」ともいう。）は、自動車用の鋼板やボルトやナットなどの鋼材からなる機械部品をはじめとして、我々の身の回りの部材に対して、耐食性を向上させるなどの目的で広汎に用いられている。亜鉛−ニッケル合金、亜鉛−鉄合金、すず−亜鉛合金など、亜鉛合金めっき皮膜も、耐食性に加えて耐熱性や耐塩水性の向上などが求められる場合には、広く利用されている。 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.
亜鉛系めっき皮膜は、亜鉛系めっき皮膜を形成するためのめっき浴（本明細書において「亜鉛系めっき浴」ともいう。）に被めっき部材を浸漬した状態で電解を行う電気めっきにて形成される。この亜鉛系めっき浴は、アルカリ浴と酸性浴とに大別され、アルカリ浴にはシアン化物浴やジンケート型亜鉛系めっき浴、酸性浴には塩化亜鉛浴や硫酸亜鉛浴がある。求める亜鉛系めっき皮膜の硬度や光沢性、被めっき部材の形状や大きさ、作業環境などの様々な条件を勘案して、これらの亜鉛系めっき浴から適切な浴が選択されている。 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.
これらの亜鉛系めっき浴の中でも、ジンケート型亜鉛系めっき浴は、排水処理の負担が大きいシアン化物を使用しない上、浴組成が比較的単純で管理しやすく、プレス小物、ボルト、ナットなどにも適用できる利点があるため、好まれて工業的な実施がなされている。また、めっき皮膜の特性を向上させたり、浴の安定性を向上させたりする観点から、多くの改良型浴が開発されている。 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.
例えば、特許文献１には、対象物の表面の箇所ごとでの膜厚のばらつきの幅が小さい亜鉛皮膜を速やかに形成することを可能にする亜鉛めっき浴添加剤および非シアン系アルカリ性亜鉛めっき浴を提供することを目的として、下記式（ｉ）で示される構成単位（ａ）および下記式（ｉｉ）で示される構成単位（ｂ）を含む水溶性共重合体を含有する亜鉛めっき浴添加剤が開示されている。 For example, Patent Document 1 discloses a zinc plating bath additive and a non-cyan alkaline galvanizing bath that can quickly form a zinc film having a small variation in film thickness at each location on the surface of an object. A zinc plating bath additive containing a water-soluble copolymer containing a structural unit (a) represented by the following formula (i) and a structural unit (b) represented by the following formula (ii) Is disclosed.
特許文献１に開示された亜鉛めっき浴添加剤は、１５Ａ／ｄｍ２程度までの電流密度の範囲であれば、異常析出を生じにくく、すぐれた特性を有する亜鉛めっき皮膜を形成することができる。 If the galvanizing bath additive disclosed in Patent Document 1 is in a current density range up to about 15 A / dm 2 , abnormal precipitation hardly occurs and a galvanized film having excellent characteristics can be formed.
ところで、めっき対象物の形状などの理由により、めっき浴中の電流密度が、局所的に５０Ａ／ｄｍ２程度以上に達する場合がある。具体的には、ラックなどの引掛け治具を用いてめっきを行う場合には、引掛け治具の引掛け部の先端部のように突出した部分では、その形状的な特徴に基づき、電流密度が５０Ａ／ｄｍ２程度以上となることがある。本明細書において、このような、電流密度が特に高くなる部分を、「超高電流密度部分」ともいう。 Incidentally, the current density in the plating bath may locally reach about 50 A / dm 2 or more for reasons such as the shape of the plating object. Specifically, when plating is performed using a hooking jig such as a rack, the projecting portion such as the tip of the hooking part of the hooking jig has a current characteristic based on its shape characteristics. The density may be about 50 A / dm 2 or more. In this specification, such a portion where the current density is particularly high is also referred to as an “ultra-high current density portion”.
従来技術に係る亜鉛系めっき浴では、このような局所的な超高電流密度部分では、正常なめっき皮膜が形成されず、針状結晶のような異常析出が生じやすかった。この異常析出しためっき金属は、被めっき部材から脱離しやすく、めっき浴中に分散する異物となっていた。この異物がストレーナーのようなフィルター部材により適切に回収されれば、特段の問題は生じないが、この異物が回収される前に被めっき部材の正常な析出が行われるべき部位に付着すると、付着した異物がめっき皮膜内に取り込まれ、結果的に、めっき皮膜の外観不良をもたらす場合があった。すなわち、超高電流密度部分において生じた異常析出が、めっき皮膜の外観不良の原因となる場合があった。 In the zinc-based plating bath according to the prior art, a normal plating film is not formed in such a local ultrahigh current density portion, and abnormal precipitation such as needle crystals is likely to occur. The abnormally precipitated plating metal was easily detached from the member to be plated and was a foreign substance dispersed in the plating bath. If this foreign matter is properly collected by a filter member such as a strainer, no particular problem will occur. However, if this foreign matter adheres to a site where normal deposition of the member to be plated should occur before it is collected, In some cases, the foreign matter is taken into the plating film, resulting in poor appearance of the plating film. That is, abnormal precipitation that occurs in the ultrahigh current density portion may cause the appearance defect of the plating film.
本発明は、超高電流密度部分においても異常析出が生じにくいジンケート型亜鉛系めっき浴を形成しうる亜鉛系めっき浴添加剤、かかる亜鉛系めっき浴添加剤に含まれる水溶性共重合体を含有する亜鉛系めっき浴、および上記亜鉛系めっき浴を用いて形成される亜鉛系めっき部材の製造方法を提供することを目的とする。
なお、亜鉛系めっき部材とは、被めっき部材と、この被めっき部材の被めっき面上に積層された亜鉛系めっき皮膜とを備えた部材をいう。
The present invention includes a zinc-based plating bath additive capable of forming a zincate-type zinc-based plating bath that is unlikely to cause abnormal precipitation even in an ultrahigh current density portion, and a water - soluble copolymer contained in such a zinc-based plating bath additive. It is an object of the present invention to provide 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.
上記課題を解決するために提供される本発明は次のとおりである。
〔１〕下記式（１）で示される構造からなる構成単位（Ｕ１）（下記式（１）中、Ｘは酸素元素または硫黄元素を表し、ｚは２または３を表す。）（ただし、下記構成単位（Ｕ２）の一部として存在する構成単位は除く。）および下記式（２）で示される構造からなる構成単位（Ｕ２）（下記式（２）中、Ｘは酸素元素または硫黄元素を表す。）を含む水溶性共重合体のそれぞれを含有することを特徴とする亜鉛系めっき浴添加剤。
[1] Configuration unit comprising structure represented by the following formula (1) (U1) (In the following formula (1), X represents an oxygen element or sulfur element, z represents 2 or 3.) (However, the following The structural unit existing as a part of the structural unit (U2) is excluded.) And the structural unit (U2) having a structure represented by the following formula (2) (in the following formula (2), X represents an oxygen element or a sulfur element. A zinc-based plating bath additive characterized by containing each of the water-soluble copolymers including
〔２〕前記水溶性共重合体は、前記構成単位（Ｕ１）と前記構成単位（Ｕ２）とが連結基を介して結合している部分を有する、上記〔１〕に記載の亜鉛系めっき浴添加剤。 [2] The zinc-based plating bath according to [1], wherein the water-soluble copolymer has a portion in which the structural unit (U1) and the structural unit (U2) are bonded via a linking group. Additive.
〔３〕前記水溶性共重合体は、前記構成単位（Ｕ１）同士、前記構成単位（Ｕ２）同士、または前記構成単位（Ｕ１）と前記構成単位（Ｕ２）とが、下記式（３）で示される連結基（Ｕ３）および／または下記式（４）で示される連結基（Ｕ４）を介して連結している部分を有する、上記〔１〕または〔２〕に記載の亜鉛系めっき浴添加剤。
〔４〕前記連結基（Ｕ３）を示す上記式（３）中のａ、ｂ、ｄおよびｅはいずれも１であり、前記連結基（Ｕ４）を示す上記式（４）中のｆ、ｇ、ｈおよびｉはいずれも１である、上記〔３〕に記載の亜鉛めっき浴添加剤。 [4] a, b, d and e in the above formula (3) representing the linking group (U3) are all 1, and f, g in the above formula (4) representing the linking group (U4). , H and i are all 1, the galvanizing bath additive according to [3] above.
〔５〕上記〔１〕から〔４〕のいずれかに記載される亜鉛めっき浴添加剤に含まれる前記水溶性共重合体および浴可溶性亜鉛含有物質を含有することを特徴とするジンケート型亜鉛系めっき浴。
[5] A zincate-type zinc system comprising the water - soluble copolymer and the bath-soluble zinc-containing substance contained in the zinc plating bath additive according to any one of [1] to [4] Plating bath.
〔６〕前記水溶性共重合体を塩化物換算で０．１ｇ／Ｌ以上５０ｇ／Ｌ以下含む、上記〔５〕に記載のめっき浴。 [6] The plating bath as described in [5] above, which contains the water-soluble copolymer in an amount of 0.1 g / L to 50 g / L in terms of chloride.
〔７〕シアン化物を含有しない、上記〔５〕または〔６〕に記載のめっき浴。 [7] The plating bath according to the above [5] or [6], which does not contain cyanide.
〔８〕二次光沢剤を含有する、上記〔５〕から〔７〕のいずれか一項〕に記載のめっき浴。 [8] The plating bath according to any one of [5] to [7] above, which contains a secondary brightener.
〔９〕浴可溶性亜鉛含有物質を亜鉛換算で２ｇ／Ｌ以上６０ｇ／Ｌ含有する上記〔５〕から〔８〕のいずれか一項に記載のめっき浴。 [9] The plating bath according to any one of [5] to [8], 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.
〔１０〕浴可溶性金属含有物質をさらに含有し、当該浴可溶性金属含有物質に含まれる金属元素は鉄、ニッケル、コバルトおよびマンガンからなる群から選ばれる一種または二種以上である上記〔５〕から〔９〕のいずれか一項に記載のめっき浴。 [10] From the above [5], further comprising a bath-soluble metal-containing material, wherein the metal element contained in the bath-soluble metal-containing material is one or more selected from the group consisting of iron, nickel, cobalt and manganese [9] The plating bath according to any one of [9].
〔１１〕被めっき部材と、該被めっき部材の被めっき面上に積層された亜鉛系めっき皮膜とを備えた亜鉛系めっき部材の製造方法であって、上記〔５〕から〔１０〕のいずれかに記載されるジンケート型亜鉛系めっき浴を用いることを特徴とする亜鉛系めっき部材の製造方法。 [11] A method for producing a zinc-based plated member comprising a member to be plated and a zinc-based plated film laminated on the surface to be plated of the member to be plated, wherein any one of the above [5] to [10] A method for producing a zinc-based plated member, comprising using a zincate-type zinc-based plating bath described in (1).
上記の発明に係るジンケート型亜鉛系めっき浴は、超高電流密度部分においても異常析出が生じにくい。 In the zincate-type zinc plating bath according to the above-described invention, abnormal precipitation hardly occurs even in the ultrahigh current density portion.
以下、本発明について詳しく説明する。
１．ジンケート型亜鉛系めっき浴
本発明の一実施形態に係る亜鉛系めっき浴は、ジンケート型のめっき浴であるから、液性はアルカリ性である。また、本実施形態の好ましい一例に係る亜鉛系めっき浴はシアン化物を含有せず、有害なシアンガスが発生しないため、作業性に優れ、環境に優しい。
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）金属成分
（１−１）浴可溶性亜鉛含有物質
本実施形態に係る亜鉛系めっき浴は、浴可溶性亜鉛含有物質を含有する。本明細書において浴可溶性亜鉛含有物質とは、亜鉛系めっき皮膜として析出する亜鉛の供給源であって、亜鉛の陽イオンおよびこれを含有する浴可溶性物質からなる群から選ばれる一種または二種以上の成分をいう。本実施形態に係る亜鉛系めっき浴はジンケート型の浴であるから、めっき浴はアルカリ性である。したがって、浴可溶性亜鉛含有物質の一例はジンケートイオン（［Ｚｎ（ＯＨ）４］２−）である。
浴可溶性亜鉛含有物質をめっき浴に供給する原料物質（本発明において、「亜鉛源」ともいう。）として、酸化亜鉛が例示される。
(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.
本実施形態に係る亜鉛系めっき浴における可溶性亜鉛含有物質の亜鉛換算含有量（可溶性亜鉛含有物質の亜鉛換算の浴中含有量）は限定されない。この含有量が過度に少ない場合には亜鉛系めっき皮膜が析出しにくくなることから、上記の亜鉛換算含有量は２ｇ／Ｌ以上であることが好ましく、４ｇ／Ｌ以上であることがより好ましく、８ｇ／Ｌ以上であることが特に好ましい。可溶性亜鉛含有物質の亜鉛換算含有量が過度に多い場合には外観不良やつきまわり性の低下が生じることが懸念されるため、上記の亜鉛換算含有量は６０ｇ／Ｌ以下であることが好ましく、４０ｇ／Ｌ以下であることがより好ましく、２０ｇ／Ｌ以下であることが特に好ましい。 The zinc equivalent content of the soluble zinc-containing substance in the zinc-based plating bath according to the present embodiment (the zinc equivalent content of the soluble zinc-containing substance in the bath) 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）浴可溶性金属含有物質
本発明の一実施形態に係る亜鉛系めっき浴は、当該めっき浴が亜鉛合金めっき浴である場合には、浴可溶性金属含有物質を含有する。本明細書において浴可溶性金属含有物質とは、亜鉛合金めっき皮膜に含有される亜鉛以外の金属の供給源であって、金属元素の陽イオンおよびこれを含有する浴可溶性物質からなる群から選ばれる一種または二種以上の成分をいう。浴可溶性金属含有物質に含有される金属元素として、鉄、ニッケル、コバルトおよびマンガンが例示される。好ましい一例において、金属含有物質に含まれる金属元素は鉄、ニッケル、コバルトおよびマンガンからなる群から選ばれる。
(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.
浴可溶性金属含有物質をめっき浴に供給する原料物質（本発明において、「金属源」ともいう。）はその浴可溶性金属含有物質に含有される金属元素の種類に応じて適宜選択すればよい。例えば、浴可溶性金属含有物質に含有される金属元素が鉄である場合、すなわち、亜鉛合金めっき浴が浴可溶性鉄含有物質を含有する場合には、Ｆｅ２（ＳＯ４）３・７Ｈ２Ｏ、ＦｅＳＯ４・７Ｈ２Ｏ、Ｆｅ（ＯＨ）３、ＦｅＣｌ３・６Ｈ２Ｏ、ＦｅＣｌ２・４Ｈ２Ｏなどが鉄源として例示される。浴可溶性金属含有物質に含有される金属元素がニッケルである場合、すなわち、亜鉛合金めっき浴が浴可溶性ニッケル含有物質を含有する場合には、ＮｉＳＯ４・６Ｈ２Ｏ、ＮｉＣｌ２・６Ｈ２Ｏ，Ｎｉ（ＯＨ）２などがニッケル源として例示される。浴可溶性金属含有物質に含有される金属元素がマンガンである場合、すなわち、亜鉛合金めっき浴が浴可溶性マンガン含有物質を含有する場合には、ＭｎＳＯ４，ＭｎＳＯ４・Ｈ２Ｏ，ＭｎＣｌ２・４Ｈ２Ｏなどがマンガン源として例示される。 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.
本実施形態に係る亜鉛系めっき浴における可溶性金属含有物質の金属換算含有量は、目的とする亜鉛合金めっきの組成に応じて適宜設定される。亜鉛系めっき浴が浴可溶性鉄含有物質を含有する場合には、可溶性鉄含有物質の鉄換算含有量を５ｍｇ／Ｌ以上３００ｍｇ／Ｌ以下程度とすることが例示され、１０ｍｇ／Ｌ以上１５０ｍｇ／Ｌ以下程度とすることや、２０ｍｇ／Ｌ以上７０ｍｇ／Ｌ以下程度とすることが好ましい場合もある。亜鉛系めっき浴が浴可溶性ニッケル含有物質を含有する場合には、可溶性ニッケル含有物質のニッケル換算含有量を５０ｍｇ／Ｌ以上１００００ｍｇ／Ｌ以下程度とすることが例示され、１００ｍｇ／Ｌ以上４０００ｍｇ／Ｌ以下程度とすることや、２００ｍｇ／Ｌ以上２０００ｍｇ／Ｌ以下程度とすることが好ましい場合もある。亜鉛系めっき浴が浴可溶性マンガン含有物質を含有する場合には、可溶性マンガン含有物質のマンガン換算含有量を２ｇ／Ｌ以上８０ｇ／Ｌ以下程度とすることが例示され、５ｇ／Ｌ以上５０ｇ／Ｌ以下程度とすることや、１０ｇ／Ｌ以上２０ｇ／Ｌ以下程度とすることが好ましい場合もある。 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）添加剤成分
本実施形態に係るめっき浴は次に説明する水溶性共重合体（Ａ）を添加剤成分として含有し、必要に応じてさらに他の添加剤成分も含有する。
(2) Additive Component The plating bath according to this embodiment contains a water-soluble copolymer (A) described below as an additive component, and further contains other additive components as necessary.
（２−１）水溶性共重合体（Ａ）
本実施形態に係るめっき浴は、下記式（１）で示される構造からなる構成単位（Ｕ１）（下記式（１）中、Ｘは酸素元素または硫黄元素を表す。）および下記式（２）で示される構造からなる構成単位（Ｕ２）（下記式（２）中、Ｘは酸素元素または硫黄元素を表し、ｚは２または３を表す。）を含む水溶性共重合体を含有する。
The plating bath according to this embodiment includes a structural unit (U1) having a structure represented by the following formula (1) (in the following formula (1), X represents an oxygen element or a sulfur element) and the following formula (2). The water-soluble copolymer containing the structural unit (U2) which consists of a structure shown by (In the following formula (2), X represents an oxygen element or a sulfur element, and z represents 2 or 3) is contained.
本明細書において、かかる水溶性共重合体を水溶性共重合体（Ａ）ともいう。水溶性共重合体（Ａ）の一分子に含まれる構成単位（Ｕ１）および構成単位（Ｕ２）は、それぞれ、一種類であってもよいし、複数種類から構成されていてもよい。複数種類の場合における各種の配列は限定されず、一種類が連続的に配置されている部分を備えてもよいし、各種がランダムに配置されていてもよい。 In the present specification, such a water-soluble copolymer is also referred to as a water-soluble copolymer (A). Each of the structural unit (U1) and the structural unit (U2) contained in one molecule of the water-soluble copolymer (A) may be one type or a plurality of types. Various arrangements in the case of a plurality of types are not limited, and one type may be provided continuously, or various types may be arranged randomly.
水溶性共重合体（Ａ）の一分子に含まれるＸはすべてが硫黄元素または酸素元素であってもよいし、硫黄元素および酸素元素を含んでいてもよい。水溶性共重合体（Ａ）の一分子がＸとして硫黄元素および酸素元素を含む場合において、いずれか一方の元素を有する部分が連続的に配置されている部分を備えてもよいし、それぞれの元素を有する部分がランダムに配置されていてもよい。 All X contained in one molecule of the water-soluble copolymer (A) may be elemental sulfur or oxygen, or may contain elemental sulfur and oxygen. In the case where one molecule of the water-soluble copolymer (A) contains sulfur element and oxygen element as X, it may have a portion in which a portion having any one element is continuously arranged, The part which has an element may be arrange | positioned at random.
水溶性共重合体（Ａ）は、構成単位（Ｕ１）と構成単位（Ｕ２）とが連結基を介して結合している部分を有していてもよい。すなわち、水溶性共重合体（Ａ）の一分子中に、構成単位（Ｕ１）および構成単位（Ｕ２）が含まれていてもよい。 The water-soluble copolymer (A) may have a portion in which the structural unit (U1) and the structural unit (U2) are bonded via a linking group. That is, the structural unit (U1) and the structural unit (U2) may be contained in one molecule of the water-soluble copolymer (A).
水溶性共重合体（Ａ）の一分子中に、構成単位（Ｕ１）および構成単位（Ｕ２）が含まれている場合において、それらの含有比率は特に限定されない。超高電流密度部分における異常析出が発生する可能性をより安定的に低減させる観点から、水溶性共重合体（Ａ）の一分子中に含まれる構成単位（Ｕ１）の構成単位（Ｕ２に対するモル比率は、０．５以上２以下とすることが好ましく、０．７以上１．５以下とすることがより好ましく、０．８以上１．２５以下とすることが特に好ましい。 When the structural unit (U1) and the structural unit (U2) are contained in one molecule of the water-soluble copolymer (A), the content ratio thereof is not particularly limited. From the viewpoint of more stably reducing the possibility of abnormal precipitation in the ultrahigh current density portion, the structural unit (M1 relative to U2) of the structural unit (U1) contained in one molecule of the water-soluble copolymer (A). The ratio is preferably 0.5 or more and 2 or less, more preferably 0.7 or more and 1.5 or less, and particularly preferably 0.8 or more and 1.25 or less.
水溶性共重合体（Ａ）は、構成単位（Ｕ１）同士、構成単位（Ｕ２）同士、または構成単位（Ｕ１）と構成単位（Ｕ２）とが、下記式（３）で示される連結基（Ｕ３）および／または下記式（４）で示される連結基（Ｕ４）を介して連結している部分を有してもよい。
ここで、上記式（３）中において、ａは１〜５の整数のいずれか、ｂは１〜５の整数のいずれか、ｄは１〜５の整数のいずれか、ｅは１〜５の整数のいずれか、ｍは０〜５の整数のいずれかを表す。上記式（４）中において、ｆは１〜５の整数のいずれか、ｇは１〜５の整数のいずれか、ｈは１〜５の整数のいずれか、ｉは１〜５の整数のいずれか、ｎは０〜５の整数のいずれかを表す。 Here, in the formula (3), a is an integer of 1 to 5, b is an integer of 1 to 5, d is an integer of 1 to 5, and e is 1 to 5. Any of integers, m represents any of 0-5 integers. In the above formula (4), f is an integer of 1 to 5, g is an integer of 1 to 5, h is an integer of 1 to 5, and i is an integer of 1 to 5. Or n represents an integer of 0 to 5.
水溶性共重合体（Ａ）の一具体例として、上記の連結基（Ｕ３）を示す上記式（３）中のａ、ｂ、ｄおよびｅがいずれも１であって、連結基（Ｕ４）を示す上記式（４）中のｆ、ｇ、ｈおよびｉがいずれも１である場合が挙げられる。 As a specific example of the water-soluble copolymer (A), a, b, d and e in the above formula (3) representing the above linking group (U3) are all 1, and the linking group (U4) The case where all of f, g, h and i in the above formula (4) showing 1 is 1 is mentioned.
上記の水溶性共重合体（Ａ）は、亜鉛めっき浴においても、亜鉛合金めっき浴においても、優れた添加剤として機能することができる。すなわち、構成単位（Ｕ２）の２つのエタンジイル基（−ＣＨ２−ＣＨ２−）がそれぞれｎ−プロパンジイル基（−ＣＨ２−ＣＨ２−ＣＨ２−）である水溶性共重合体に比べて、超高電流密度部分において異常析出が発生しにくいめっき浴とすることができる。また、構成単位（Ｕ２）を有さず構成単位（Ｕ１）のみを部分構造として有する水溶性共重合体に比べて、厚さの電流密度依存性が低いめっき皮膜を得ることができる。上記の異常析出の発生をより安定的に抑制する観点から、構成単位（Ｕ１）のｚは３であること、すなわち、ｎ−プロパンジイル基を有する構成単位であることが好ましい。 The water-soluble copolymer (A) can function as an excellent additive in both a zinc plating bath and a zinc alloy plating bath. That is, compared with the water-soluble copolymer in which the two ethanediyl groups (—CH 2 —CH 2 —) of the structural unit (U2) are each n-propanediyl groups (—CH 2 —CH 2 —CH 2 —). Thus, it is possible to provide a plating bath in which abnormal precipitation is unlikely to occur in the ultrahigh current density portion. Moreover, compared with the water-soluble copolymer which does not have a structural unit (U2) but has only a structural unit (U1) as a partial structure, the plating film with low current density dependence can be obtained. From the viewpoint of more stably suppressing the occurrence of the abnormal precipitation, z of the structural unit (U1) is preferably 3, that is, a structural unit having an n-propanediyl group.
本実施形態に係る水溶性共重合体（Ａ）は、構成単位（Ｕ１）および構成単位（Ｕ２）を含有することに基づき、カチオン性の共重合体である。水溶性共重合体（Ａ）を亜鉛系めっき浴に添加する際の形態は特に限定されない。固体の成分として添加されてもよいし、液体の成分として添加されてもよい。一具体例として、カウンターアニオンも含む液体の成分として添加される場合が例示される。この場合において、カウンターアニオンの種類も特に限定されない。塩化物イオンなどのハロゲンイオンが具体例として挙げられる。なお、ハロゲンイオンの中でもフッ化物イオンは、取り扱い性を低下させ、廃液処理の負荷を増大させるおそれがあるため、使用しないことが好ましい。 The water-soluble copolymer (A) according to this embodiment is a cationic copolymer based on containing the structural unit (U1) and the structural unit (U2). The form at the time of adding a water-soluble copolymer (A) to a zinc-type plating bath is not specifically limited. It may be added as a solid component or may be added as a liquid component. As a specific example, a case where it is added as a liquid component including a counter anion is exemplified. In this case, the type of the counter anion is not particularly limited. Specific examples include halogen ions such as chloride ions. Of the halogen ions, fluoride ions are preferably not used because they may reduce the handleability and increase the load of waste liquid treatment.
本実施形態に係る水溶性共重合体（Ａ）の亜鉛系めっき浴中含有量も特に限定されない。水溶性共重合体（Ａ）の添加量が過度に少ない場合には添加させたことの効果が適切に得られにくくなり、水溶性共重合体（Ａ）の添加量が過度に多い場合には経済的観点、廃液処理の観点等の観点から不利益が生じる場合があり、さらに好ましくない効果が得られるおそれも高まることを考慮して、適宜設定すればよい。好ましい範囲について具体例として示せば、亜鉛系めっき浴が亜鉛めっき浴である場合には、水溶性共重合体（Ａ）の浴中含有量を塩化物換算で（水溶性共重合体（Ａ）の全てのカチオンに対して塩化物イオンが対応して存在しているとした場合における含有量として）０．１ｇ／Ｌ以上５０ｇ／Ｌ以下とすることが挙げられ、浴中含有量を水溶性共重合体（Ａ）の塩化物換算で０．５ｇ／Ｌ以上２０ｇ／Ｌ以下とすることがより好ましい。めっき浴が亜鉛合金めっき浴である場合には、水溶性共重合体（Ａ）の浴中含有量を塩化物換算で０．１ｇ／Ｌ以上２０ｇ／Ｌ以下とすることが挙げられる。 The content of the water-soluble copolymer (A) according to this embodiment in the zinc-based plating bath is not particularly limited. When the addition amount of the water-soluble copolymer (A) is excessively small, it is difficult to appropriately obtain the effect of the addition, and when the addition amount of the water-soluble copolymer (A) is excessively large. It may be set as appropriate in consideration of the disadvantage that there may be disadvantages from the viewpoint of economic viewpoint, waste liquid treatment, etc., and the possibility that an undesirable effect is further increased. As a specific example of the preferred range, when the zinc-based plating bath is a galvanizing bath, the content of the water-soluble copolymer (A) in the bath is calculated in terms of chloride (water-soluble copolymer (A)). The content in the bath is 0.1 g / L or more and 50 g / L or less, and the content in the bath is water-soluble. More preferably, it is 0.5 g / L or more and 20 g / L or less in terms of chloride of the copolymer (A). When the plating bath is a zinc alloy plating bath, the content of the water-soluble copolymer (A) in the bath may be 0.1 g / L or more and 20 g / L or less in terms of chloride.
本実施形態に係る水溶性共重合体（Ａ）の製造方法は特に限定されない。一例を挙げれば、Ｎ−［２−（ジメチルアミノ）エチル］尿素またはＮ−［３−（ジメチルアミノ）プロピル］尿素、およびＮ，Ｎ’−ビス［２−（ジメチルアミノ）エチル］尿素を、ジハロゲン化エチルエーテルおよびエピハロヒドリンにて縮重合させることにより、水溶性共重合体（Ａ）を含む組成物を得ることができる。 The manufacturing method of the water-soluble copolymer (A) which concerns on this embodiment is not specifically limited. In one example, N- [2- (dimethylamino) ethyl] urea or N- [3- (dimethylamino) propyl] urea and N, N′-bis [2- (dimethylamino) ethyl] urea are A composition containing the water-soluble copolymer (A) can be obtained by condensation polymerization with dihalogenated ethyl ether and epihalohydrin.
（２−２）その他の添加剤成分
本実施形態に係る亜鉛系めっき浴は、上記の水溶性共重合体（Ａ）以外の添加剤成分を含有してもよい。そのような添加剤成分または亜鉛系めっき浴中で添加剤成分を与える材料として、次のようなものが例示される。
(2-2) Other additive components The zinc-based plating bath according to the present embodiment may contain additive components other than the water-soluble copolymer (A). Examples of materials that provide such additive components or additive components in a zinc-based plating bath include the following.
ｉ）一次光沢剤
本実施形態に係る亜鉛系めっき浴は、添加剤成分の一種として一次光沢剤を含有してもよい。かかる一次光沢剤の例として、各種亜鉛めっき浴に使用されるアニオン系界面活性剤、ノニオン系界面活性剤、ポリアミン化合物および水溶性カチオン高分子化合物などの水溶性の有機化合物などを挙げることができる。
このポリアミン化合物および水溶性カチオン高分子化合物として、ポリアリルアミン、ポリエポキシポリアミン、ポリアミドポリアミン、およびポリアルキレンポリアミン、などが例示される。前述の化合物（Ｚ）も一次光沢剤の一種に位置付けられる。
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. The aforementioned compound (Z) is also positioned as a kind of primary brightener.
ポリアリルアミンの具体例として、ジアリルジメチルアンモニウムクロライドと二酸化硫黄の共重合体などが挙げられる。ポリエポキシポリアミンの具体例として、エチレンジアミンとエピクロルヒドリンとの縮合重合体、ジメチルアミノプロピルアミンとエピクロルヒドリンとの縮合重合体、イミダゾールとエピクロルヒドリンとの縮合重合体、１−メチルイミダゾールや２−メチルイミダゾール等のイミダゾール誘導体とエピクロルヒドリンとの縮合重合体、アセトグアナミン、ベンゾグアナミン等のトリアジン誘導体などを含む複素環状アミンとエピクロルヒドリンとの縮合重合体などが挙げられる。ポリアミドポリアミンの具体例として、３−ジメチルアミノプロピル尿素とエピクロルヒドリンとの縮合重合体、ビス（Ｎ，Ｎ−ジメチルアミノプロピル）尿素とエピクロルヒドリンとの縮合重合体等のポリアミンポリ尿素樹脂、Ｎ，Ｎ−ジメチルアミノプロピルアミンとアルキレンジカルボン酸とエピクロルヒドリンとの縮合重合体等の水溶性ナイロン樹脂などが挙げられる。また、ポリアルキレンポリアミンの具体例として、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ヘキサメチレンペンタミン、ジメチルアミノプロピルアミンと２，２’−ジクロルジエチルエーテルとの縮合重合体、ジメチルアミノプロピルアミンと１，３−ジクロルプロパンとの縮合重合体、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノプロパンと２，２’−ジクロルジエチルエーテルとの縮合重合体、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノプロパンと１，４−ジクロルブタンとの縮合重合体、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノプロパンと１，３−ジクロルプロパン−２−オールとの縮合重合体などが挙げられる。 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.
一次光沢剤の亜鉛系めっき浴中含有量は限定されない。一次光沢剤の種類や、被めっき部材の形状、めっき条件などを勘案して適宜設定すればよい。一例を挙げれば、一次光沢剤の含有量は０．１ｇ／Ｌ以上１００ｇ／Ｌ以下とすることが好ましく、０．５ｇ／Ｌ以上２０ｇ／Ｌ以下とすることがより好ましい。 The content of the primary brightener in the zinc plating bath is not limited. What is necessary is just to set suitably in consideration of the kind of primary brightener, the shape of a to-be-plated member, plating conditions, etc. For example, the content of the primary brightener is preferably 0.1 g / L or more and 100 g / L or less, and more preferably 0.5 g / L or more and 20 g / L or less.
ｉｉ）二次光沢剤
本実施形態に係る亜鉛系めっき浴は、添加剤成分の一種として二次光沢剤を含有してもよい。特に、光沢性の向上などの観点からは、二次光沢剤として、芳香族アルデヒドおよびピリジニウム化合物のうち少なくとも一方を含有してもよい。
二次光沢剤として機能することができる芳香族アルデヒドとしては、アニスアルデヒド、ベラトルアルデヒド、サリチルアルデヒド、バニリン、ピペロナール、およびｐ−ヒドロキシベンズアルデヒドなどを挙げることができる。光沢性の向上と亜鉛系めっき浴に含有される化合物の安定性の観点から、二次光沢剤として含有されることが好ましい芳香族アルデヒドとして、ベラトルアルデヒド、およびバニリンが例示される。
ii) Secondary brightener The zinc-based plating bath according to the present embodiment may contain a secondary brightener as a kind of additive component. In particular, from the viewpoint of improving glossiness, 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.
二次光沢剤として機能することができるピリジニウム化合物としては、ベンジルピリジニウムカルボキシレート（塩化３−カルボキシベンジルピリジニウム）、および塩化３−カルバモイルベンジルピリジニウムなどを挙げることができる。 Examples of the pyridinium compound that can function as a secondary brightener include benzylpyridinium carboxylate (3-carboxybenzylpyridinium chloride) and 3-carbamoylbenzylpyridinium chloride.
これらのピリジニウム化合物の中でも、４級アミノ基を有するピリジニウム化合物が好ましい。以下、このピリジニウム化合物を「ピリジニウム化合物（α）」ともいう。ピリジニウム化合物（α）はポリカチオン化合物であり、亜鉛系めっき浴中で加水分解されたりめっき析出のための電解処理によって電気分解されたりしても、この化合物の分解物や重合体が可溶性を維持することができるため、めっき浴中に不溶性物質が発生しにくく、不溶性物質の被めっき面への吸着に基づくめっき皮膜の外観不良が生じにくい。また、一次光沢剤と同等の機能をも示す場合があり、そのような場合には、ピリジニウム化合物（α）単独で、亜鉛系めっき皮膜の均一電着性を高めるとともに皮膜の光沢度を高めることができる。 Among these pyridinium compounds, pyridinium compounds having a quaternary amino group are preferable. Hereinafter, this pyridinium compound is also referred to as “pyridinium compound (α)”. The pyridinium compound (α) is a polycation compound, and its degradation products and polymers remain soluble even if they are hydrolyzed in a zinc-based plating bath or electrolyzed by electrolytic treatment for plating deposition. Therefore, insoluble substances are hardly generated in the plating bath, and appearance defects of the plating film based on adsorption of the insoluble substances to the surface to be plated are unlikely to occur. Also, it may exhibit the same function as the primary brightener. In such a case, the pyridinium compound (α) alone can improve the uniform electrodeposition of the zinc plating film and increase the gloss of the film. Can do.
ピリジニウム化合物（α）の亜鉛系めっき浴への添加量は特に限定されない。ピリジニウム化合物（α）の具体的な構造や亜鉛系めっき浴の組成などに応じて適宜設定されるべきものである。亜鉛系めっき浴中の上記のピリジニウム化合物の浴中含有量を０．０５ｇ／Ｌ以上５ｇ／Ｌ以下とすることが、ピリジニウム化合物（α）の具体的な構造や亜鉛系めっき浴の組成がどのような場合であっても所望の効果を得ることができることが多いため好ましく、０．１ｇ／Ｌ以上３ｇ／Ｌ以下とすることがより好ましい。 The addition amount of the pyridinium compound (α) to the zinc-based plating bath is not particularly limited. It should be appropriately set according to the specific structure of the pyridinium compound (α), the composition of the zinc-based plating bath, and the like. The specific content of the pyridinium compound (α) and the composition of the zinc plating bath can be adjusted so that the content of the pyridinium compound in the zinc plating bath is 0.05 g / L or more and 5 g / L or less. Even in such a case, a desired effect can often be obtained, and therefore, it is preferable, and it is more preferably 0.1 g / L or more and 3 g / L or less.
ｉｉｉ）めっき促進剤
「めっき促進剤」とは、めっき金属の析出を促進させる機能を有するものであって、被めっき面に吸着してその吸着した領域近傍で金属イオンの還元反応が生じることを促進しているものと推測される。
そのようなめっき促進剤として、チアジアゾール骨格を有する化合物であるチアジアゾール化合物が例示される。チアジアゾール骨格に含まれる３つの硫黄が被めっき面に化学吸着し、この化学吸着した領域での金属イオンの還元反応を促進している可能性がある。チアジアゾール化合物の具体例として、２，５−ジメルカプト−１，３，４−チアジアゾール、２−チオ酢酸−５−メルカプト−１，３，４−チアジアゾール、２，５−ジチオ酢酸−１，３，４−チアジアゾール、２−ヒドロキシエチルチオ−５−メルカプト−１，３，４−チアジアゾール、２，５−ジヒドロキシエチルチオ−１，３，４−チアジアゾール、エピクロルヒドリン改質２，５−ジメルカプト−１，３，４−チアジアゾール、ビス（１，３，４−チアジアゾール−２，５−ジイル）などが挙げられる。
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.
めっき促進剤の亜鉛系めっき浴中含有量は限定されない。めっき促進剤の種類や、被めっき部材の形状、めっき条件などを勘案して適宜設定すればよい。一例を挙げれば、めっき促進剤の含有量は０．１ｇ／Ｌ以上１００ｇ／Ｌ以下とすることが好ましく、０．５ｇ／Ｌ以上２０ｇ／Ｌ以下とすることがより好ましい。 The content of the plating accelerator in the zinc plating bath is not limited. What is necessary is just to set suitably in consideration of the kind of plating accelerator, the shape of a to-be-plated member, plating conditions, etc. For example, the content of the plating accelerator is preferably 0.1 g / L or more and 100 g / L or less, and more preferably 0.5 g / L or more and 20 g / L or less.
ｉｖ）キレート剤
本実施形態に係る亜鉛系めっき浴は、キレート剤を含有してもよい。
キレート剤の具体例として、酒石酸、クエン酸、グルコン酸、エチレンジアミン、ヘキサミン、１，２−ジアミノプロパン、１，３−ジアミノプロパン、１，２−ジアミノブタン、１，４−ジアミノブタン、トリアミノトリエチルアミン、メチルアミノプロピルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエタノールアミノプロピルアミン、２−ヒドロキシエチルアミノプロピルアミン、１，３−ビス−（３−アミノプロポキシ）エタン、ニトリロトリ酢酸（ＮＴＡ）、エチレンジアミン四酢酸（ＥＤＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、トリエチレンテトラミン六酢酸（ＴＴＨＡ）などが例示される。このキレート剤は、例えばジエチレントリアミンやトリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミンなどのポリアミン化合物のように、一次光沢剤としての機能も有するキレート剤であってもよい。なお、キレート剤がカルボン酸など酸の部分構造を有する場合には、キレート剤はフリーの酸の形態として亜鉛系めっき浴に添加されてもよいし、ナトリウム塩などの塩の形態として添加されてもよい。あるいは、アルカリ性である亜鉛合金めっき浴中で加水分解されることにより酸イオンを形成しうる誘導体（例えばエステル）の形態で亜鉛系めっき浴に添加されてもよい。
iv) Chelating agent The zinc-based plating bath according to this embodiment may contain a chelating agent.
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 plating bath as a free acid form or as a salt form such as a sodium salt. Also good. Alternatively, it may be added to the zinc-based plating bath in the form of a derivative (for example, ester) that can form an acid ion by being hydrolyzed in an alkaline zinc alloy plating bath.
キレート剤の亜鉛系めっき浴中含有量は限定されない。キレート剤の種類や、被めっき部材の形状、めっき条件などを勘案して適宜設定すればよい。一例を挙げれば、キレート剤の含有量は０．１ｇ／Ｌ以上１００ｇ／Ｌ以下とすることが好ましく、０．５ｇ／Ｌ以上２０ｇ／Ｌ以下とすることがより好ましい。 The content of the chelating agent in the zinc plating bath is not limited. What is necessary is just to set suitably in consideration of the kind of chelating agent, the shape of a to-be-plated member, plating conditions, etc. For example, the content of the chelating agent is preferably 0.1 g / L or more and 100 g / L or less, and more preferably 0.5 g / L or more and 20 g / L or less.
ｖ）その他
本実施形態に係る亜鉛系めっき浴は、上記の成分以外の添加剤成分を含有してもよい。そのような添加剤成分として、酸化防止剤、消泡剤、金属封鎖剤などが例示される。
酸化防止剤として、フェノール、カテコール、レゾルシン、ヒドロキノン、ピロガロール等のヒドロキシフェニル化合物や、Ｌ−アスコルビン酸、ソルビトール等が例示される。なお、上記のキレート剤が還元性物質である場合には、そのキレート剤が酸化防止剤の機能を有しているため、酸化防止剤を含有させなくともよい。
消泡剤として、シリコーン系消泡剤や、界面活性剤、ポリエーテル、高級アルコール等の有機系消泡剤が例示される。
金属封鎖剤として、珪酸塩（具体例としてケイ酸ナトリウムが挙げられる。）、シリカ（具体例としてコロイダルシリカが挙げられる。）などが例示される。金属封鎖剤の亜鉛系めっき浴中含有量は限定されない。金属封鎖剤の種類や、溶媒の組成などを勘案して適宜設定すればよい。一例を挙げれば、金属封鎖剤の含有量は０．１ｇ／Ｌ以上１００ｇ／Ｌ以下とすることが好ましく、０．５ｇ／Ｌ以上２０ｇ／Ｌ以下とすることがより好ましい。キレート剤が金属封鎖剤としての機能を有する場合もある。
v) Others The zinc-based plating bath according to the present embodiment may contain additive components other than the above components. Examples of such additive components include antioxidants, antifoaming agents, metal sequestering agents and the like.
Examples of the antioxidant 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.
Examples of the metal sequestering agent include silicate (specific examples include sodium silicate), silica (specific examples include colloidal silica), and the like. The content of the metal sequestering agent in the zinc plating bath is not limited. What is necessary is just to set suitably considering the kind of metal sequestering agent, a composition of a solvent, etc. For example, the content of the metal sequestering agent is preferably 0.1 g / L or more and 100 g / L or less, and more preferably 0.5 g / L or more and 20 g / L or less. The chelating agent may have a function as a metal sequestering agent.
（３）溶媒、液性
本実施形態に係るめっき浴の溶媒は水を主成分とする。水以外の溶媒としてアルコール、エーテル、ケトンなど水への溶解度が高い有機溶媒を混在させてもよい。この場合には、めっき浴全体の安定性および廃液処理への負荷の緩和の観点から、その比率は全溶媒に対して１０体積％以下とすることが好ましい。
(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.
本実施形態に係る亜鉛系めっき浴はジンケート型のめっき浴であるから、アルカリ性である。めっき浴をアルカリ性とするために用いられる材料（本明細書において「アルカリ成分」ともいう。）の種類は特に限定されない。水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物など公知の材料を用いればよい。 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.
本実施形態に係る亜鉛系めっき浴に含まれるアルカリ成分の含有量は特に限定されない。過度に少ない場合には亜鉛系めっき浴の液性をアルカリ性とすることができず、めっき浴中でジンケートイオンを生成することが困難となる。一方、アルカリ成分の含有量が過度に高い場合には、亜鉛系めっき浴の安定性が低下して、得られる亜鉛系めっき皮膜の外観が低下したり付き廻り性が低下したりすることが懸念される。したがって、亜鉛系めっき浴に含まれるアルカリ成分の浴中含有量は、水酸化ナトリウム換算で４０ｇ／Ｌ以上４００ｇ／Ｌ以下とすることが好ましく、８０ｇ／Ｌ以上２５０ｇ／Ｌ以下とすることがより好ましく、１００ｇ／Ｌ以上２００ｇ／Ｌ以下とすることが特に好ましい。 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 is lowered, and there is a concern that the appearance of the obtained zinc-based plating film may be deteriorated or the throwing power may be lowered. Is done. Therefore, the content of the alkaline component contained in the zinc 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 preferably 100 g / L or more and 200 g / L or less.
（４）調製方法
本実施形態に係る亜鉛系めっき浴の調製方法は特に限定されない。亜鉛系めっき浴が亜鉛めっき浴の場合には、アルカリ成分、亜鉛源および浴中で水溶性共重合体（Ａ）を与える成分（水溶性共重合体（Ａ）の塩化物などが例示され、以下、「水溶性共重合体（Ａ）源」ともいう。）、ならびに必要に応じ任意添加成分として前述のその他の添加剤成分などを水などの溶媒に溶解させることによって調製することができる。亜鉛合金めっき浴の場合には、アルカリ成分、亜鉛源、金属源および水溶性共重合体（Ａ）源、ならびに必要に応じ任意添加成分として前述のその他の添加剤成分などを溶媒に溶解させることによって調製することができる。通常は、溶媒にアルカリ成分を添加し、続いて他の成分を添加することによって、作業性を低下させることなくかつ安全に亜鉛系めっき浴を調製することができる。
(4) Preparation method The preparation method of the zinc-type plating bath which concerns on this embodiment is not specifically limited. When the zinc-based plating bath is a galvanizing bath, an alkali component, a zinc source, and a component that gives the water-soluble copolymer (A) in the bath (such as chloride of the water-soluble copolymer (A)) Hereinafter, it is also referred to as “source of water-soluble copolymer (A)”), and if necessary, it can be prepared by dissolving the above-mentioned other additive components as optional additional components in a solvent such as water. In the case of a zinc alloy plating bath, an alkali component, a zinc source, a metal source, a water-soluble copolymer (A) source, and, if necessary, the above-mentioned other additive components as an optional additive component are dissolved in a solvent. Can be prepared. 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．ジンケート型亜鉛系めっき浴用添加剤
本実施形態に係るジンケート型亜鉛系めっき浴用添加剤は、上記の本実施形態に係る亜鉛系めっき浴に含有される添加剤成分を含有する。すなわち、本実施形態に係るジンケート型亜鉛系めっき浴用添加剤は水溶性共重合体（Ａ）を含有し、必要に応じ、さらに、一次光沢剤、二次光沢剤、めっき促進剤などの前述の他の添加剤成分を含有する。
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 zincate-type zinc-based plating bath additive according to this embodiment contains a water-soluble copolymer (A), and if necessary, the above-described primary brightener, secondary brightener, plating accelerator, and the like. Contains other additive ingredients.
本実施形態に係るジンケート型亜鉛系めっき浴用添加剤における水溶性共重合体（Ａ）の含有量は特に限定されない。水溶性共重合体（Ａ）の塩化物など水溶性共重合体（Ａ）源は溶解度が高いため、１０ｇ／Ｌ程度まで浴中含有量を高めることができる。
本実施形態に係るジンケート型亜鉛系めっき浴用添加剤が水溶性共重合体（Ａ）以外の成分を含有する場合におけるそれらの含有量は、その添加剤の機能との関係で適宜設定されるべきものである。
The content of the water-soluble copolymer (A) in the zincate zinc plating bath additive according to this embodiment is not particularly limited. Since the water-soluble copolymer (A) source such as chloride of the water-soluble copolymer (A) has high solubility, the content in the bath can be increased to about 10 g / L.
In the case where the additive for zincate-type zinc plating bath according to the present embodiment contains components other than the water-soluble copolymer (A), their contents should be appropriately set in relation to the function of the additive. Is.
３．亜鉛系めっき部材の製造方法
亜鉛系めっき部材は、本実施形態に係る亜鉛系めっき浴に被めっき部材を浸漬させ、被めっき部材をカソード（陰極）として電解を行うことによって得ることができる。被めっき部材の材質は導電性を有する限り特に限定されない。鉄系材料などの金属系材料、および樹脂系材料やセラミックス系材料などからなる導電性を有さない材料の表面に無電解めっきなどにより導電性材料からなる層が形成されたものが例示される。被めっき部材の形状も特に限定されない。板材や棒材、線材などの一次加工品、ねじ、ボルト、プレス加工品などの二次加工品が挙げられる。
なお、アノード（陽極）を構成する材料は特に限定されない。通常は、安価で入手しやすい鉄系材料が用いられる。
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.
電解における電流密度は特に限定されない。電流密度が過度に低い場合には得られる亜鉛系めっき皮膜の析出速度が低く生産性に劣り、電流密度が過度に高い場合には得られる亜鉛めっき皮膜の外観が劣化したり、均一電着性、付き廻り性などが低下したりすることが懸念されることを考慮して、適宜設定すればよい。生産性を高めることとめっき皮膜の品質を高めることとを両立する観点から、０．０１Ａ／ｄｍ２以上３０Ａ／ｄｍ２以下とすることが好ましく、０．５Ａ／ｄｍ２以上１５Ａ／ｄｍ２以下とすることがより好ましく、０．５Ａ／ｄｍ２以上７Ａ／ｄｍ２以下とすることが特に好ましい。前述のように、被めっき物の形状的理由などにより局所的に電流密度が特に高くなる超高電流密度部分においても、本実施形態に係る亜鉛系めっき浴では異常析出が生じにくい。 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 will be lowered, it may be set as appropriate. From the standpoint of improving productivity and improving the quality of the plating film, it is preferably 0.01 A / dm 2 or more and 30 A / dm 2 or less, preferably 0.5 A / dm 2 or more and 15 A / dm 2 or less. And more preferably 0.5 A / dm 2 or more and 7 A / dm 2 or less. As described above, abnormal precipitation is unlikely to occur in the zinc-based plating bath according to the present embodiment even in the ultrahigh current density portion where the current density is particularly high locally due to the shape of the object to be plated.
電解におけるめっき浴の温度（めっき浴温度）は室温程度（２５℃程度）で行えばよい。めっき浴温度が過度に高い場合には、めっき外観光沢が低下し、特に低電部の光沢性が低下するめっき浴温度が過度に低い場合には、めっき皮膜の析出速度が低下するなど生産性に悪影響を及ぼすことが懸念される。 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, the gloss of the plating appearance decreases, and particularly when the plating bath temperature is excessively low. There is concern that it will adversely affect
電解時間（めっき時間）は、めっき浴の組成、上記の電流密度、めっき浴温度などによって決定されるめっき皮膜の析出速度と求めるめっき皮膜の厚さとから適宜設定される。 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.
めっき設備の構成は特に限定されない。板状または棒状のアノードに対向するようにカソードとしての被めっき部材を亜鉛系めっき浴中に配置し、亜鉛系めっき浴内で液攪拌を適宜行いながら電解して被めっき部材に亜鉛系めっき皮膜を形成してもよいし、ボルトなどの被めっき部材がその内部に入っているバレルを亜鉛系めっき浴中に浸漬させ、バレルを回転させながら電解を行うことで被めっき部材に亜鉛系めっき皮膜を形成してもよい。 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.
以下、本発明の効果を実施例に基づいて説明するが、本発明はこれに限定されるものではない。 Hereinafter, although the effect of the present invention is explained based on an example, the present invention is not limited to this.
１．亜鉛系めっき浴の調製および亜鉛系めっき皮膜を有する部材の作製
［実施例１］
（１）水溶性共重合体（Ａ１）の塩化物の製造
Ｎ−［２−（ジメチルアミノ）エチル］尿素１ｍｏｌと、Ｎ，Ｎ’−ビス［２−（ジメチルアミノ）エチル］尿素１ｍｏｌとを、フラスコに入れ撹拌し、エピクロルヒドリン１ｍｏｌおよびジクロロエチルエーテル１ｍｏｌをさらにフラスコに入れて、これらの重縮合反応物を含む液体を、水溶性共重合体（Ａ）の一種（本明細書において、「水溶性共重合体（Ａ１）」ともいう。）を含む液体として得た。以下、上記の液体を「液体（Ａ１）」ともいう。水溶性共重合体（Ａ１）が含む構成単位（Ｕ１）は、上記式（１）において、Ｘが酸素元素であってｚが２であった。水溶性共重合体（Ａ１）が含む構成単位（Ｕ２）は、上記式（２）において、Ｘが酸素元素であった。水溶性共重合体（Ａ１）が含みうる連結基（Ｕ３）は、ａ、ｂ、ｄおよびｅがいずれも１であった。水溶性共重合体（Ａ１）が含みうる連結基（Ｕ３）は、ｆ、ｇ、ｈおよびｉがいずれも１であった。
1. Preparation of a zinc-based plating bath and production of a member having a zinc-based plating film [Example 1]
(1) Production of chloride of water-soluble copolymer (A1) 1 mol of N- [2- (dimethylamino) ethyl] urea and 1 mol of N, N′-bis [2- (dimethylamino) ethyl] urea Then, 1 mol of epichlorohydrin and 1 mol of dichloroethyl ether are further added to the flask, and the liquid containing these polycondensation products is added to a kind of water-soluble copolymer (A) (in this specification, “water-soluble” It was also obtained as a liquid containing the functional copolymer (A1) ”. Hereinafter, the liquid is also referred to as “liquid (A1)”. Regarding the structural unit (U1) contained in the water - soluble copolymer (A1), X is an oxygen element and z is 2 in the above formula (1). In the structural unit (U2) contained in the water - soluble copolymer (A1), X is an oxygen element in the above formula (2). In the linking group (U3) that the water - soluble copolymer (A1) can contain, a, b, d, and e were all 1. In the linking group (U3) that the water - soluble copolymer (A1) can contain, f, g, h, and i were all 1.
（２）亜鉛めっき浴の調製
亜鉛源としての酸化亜鉛を、これに由来する浴可溶性亜鉛含有物質のめっき浴中の亜鉛換算含有量が１０ｇ／Ｌとなる量、アルカリ成分としての水酸化ナトリウムを、めっき浴１Ｌあたりの溶解量が１２０ｇとなる量、液体（Ａ１）を、めっき浴中の水溶性共重合体（Ａ１）の塩化物換算含有量が１ｇ／Ｌとなる量、および補助光沢剤としてメタスＺＥＳ−Ｖ（ユケン工業（株）製）を１ｍｌ／Ｌ含有するアルカリ性のジンケート型亜鉛めっき浴を調製した。
(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 10 g / L, sodium hydroxide as an alkali component , An amount so that the dissolution amount per liter of the plating bath is 120 g, a liquid (A1), an amount so that the chloride equivalent content of the water-soluble copolymer (A1) in the plating bath is 1 g / L, and an auxiliary brightener As an alkaline zincate galvanizing bath containing 1 ml / L of METASU ZES-V (manufactured by Yuken Industry Co., Ltd.) was prepared.
（３）亜鉛めっき皮膜を有する亜鉛系めっき部材の作製
ハルセル試験器（山本めっき試験器社製）を用意した。この試験器のめっき槽内の所定の位置に、縦４５ｍｍ、横４５ｍｍ、厚さ１ｍｍのアノードとしての鉄板、および縦６７ｍｍ、横１００ｍｍ、厚さ０．３ｍｍの被めっき部材（カソード）としての冷間圧延鋼板（ＳＰＣＣ）を配置した。めっき槽内に上記のめっき浴を液面が所定の高さとなるまで入れた。アノードおよびカソードをめっき電源に接続し、次の条件１から条件３のいずれかの条件にて電気めっきを行って、亜鉛めっき皮膜を有する亜鉛系めっき部材を３つ得た。
(3) Production of a zinc-based plating member having a zinc plating film A Hull Cell tester (manufactured by Yamamoto Plating Tester Co., Ltd.) was prepared. In a predetermined position 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 a cold 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. A cold rolled steel plate (SPCC) was placed. The above-described plating bath was placed in the plating tank until the liquid level reached a predetermined height. The anode and cathode were connected to a plating power source, and electroplating was performed under any one of the following conditions 1 to 3 to obtain three zinc-based plated members having a zinc plating film.
（条件１）
電流：４Ａ
通電時間：５分
めっき浴温度：２５℃
めっき面積の調整：電流密度を高めるために、アノード鉄板のめっき面積を通常ハルセルの１／４の面積（縦方向の長さを１／４とした。）としてめっきを行った。
上記の電流では、カソードの電流密度は８０Ａ／ｄｍ２から２Ａ／ｄｍ２の範囲であった。
(Condition 1)
Current: 4A
Energizing time: 5 minutes Plating bath temperature: 25 ° C
Adjustment of plating area: In order to increase the current density, plating was performed with the plating area of the anode iron plate set to 1/4 of that of a normal hull cell (length in the longitudinal direction was set to 1/4).
In the above current, cathode current density ranged from 80A / dm 2 of 2A / dm 2.
（条件２）
電流：２Ａ
通電時間：２０分
めっき浴温度：２５℃
上記の電流では、カソードの電流密度は１０Ａ／ｄｍ２から０．２Ａ／ｄｍ２の範囲であった。
(Condition 2)
Current: 2A
Energizing time: 20 minutes Plating bath temperature: 25 ° C
At the above current, the cathode current density ranged from 10 A / dm 2 to 0.2 A / dm 2 .
（条件３）
電流：０．５Ａ
通電時間：２０分
めっき浴温度：２５℃
上記の電流では、カソードの電流密度は２．５Ａ／ｄｍ２から０．１Ａ／ｄｍ２の範囲であった。
(Condition 3)
Current: 0.5A
Energizing time: 20 minutes Plating bath temperature: 25 ° C
At the above current, the cathode current density ranged from 2.5 A / dm 2 to 0.1 A / dm 2 .
［実施例２］
Ｎ−［２−（ジメチルアミノ）プロピル］尿素1ｍｏｌと、Ｎ，Ｎ’−ビス［２−（ジメチルアミノ）エチル］尿素１ｍｏｌとを、フラスコに入れ撹拌し、エピクロルヒドリン１ｍｏｌおよびジクロロエチルエーテル１ｍｏｌをさらにフラスコに入れて、これらの重縮合反応物を含む液体を得た。水溶性共重合体（Ａ）の一種（本明細書において、「水溶性共重合体（Ａ２）」ともいう。）を含む液体として得た。以下、上記の液体を「液体（Ａ２）」ともいう。水溶性共重合体（Ａ２）が含む構成単位（Ｕ１）は、上記式（１）において、Ｘが酸素元素であってｚが３であった。水溶性共重合体（Ａ２）が含む構成単位（Ｕ２）は、上記式（２）において、Ｘが酸素元素であった。水溶性共重合体（Ａ２）が含みうる連結基（Ｕ３）は、ａ、ｂ、ｄおよびｅがいずれも１であった。水溶性共重合体（Ａ２）が含みうる連結基（Ｕ３）は、ｆ、ｇ、ｈおよびｉがいずれも１であった。
以下、液体（Ａ１）に代えて液体（Ａ２）を用いて、実施例１と同様の操作を行って、浴可溶性亜鉛含有物質および水溶性共重合体（Ａ２）を含有するアルカリ性のジンケート型亜鉛めっき浴を調製した。かかるジンケート型亜鉛めっき浴を用いて、実施例１に示される３種の異なるめっき条件で電気めっきを行って、亜鉛めっき皮膜を有する亜鉛系めっき部材を３つ得た。
[Example 2]
1 mol of N- [2- (dimethylamino) propyl] urea and 1 mol of N, N′-bis [2- (dimethylamino) ethyl] urea are placed in a flask and stirred to further add 1 mol of epichlorohydrin and 1 mol of dichloroethyl ether. It put into the flask and the liquid containing these polycondensation reaction products was obtained. It was obtained as a liquid containing one type of water-soluble copolymer (A) (also referred to herein as “water-soluble copolymer (A2)”). Hereinafter, the liquid is also referred to as “liquid (A2)”. In the structural unit (U1) contained in the water - soluble copolymer (A2), in the above formula (1), X was an oxygen element and z was 3. In the structural unit (U2) contained in the water - soluble copolymer (A2), X is an oxygen element in the above formula (2). In the linking group (U3) that the water - soluble copolymer (A2) can contain, a, b, d, and e were all 1. In the linking group (U3) that the water - soluble copolymer (A2) can contain, f, g, h, and i were all 1.
Thereafter, using the liquid (A2) instead of the liquid (A1), the same operation as in Example 1 was performed, and the alkaline zincate-type zinc containing the bath-soluble zinc-containing substance and the water-soluble copolymer (A2) was used. A plating bath was prepared. Using such a zincate-type zinc plating bath, electroplating was performed under the three different plating conditions shown in Example 1 to obtain three zinc-based plated members having a zinc plating film.
［比較例１］
Ｎ−［２−（ジメチルアミノ）プロピル］尿素１ｍｏｌと、Ｎ，Ｎ’−ビス［２−（ジメチルアミノ）プロピル］尿素１ｍｏｌとを、フラスコに入れ撹拌し、エピクロルヒドリン１ｍｏｌおよびジクロロエチルエーテル１ｍｏｌをさらにフラスコに入れて、これらの重縮合反応物を含む液体を得た。この液体は、水溶性共重合体（Ａ２）と類似した構造であるが、水溶性共重合体（Ａ２）に含まれる構成単位（Ｕ１）の２つのエタンジイル基がいずれもｎ−プロパンジイル基に変更された構造を有する水溶性共重合体（本明細書において、「水溶性共重合体（Ｂ１）」ともいう。）を含有する。以下、この液体を「液体（Ｂ１）」ともいう。
亜鉛源としての酸化亜鉛を、これに由来する浴可溶性亜鉛含有物質のめっき浴中の亜鉛換算含有量が１０ｇ／Ｌとなる量、アルカリ成分としての水酸化ナトリウムを、めっき浴１Ｌあたりの溶解量が１２０ｇとなる量、液体（Ｂ１）を、めっき浴中の水溶性共重合体（Ｂ１）の塩化物換算含有量が１ｇ／Ｌとなる量、および補助光沢剤としてメタスＺＥＳ−Ｖ（ユケン工業（株）製）を１ｍｌ／Ｌ含有するアルカリ性のジンケート型亜鉛めっき浴を調製した。 以下、かかるジンケート型亜鉛めっき浴を用いて、実施例１に示される３種の異なるめっき条件で電気めっきを行って、亜鉛めっき皮膜を有する亜鉛系めっき部材を３つ得た。
[Comparative Example 1]
1 mol of N- [2- (dimethylamino) propyl] urea and 1 mol of N, N′-bis [2- (dimethylamino) propyl] urea are placed in a flask and stirred, and 1 mol of epichlorohydrin and 1 mol of dichloroethyl ether are further added. It put into the flask and the liquid containing these polycondensation reaction products was obtained. This liquid is a similar structure with a water-soluble co polymer (A2), the two-ethanediyl groups both are n- propanediyl group of the structural unit (U1) contained in the water-soluble co polymer (A2) A water-soluble copolymer having a changed structure (also referred to as “water-soluble copolymer (B1)” in the present specification) is contained. Hereinafter, this liquid is also referred to as “liquid (B1)”.
Zinc oxide as a zinc source, an amount of a bath-soluble zinc-containing substance derived from the zinc equivalent in the plating bath in an amount of 10 g / L, and sodium hydroxide as an alkali component dissolved in 1 L of the plating bath Of the water-soluble copolymer (B1) in the plating bath in an amount of 1 g / L, and Metas ZES-V (YUKEN INDUSTRY CO., LTD.) As an auxiliary brightener. An alkaline zincate-type galvanizing bath containing 1 ml / L of Co., Ltd. was prepared. Hereinafter, using this zincate-type zinc plating bath, electroplating was performed under the three different plating conditions shown in Example 1 to obtain three zinc-based plating members having a zinc plating film.
２．評価
（１）異常析出の発生およびその程度の評価
実施例１および２ならびに比較例１において条件１のめっき条件にて作製した亜鉛系めっき部材における、めっき槽内に配置されていた際にめっき液高さの１／２に相当する位置のめっき皮膜の表面を目視にて観察して、異常析出の発生の有無を確認した。異常析出が発生している場合には、異常析出が析出している領域の高電流密度側端部からの距離を測定した。
2. Evaluation (1) Occurrence of abnormal precipitation and evaluation of its degree Plating solution when disposed in a plating tank in the zinc-based plating member produced under the plating conditions of conditions 1 and 2 and comparative example 1 The surface of the plating film at a position corresponding to ½ of the height was visually observed to confirm the occurrence of abnormal precipitation. When abnormal precipitation occurred, the distance from the end portion on the high current density side in the region where the abnormal precipitation occurred was measured.
（２）めっき膜厚分布
実施例１および２ならびに比較例１において条件２のめっき条件にて作製した亜鉛系めっき部材における、めっき槽内に配置されていた際にめっき液高さの１／２に相当する位置のめっき皮膜の厚さ（単位：μｍ）を、高電流密度側端部から１０ｍｍ、５０ｍｍ、８０ｍｍの位置で、蛍光Ｘ線膜厚計（ＳＩＩ社製：ＳＦＴ−９２００）により測定した。
(2) Plating film thickness distribution In the zinc-based plating member produced under the plating conditions of conditions 2 in Examples 1 and 2 and Comparative Example 1, it was 1/2 of the plating solution height when placed in the plating tank. Is measured with a fluorescent X-ray film thickness meter (SFT: 9FT) at positions of 10 mm, 50 mm, and 80 mm from the end portion on the high current density side. did.
（３）めっき皮膜の外観の観察
実施例１および２ならびに比較例１において条件２のめっき条件にて作製した亜鉛系めっき部材における、めっき槽内に配置されていた際にめっき液高さの１／２に相当する位置のめっき皮膜の表面を目視にて観察して、次の基準で評価した。
Ａ：全面光沢外観
Ｂ：高電流密度部から中電流密度部光沢外観であるが、低電流密度部に曇った外観を有する
Ｃ：高電流密度部から中電流密度部光沢外観であるが、低電流密度部において、曇った外観を有し、さらに白く曇った外観も有する
Ｄ：高電流密度部から中電流密度部光沢外観であるが、低電流密度部において、白く曇った外観を有し、さらに灰色となる外観も有する
(3) Observation of the appearance of the plating film In the zinc-based plating member produced under the conditions of the conditions 2 in Examples 1 and 2 and Comparative Example 1, the height of the plating solution was 1 when placed in the plating tank. The surface of the plating film at the position corresponding to / 2 was visually observed and evaluated according to the following criteria.
A: Overall gloss appearance B: High current density part to medium current density part gloss appearance, but low current density part has a cloudy appearance C: High current density part to medium current density part gloss appearance, but low In the current density part, it has a cloudy appearance, and also has a white cloudy appearance. D: From a high current density part to a medium current density part glossy appearance, but in a low current density part, it has a white cloudy appearance, It also has a gray appearance
（４）光沢付き廻りの評価ハルセル外観を目視にて観察し、次の基準で評価した。
実施例１および２ならびに比較例１において条件３のめっき条件にて作製した亜鉛系めっき部材における、めっき槽内に配置されていた際にめっき液高さの１／２に相当する位置のめっき皮膜の表面を目視にて観察して、次の基準で評価した。
Ａ：全面光沢外観
Ｂ：高電流密度部から中電流密度部光沢外観であるが、低電流密度部に曇った外観を有する
Ｃ：高電流密度部から中電流密度部光沢外観であるが、低電流密度部において、曇った外観を有し、さらに白く曇った外観も有する
Ｄ：高電流密度部から中電流密度部光沢外観であるが、低電流密度部において、白く曇った外観を有し、さらに灰色となる外観も有する
(4) Evaluation of glossy area The appearance of the hull cell was visually observed and evaluated according to the following criteria.
In the zinc-based plated member produced under the plating conditions of conditions 3 in Examples 1 and 2 and Comparative Example 1, the plating film at a position corresponding to ½ of the plating solution height when placed in the plating tank The surface of was visually observed and evaluated according to the following criteria.
A: Overall gloss appearance B: High current density part to medium current density part gloss appearance, but low current density part has a cloudy appearance C: High current density part to medium current density part gloss appearance, but low In the current density part, it has a cloudy appearance, and also has a white cloudy appearance. D: From a high current density part to a medium current density part glossy appearance, but in a low current density part, it has a white cloudy appearance, It also has a gray appearance
３．結果
評価結果を表１に示す。
Claims (11)
当該浴可溶性金属含有物質に含まれる金属元素は鉄、ニッケル、コバルトおよびマンガンからなる群から選ばれる一種または二種以上である請求項５から９のいずれか一項に記載のめっき浴。 Further containing a bath-soluble metal-containing substance,
The plating bath according to any one of claims 5 to 9, wherein the metal element contained in the bath-soluble metal-containing material is one or more selected from the group consisting of iron, nickel, cobalt, and manganese.
請求項５から１０のいずれか一項に記載されるジンケート型亜鉛系めっき浴を用いることを特徴とする亜鉛系めっき部材の製造方法。 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,
A method for producing a zinc-based plated member, wherein the zincate-type zinc-based plating bath according to any one of claims 5 to 10 is used.
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