JP5363523B2 - Additive for electrolytic copper plating and electrolytic copper plating bath - Google Patents
Additive for electrolytic copper plating and electrolytic copper plating bath Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 134
- 239000010949 copper Substances 0.000 title claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 46
- 239000000654 additive Substances 0.000 title claims abstract description 44
- 230000000996 additive effect Effects 0.000 title claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- -1 alkenyl alcohol Chemical compound 0.000 claims description 47
- 238000007259 addition reaction Methods 0.000 claims description 31
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000002244 precipitate Substances 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 229910000365 copper sulfate Inorganic materials 0.000 description 17
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 17
- 229920001451 polypropylene glycol Polymers 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 125000001165 hydrophobic group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- RGLYKWWBQGJZGM-ZCXUNETKSA-N 4-[(z)-4-(4-hydroxyphenyl)hex-3-en-3-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(/CC)=C(/CC)C1=CC=C(O)C=C1 RGLYKWWBQGJZGM-ZCXUNETKSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 2
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- YHCCCMIWRBJYHG-UHFFFAOYSA-N 3-(2-ethylhexoxymethyl)heptane Chemical compound CCCCC(CC)COCC(CC)CCCC YHCCCMIWRBJYHG-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、電気銅めっき用添加剤及び電気銅めっき浴に関し、特に硫酸銅めっき浴の光沢剤として好適な電気銅めっき用添加剤及びその添加剤を含有した電気銅めっき浴に関する。 The present invention relates to an additive for electrolytic copper plating and an electrolytic copper plating bath, and more particularly to an additive for electrolytic copper plating suitable as a brightener for a copper sulfate plating bath and an electrolytic copper plating bath containing the additive.
従来、電気銅めっき浴に光沢剤を添加して光沢のある銅めっき被膜を与えることが行われている。その光沢剤としては、例えば有機チオ化合物、酸素含有高分子有機化合物等が知られている（例えば、特許文献１又は２参照。）。有機チオ化合物としては、ＮａＯ３ＳＣ３Ｈ６Ｓ−ＳＣ３Ｈ６ＳＯ３Ｎａなどのジスルファイド系化合物が汎用され、また酸素含有高分子有機化合物としては、オキシアルキレンポリマー、ポリエチレングリコール、ポリプロピレングリコールなどが使用されている。 Conventionally, a bright copper plating film is provided by adding a brightening agent to an electrolytic copper plating bath. As the brightener, for example, an organic thio compound, an oxygen-containing polymer organic compound, and the like are known (see, for example, Patent Document 1 or 2). The organic thio compounds, disulfide compounds such as NaO 3 SC 3 H 6 S- SC 3 H 6 SO 3 Na is universal, and as the oxygen-containing polymeric organic compound, an oxyalkylene polymer, polyethylene glycol, polypropylene glycol, etc. Is used.
また、上記化合物以外の光沢剤として、下記一般式
Ｈ−（ＥＯ）ａ−（ＰＯ）ｍ−（ＥＯ）ｂ−Ｈ
で示される、ポリプロピレングリコールにエチレンオキサイドを付加したポリマーが使用されている。なお、上記式中において、ＥＯはオキシエチレン基を表し、ＰＯはオキシプロピレン基を表し、ｎ＝ａ＋ｂとする。
Further, as brighteners other than the above compounds, the following general formula H- (EO) a- (PO) m- (EO) b-H
A polymer obtained by adding ethylene oxide to polypropylene glycol is used. In the above formula, EO represents an oxyethylene group, PO represents an oxypropylene group, and n = a + b.
しかしながら、これら従来使用されてきた光沢剤は、銅めっき被膜の低電流密度部における光沢性やつきまわり性が十分ではなく、粗雑な被膜を形成させていた。その原因として、例えば上記一般式で示されるポリマーでは、その分子構造において、疎水基の（ＰＯ）ｍが両側の（ＥＯ）ｎに挟まれているため、疎水基としての効果が弱められているためと考えられる。その結果、このポリマーからなる化合物を電気銅めっき浴の光沢剤として用いた場合には、低電流密度部や高電流密度部において電流分布が乱れ、均一な電着を阻害し、微細なピットやくもりを発生させるなど、不良めっきが生じることとなっていた。 However, these conventionally used brighteners are not sufficient in glossiness and throwing power in the low current density portion of the copper plating film, and form a rough film. As a cause thereof, for example, in the polymer represented by the above general formula, in the molecular structure, (PO) m of the hydrophobic group is sandwiched between (EO) n on both sides, so that the effect as the hydrophobic group is weakened. This is probably because of this. As a result, when this polymer compound is used as a brightening agent for an electrolytic copper plating bath, the current distribution is disturbed in the low current density part and the high current density part, and uniform electrodeposition is hindered. Defective plating would occur, such as clouding.
また、電気銅めっき用の光沢剤としては、管理し易く、不使用時においても消耗しないことが望まれている。 Moreover, as a brightener for electrolytic copper plating, it is desired to be easy to manage and not to be consumed even when not in use.
そこで、本発明は、上述のような従来の実情に鑑みてなされたものであり、低電流密度部から高電流密度部まで均一なめっき被膜を形成させて良好な光沢性を付与し、また不使用時においても消耗しない電気銅めっき用添加剤及びその添加剤を含有した電気銅めっき浴を提供することを目的とする。 Therefore, the present invention has been made in view of the above-described conventional situation, and a uniform plating film is formed from a low current density portion to a high current density portion to give a good gloss, and is not good. An object of the present invention is to provide an additive for electrolytic copper plating that does not wear even during use, and an electrolytic copper plating bath containing the additive.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、疎水基の効果を高めたブロックポリマー化合物を添加剤として用いることによって、低電流密度部から高電流密度部まで均一なめっき被膜を形成させて良好な光沢性を付与できることを見出し、本発明を完成させるに至った。 As a result of intensive studies in order to solve the above problems, the present inventors have used a block polymer compound having an enhanced effect of a hydrophobic group as an additive, so that a uniform from a low current density part to a high current density part can be obtained. It has been found that a good gloss can be imparted by forming a plating film, and the present invention has been completed.
すなわち、本発明に係る電気銅めっき用添加剤は、下記一般式（１）で示されるブロックポリマー化合物からなる。 That is, the additive for electrolytic copper plating according to the present invention comprises a block polymer compound represented by the following general formula (1).
また、本発明に係る電気銅めっき浴は、上記一般式（１）で示されるブロックポリマー化合物からなる添加剤を含有する。 Moreover, the electrolytic copper plating bath which concerns on this invention contains the additive which consists of a block polymer compound shown by the said General formula (1).
本発明によれば、低電流密度部から高電流密度部まで均一なめっき被膜を形成させて良好な光沢性を付与することができ、また不使用時においても消耗せず安定的に良好なめっき被膜を形成させることができる。 According to the present invention, a uniform plating film can be formed from a low current density part to a high current density part to give a good gloss, and stable and good plating without being consumed even when not in use. A film can be formed.
以下、本実施の形態に係る電気銅めっき用添加剤及びその添加剤を含有した電気銅めっき浴について詳細に説明する。 Hereinafter, the electrolytic copper plating additive and the electrolytic copper plating bath containing the additive according to the present embodiment will be described in detail.
本実施の形態に係る電気銅めっき用添加剤は、下記一般式（１）で示されるブロックポリマー化合物からなるものである。 The additive for electrolytic copper plating which concerns on this Embodiment consists of a block polymer compound shown by following General formula (1).
ここで、一般式（１）中、Ｒは直鎖又は分岐鎖の炭素数１〜１５のアルキル基又はアルケニル基を表し、ｍは１〜３０、ｎは１〜４０の整数である。 Here, in general formula (1), R represents a linear or branched alkyl group or alkenyl group having 1 to 15 carbon atoms, m is 1 to 30, and n is an integer of 1 to 40.
直鎖又は分岐鎖の炭素数１〜１５のアルキル基又はアルケニル基であるＲとしては、例えば、メチル基、エチル基、ｎ−プロピル基、アリル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、１−メチルヘキシル基、２−エチルヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基などを挙げることができる。 Examples of R that is a linear or branched alkyl group or alkenyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an allyl group, an n-butyl group, an n-pentyl group, and n. -Hexyl group, 1-methylhexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, Examples thereof include an n-tetradecyl group and an n-pentadecyl group.
また、一般式（１）中のｍ及びｎは、上述したＲの種類に応じて適宜設定することができる。具体的には、Ｒの炭素数が増加するにつれ疎水性が高まることから、そのＲの種類に応じてｍ及びｎのモル比を調整することによって、めっき浴への適度な溶解性を備えるようにすることができる。また、ｍ及びｎは、好ましくは上記一般式（１）で示されるブロックポリマーの分子量が５００〜２０００となるように設定することができる。 Moreover, m and n in General formula (1) can be suitably set according to the kind of R mentioned above. Specifically, since the hydrophobicity increases as the carbon number of R increases, by adjusting the molar ratio of m and n according to the type of R, it is possible to have appropriate solubility in the plating bath. Can be. Moreover, m and n can preferably be set such that the molecular weight of the block polymer represented by the general formula (1) is 500 to 2,000.
上記一般式（１）に示されるように、この添加剤は、オキシプロピレン基側の末端がアルキル基又はアルケニル基でキャップされた構造となっている。このように、オキシプロピレン基の末端をアルキル基又はアルケニル基でキャップすることによって、オキシプロピレン基の疎水基としての効果を高めることができる。 As shown in the general formula (1), this additive has a structure in which the terminal on the oxypropylene group side is capped with an alkyl group or an alkenyl group. Thus, by capping the terminal of the oxypropylene group with an alkyl group or an alkenyl group, the effect of the oxypropylene group as a hydrophobic group can be enhanced.
そしてさらに、上記一般式（１）に示す添加剤は、オキシプロピレン基（ＰＯ）とオキシエチレン基（ＥＯ）の順番が一定であり、常にＲ−Ｏ−（ＰＯ）ｍ−（ＥＯ）ｎ−Ｈの構造からなるブロックポリマーである。これにより、上述のように末端がアルキル基又はアルケニル基でキャップされたオキシプロピレン基（（ＰＯ）ｍ）により、上記一般式（１）において、「Ｒ−Ｏ−（ＰＯ）ｍ」の部分がまとめて疎水基として作用し、高い疎水性を有するようになる。 Furthermore, in the additive represented by the general formula (1), the order of the oxypropylene group (PO) and the oxyethylene group (EO) is constant, and always R—O— (PO) m— (EO) n—. It is a block polymer having a structure of H. As a result, the oxypropylene group ((PO) m) whose end is capped with an alkyl group or an alkenyl group as described above allows the portion of “RO— (PO) m” in the general formula (1) to be Collectively, it acts as a hydrophobic group and has high hydrophobicity.
このことから予測される作用としては、一般に化合物の疎水基は、水中から界面に押し出されるため、水溶液に被めっき物が浸漬されると、被めっき物のめっき面が界面となり、高い疎水性を有する添加剤はめっき面に濃縮され、添加剤の効果が高まる。その結果、低電流密度部から高電流密度部までの全体にわたって添加剤の効果が発揮されるため、均一なめっき被膜を形成させて良好な光沢性を付与できるものと考えられる。 As expected from this, the hydrophobic group of the compound is generally pushed out of the water to the interface, so when the object to be plated is immersed in an aqueous solution, the plating surface of the object becomes the interface, and the hydrophobicity is high. The additive having is concentrated on the plating surface, and the effect of the additive is enhanced. As a result, since the effect of the additive is exhibited throughout the low current density portion to the high current density portion, it is considered that a uniform plating film can be formed and good glossiness can be imparted.
さらに、このようなブロックポリマーであることにより、他方の末端のオキシエチレン基により適度な溶解性を備えるようにすることができ、電気銅めっき浴中に良好にポリマー化合物が溶解し、まためっき浴中において安定的に維持させることができ、電解処理の不使用時において経時的に消耗していくことを抑制できる。 Furthermore, by being such a block polymer, it can be made to have appropriate solubility by the oxyethylene group at the other end, and the polymer compound dissolves well in the electrolytic copper plating bath, and the plating bath It can be stably maintained inside, and can be prevented from being consumed with time when the electrolytic treatment is not used.
上記一般式（１）で示されるブロックポリマー化合物は、例えば以下の方法により製造することができる。すなわち、窒素ガスなどの不活性ガス雰囲気下において、先ず、炭素数１〜１５のアルキルアルコール又はアルケニルアルコールにプロピレンオキサイドを付加反応させる。プロピレンオキサイドの付加反応の終了後、次に、エチレンオキサイドを加えてエチレンオキサイドの付加反応を行うことによって得ることができる。 The block polymer compound represented by the general formula (1) can be produced, for example, by the following method. That is, in an inert gas atmosphere such as nitrogen gas, first, propylene oxide is subjected to addition reaction with alkyl alcohol or alkenyl alcohol having 1 to 15 carbon atoms. After completion of the addition reaction of propylene oxide, it can be obtained by adding ethylene oxide and carrying out addition reaction of ethylene oxide.
このように、ブロックポリマー化合物は、炭素数１〜１５のアルキルアルコール又はアルケニルアルコールにプロピレンオキサイドを付加反応させた後に、エチレンオキサイドを加えて付加反応させて合成することによって、アルキル基又はアルケニル基でキャップされた（ＰＯ）ｍに（ＥＯ）ｎが付加された一定の構造からなるブロック体とすることができる。 In this way, the block polymer compound is synthesized by adding propylene oxide to an alkyl alcohol or alkenyl alcohol having 1 to 15 carbon atoms and then adding ethylene oxide to carry out an addition reaction. A block body having a certain structure in which (EO) n is added to capped (PO) m can be obtained.
ブロックポリマー化合物の製造方法における反応温度としては、特に限定されないが、９０〜１６０℃とすることが好ましい。反応温度を９０℃以上とすることにより、適度な反応速度を得ることができ効率的にプロピレンオキサイド及びエチレンオキサイドの付加反応を生じさせることができる。また、反応温度を１６０℃以下とすることにより、副反応物などの生成を抑制し、生成させるブロックポリマー化合物の収率を高めることができる。なお、アルキルアルコールにプロピレンオキサイドを付加反応させた後にエチレンオキサイドを付加させるに際し、上述の９０〜１６０℃でプロピレンオキサイドを付加反応させた後、一度冷却させてから、同様の温度条件でエチレンオキサイドの付加反応を行うことが好ましい。 Although it does not specifically limit as reaction temperature in the manufacturing method of a block polymer compound, It is preferable to set it as 90-160 degreeC. By setting the reaction temperature to 90 ° C. or higher, an appropriate reaction rate can be obtained and an addition reaction of propylene oxide and ethylene oxide can be efficiently generated. Moreover, the production | generation of a side reaction product etc. can be suppressed by making reaction temperature 160 degrees C or less, and the yield of the block polymer compound to produce | generate can be raised. In addition, when adding ethylene oxide after carrying out addition reaction of propylene oxide to alkyl alcohol, after carrying out addition reaction of propylene oxide at the above-mentioned 90-160 degreeC, after making it cool once, under the same temperature conditions, it is ethylene oxide. It is preferable to perform an addition reaction.
また、反応時間としては、特に限定されず反応温度によっても異なるが、プロピレンオキサイド及びエチレンオキサイドのそれぞれの付加反応において、１５時間以内であることが好ましい。１５時間以内とすることにより、副反応物などの生成を抑制し、生成させるブロックポリマー化合物の収率を高めることができる。 In addition, the reaction time is not particularly limited and varies depending on the reaction temperature, but is preferably within 15 hours in each addition reaction of propylene oxide and ethylene oxide. By making it within 15 hours, production of by-products and the like can be suppressed, and the yield of the block polymer compound to be produced can be increased.
また、付加反応に際しては、加圧下で行うことが好ましく、付加反応開始時の圧力としては２〜５ｋｇ／ｃｍ２とすることが好ましい。 The addition reaction is preferably carried out under pressure, and the pressure at the start of the addition reaction is preferably 2 to 5 kg / cm 2 .
上記一般式（１）で示されるブロックポリマー化合物を電気銅めっきの添加剤として使用する場合、そのときの添加濃度としては０．０５〜１．０ｇ／Ｌとすることが好ましい。添加濃度を０．０５ｇ／Ｌ以上とすることによって、十分な光沢性を有するめっき被膜を形成させることができる。また、添加濃度を１．０ｇ／Ｌ以下とすることによって、有効に使用可能な電流密度範囲が狭まることを防止して、低電流密度部から高電流密度部まで均一に良好なめっき被膜を形成させることができる。 When the block polymer compound represented by the general formula (1) is used as an additive for electrolytic copper plating, the additive concentration at that time is preferably 0.05 to 1.0 g / L. By setting the additive concentration to 0.05 g / L or more, a plating film having sufficient gloss can be formed. In addition, by making the additive concentration 1.0 g / L or less, the effective current density range is prevented from narrowing, and a uniform plating film is formed uniformly from the low current density part to the high current density part. Can be made.
次に、上述した一般式（１）で示されるブロックポリマー化合物からなる添加剤が添加される電気銅めっき浴、及びその電気銅めっき浴を用いためっき処理について説明する。電気銅めっき浴としては、特に限定されないが、特に硫酸銅めっき浴とすることが好ましい。このように、硫酸銅めっき浴に上述したブロックポリマー化合物を添加させることによって、幅広い電流密度範囲において、均一に、優れた光沢性を有する銅めっき被膜を形成させることができ、装飾用めっき処理に用いるめっき浴として好適に用いることができる。 Next, an electrolytic copper plating bath to which an additive composed of the block polymer compound represented by the general formula (1) described above is added, and a plating process using the electrolytic copper plating bath will be described. The electrolytic copper plating bath is not particularly limited, but is particularly preferably a copper sulfate plating bath. Thus, by adding the block polymer compound described above to the copper sulfate plating bath, a copper plating film having excellent gloss can be uniformly formed in a wide current density range, and can be used for decorative plating treatment. It can use suitably as a plating bath to be used.
具体的に、硫酸銅めっき浴の組成としては、例えば硫酸銅（Ｃｕ２ＳＯ４・５Ｈ２Ｏ）５０〜２５０ｇ／Ｌ、濃硫酸５０〜２５０ｇ／Ｌを基本組成とするめっき浴とすることができる。なお、硫酸銅めっき浴には、通常微量（１０〜２００ｍｇ／Ｌ程度）の塩化物イオンを含有させる。具体的には、例えばＮａＣｌ等の水溶性塩化物を添加することにより含有させることができる。 Specifically, the composition of the copper sulfate plating bath is, for example, a plating bath having a basic composition of 50 to 250 g / L of copper sulfate (Cu 2 SO 4 .5H 2 O) and 50 to 250 g / L of concentrated sulfuric acid. it can. The copper sulfate plating bath usually contains a trace amount (about 10 to 200 mg / L) of chloride ions. Specifically, for example, it can be contained by adding a water-soluble chloride such as NaCl.
なお、上述した電気銅めっき浴には、さらに既知の添加剤を添加させることによって光沢性や平滑性をより向上させるようにしてもよい。具体的には、例えば有機チオ化合物や有機酸アミド類、酸素含有高分子有機化合物などを添加することができる。 In addition, you may make it improve glossiness and smoothness by adding a known additive further to the electrolytic copper plating bath mentioned above. Specifically, for example, organic thio compounds, organic acid amides, oxygen-containing polymer organic compounds, and the like can be added.
上述した電気銅めっき浴を用いためっき処理条件として、ｐＨは１以下とする。また、めっき温度としては２０〜５０℃の範囲とし、陰極電流密度としては０．１〜８Ａ／ｄｍ２とすることが好ましい。また、陽極としては、銅板、不溶性陽極を用いることができる。さらに、より均一な光沢性を有するめっき被膜を形成させるため、空気攪拌、カソードロッキング等の攪拌を十分に行うことが好ましい。 As a plating treatment condition using the above-described electrolytic copper plating bath, the pH is set to 1 or less. The plating temperature is preferably in the range of 20 to 50 ° C., and the cathode current density is preferably 0.1 to 8 A / dm 2 . Moreover, a copper plate and an insoluble anode can be used as the anode. Furthermore, in order to form a plating film having more uniform gloss, it is preferable to sufficiently perform stirring such as air stirring and cathode locking.
また、上述しためっき処理が施される被めっき処理物としては、特に制限されないが、例えばプラスチックなどの被めっき処理物に対して装飾めっきを施すことを目的として、上述した添加剤を添加した電気銅めっき浴を好適に用いることができる。なお、その他、スルホールを有するプリント配線基板や電気・電子部品などを対象としてめっき処理を施してもよい。このように、上述した添加剤を添加した電気銅めっき浴は、装飾的な用途から機能的な目的まで、幅広く適用することができる。 In addition, the object to be plated to be subjected to the above-described plating treatment is not particularly limited, but for example, an electric to which the above-mentioned additives are added for the purpose of performing decorative plating on the object to be plated such as plastic. A copper plating bath can be suitably used. In addition, a plating process may be applied to a printed wiring board having a through hole or an electric / electronic component. Thus, the electrolytic copper plating bath to which the above-mentioned additive is added can be widely applied from a decorative use to a functional purpose.
以下、本発明の具体的な実施例について説明する。なお、下記のいずれかの実施例に本発明が限定されるものではない。 Hereinafter, specific examples of the present invention will be described. Note that the present invention is not limited to any of the following examples.
下記に説明する各実施例では、表１に示すブロックポリマー（Ｒ−Ｏ−（ＰＯ）ｍ−（ＥＯ）ｎ−Ｈ）を合成し、そのブロックポリマー化合物を添加剤として添加した銅めっき浴を用いてめっき処理を行い、析出形成されためっき被膜を評価した。なお、銅めっき浴には、空気を吹き込んで十分攪拌し、特に陰極の近傍が攪拌されるように空気を被めっき物に当たるようにした。 In each example described below, a copper plating bath in which the block polymer (RO— (PO) m— (EO) n—H) shown in Table 1 was synthesized and the block polymer compound was added as an additive was prepared. Using this, plating treatment was performed, and the plating film formed by precipitation was evaluated. Note that air was blown into the copper plating bath and sufficiently stirred, and air was applied to the object to be plated so that the vicinity of the cathode was particularly stirred.
＜実施例１＞
（ブロックポリマーの合成）
気密反応容器に、ｎ−プロパノール６００ｇ（１０モル）と水酸化カリウム５.６ｇ（０．１モル）を採り、窒素ガス雰囲気下でプロピレンオキサイド８７０ｇ（１５モル）を９０〜１３０℃、２〜５ｋｇ／ｃｍ２の加圧下で付加反応させた。プロピレンオキサイドの付加反応終了後、反応容器を冷却し、次にエチレンオキサイド６６０ｇ（１５モル）を加えて、同様の条件で付加反応させた。
<Example 1>
(Synthesis of block polymer)
In an airtight reaction vessel, 600 g (10 mol) of n-propanol and 5.6 g (0.1 mol) of potassium hydroxide are taken, and 870 g (15 mol) of propylene oxide is 90 to 130 ° C. and 2 to 5 kg in a nitrogen gas atmosphere. The addition reaction was carried out under a pressure of / cm 2 . After completion of the addition reaction of propylene oxide, the reaction vessel was cooled, and then 660 g (15 mol) of ethylene oxide was added to carry out the addition reaction under the same conditions.
次に、反応容器に、合成吸着材（キョーワード６００、協和化学工業株式会社製）を５０ｇ添加し、７０℃で３０分攪拌処理後にろ過して、ポリオキシエチレン（15）ポリオキシプロピレン（15）プロピルエーテル２０７０ｇを得た。 Next, 50 g of a synthetic adsorbent (KYOWARD 600, manufactured by Kyowa Chemical Industry Co., Ltd.) is added to the reaction vessel, followed by stirring at 70 ° C. for 30 minutes, followed by filtration to obtain polyoxyethylene (15) polyoxypropylene (15 ) 2070 g of propyl ether was obtained.
（めっき処理及びめっき被膜評価）
下記組成
硫酸銅（Ｃｕ２ＳＯ４・５Ｈ２Ｏ） ２００ｇ／Ｌ
濃硫酸 ５０ｇ／Ｌ
ＮａＣｌ １１５ｍｇ／Ｌ
からなる硫酸銅めっき液に、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及び上述のようにして合成したポリオキシエチレン（15）ポリオキシプロピレン（15）プロピルエーテル０．２ｇ／Ｌを加えためっき浴を用い、総電流２Ａ、時間１０分でハルセル試験器を用いてめっき処理を行った。なお、ｐＨ＜１、温度２５℃、陰極電流密度０．１５〜４Ａ／ｄｍ２のめっき処理条件とした。
(Plating treatment and plating film evaluation)
Following composition Copper sulfate (Cu 2 SO 4 · 5H 2 O) 200g / L
Concentrated sulfuric acid 50g / L
NaCl 115mg / L
As an additive, a copper sulfate plating solution composed of bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, a diazotized product of diethyl safranin 50 mg / L, and the polyoxy synthesized as described above Using a plating bath to which 0.2 g / L of ethylene (15) polyoxypropylene (15) propyl ether was added, plating treatment was performed using a Hull Cell tester at a total current of 2 A and time of 10 minutes. The plating conditions were pH <1, temperature 25 ° C., cathode current density 0.15 to 4 A / dm 2 .
その結果、低電流密度部から高電流密度部まで良好な光沢を有する析出物を均一に形成させることができた。 As a result, precipitates having good gloss from the low current density part to the high current density part could be uniformly formed.
また、上述したハルセル試験器に銅板を入れたまま一晩放置した後、同様にしてめっき処理を行った場合でも、最初のめっき処理と同様に良好な光沢を有する析出物を均一に形成させることができた。このことから、添加剤は、不使用時においてもめっき浴中で消耗することなく安定的に維持されることがわかった。 In addition, even if the plating process is performed after leaving the copper plate in the above-described Hull Cell tester overnight, the precipitate having a good gloss should be uniformly formed as in the first plating process. I was able to. From this, it was found that the additive was stably maintained without being consumed in the plating bath even when not in use.
＜実施例２＞
（ブロックポリマーの合成）
気密反応容器に、アリルアルコール（２−プロペン−１−オール）５８０ｇ（１０モル）と水酸化カリウム５.６ｇ（０．１モル）を採り、窒素ガス雰囲気下でプロピレンオキサイド８７０ｇ（１５モル）を９０〜１３０℃、２〜５ｋｇ／ｃｍ２の加圧下で付加反応させた。プロピレンオキサイドの付加反応終了後、反応容器を冷却し、次にエチレンオキサイド６６０ｇ（１５モル）を加えて、同様の条件で付加反応させた。
<Example 2>
(Synthesis of block polymer)
In an airtight reaction vessel, 580 g (10 mol) of allyl alcohol (2-propen-1-ol) and 5.6 g (0.1 mol) of potassium hydroxide are taken, and 870 g (15 mol) of propylene oxide is added in a nitrogen gas atmosphere. The addition reaction was performed at 90 to 130 ° C. under a pressure of 2 to 5 kg / cm 2 . After completion of the addition reaction of propylene oxide, the reaction vessel was cooled, and then 660 g (15 mol) of ethylene oxide was added to carry out the addition reaction under the same conditions.
次に、反応容器に、合成吸着材（キョーワード６００、協和化学工業株式会社製）を５０ｇ添加し、７０℃で３０分攪拌処理後にろ過して、ポリオキシエチレン（15）ポリオキシプロピレン（15）アリルエーテル２０５０ｇを得た。 Next, 50 g of a synthetic adsorbent (KYOWARD 600, manufactured by Kyowa Chemical Industry Co., Ltd.) is added to the reaction vessel, followed by stirring at 70 ° C. for 30 minutes, followed by filtration to obtain polyoxyethylene (15) polyoxypropylene (15 ) 2050 g of allyl ether was obtained.
（めっき処理及びめっき被膜評価）
実施例２では、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及び上述のようにして合成したポリオキシエチレン（15）ポリオキシプロピレン（15）アリルエーテル０．２ｇ／Ｌを加えた硫酸銅めっき浴を用いたこと以外は、実施例１と同様にしてハルセル試験器を用いてめっき処理を行った。
(Plating treatment and plating film evaluation)
In Example 2, as additives, bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, diazotized product of diethyl safranin 50 mg / L, and polyoxyethylene (15 ) Plating was performed using a Hull cell tester in the same manner as in Example 1 except that a copper sulfate plating bath to which 0.2 g / L of polyoxypropylene (15) allyl ether was added was used.
その結果、低電流密度部から高電流密度部まで良好な光沢を有する析出物を均一に形成させることができた。また、上述したハルセル試験器に銅板を入れたまま一晩放置した後、同様にしてめっき処理を行った場合でも、最初のめっき処理と同様に良好な光沢を有する析出物を均一に形成させることができた。 As a result, precipitates having good gloss from the low current density part to the high current density part could be uniformly formed. In addition, even if the plating process is performed after leaving the copper plate in the above-described Hull Cell tester overnight, the precipitate having a good gloss should be uniformly formed as in the first plating process. I was able to.
＜実施例３＞
（ブロックポリマーの合成）
気密反応容器に、ｎ−ブタノール７４０ｇ（１０モル）と水酸化カリウム５.６ｇ（０．１モル）を採り、窒素ガス雰囲気下でプロピレンオキサイド５８０ｇ（１０モル）を９０〜１３０℃、２〜５ｋｇ／ｃｍ２の加圧下で付加反応させた。プロピレンオキサイドの付加反応終了後、反応容器を冷却し、次にエチレンオキサイド６６０ｇ（１５モル）を加えて、同様の条件で付加反応させた。
<Example 3>
(Synthesis of block polymer)
In an airtight reaction vessel, 740 g (10 mol) of n-butanol and 5.6 g (0.1 mol) of potassium hydroxide are taken, and 580 g (10 mol) of propylene oxide is 90 to 130 ° C. and 2 to 5 kg in a nitrogen gas atmosphere. The addition reaction was carried out under a pressure of / cm 2 . After completion of the addition reaction of propylene oxide, the reaction vessel was cooled, and then 660 g (15 mol) of ethylene oxide was added to carry out the addition reaction under the same conditions.
次に、反応容器に、合成吸着材（キョーワード６００、協和化学工業株式会社製）を５０ｇ添加し、７０℃で３０分攪拌処理後にろ過して、ポリオキシエチレン（15）ポリオキシプロピレン（10）ブチルエーテル１９２０ｇを得た。 Next, 50 g of a synthetic adsorbent (KYOWARD 600, manufactured by Kyowa Chemical Industry Co., Ltd.) is added to the reaction vessel, followed by stirring at 70 ° C. for 30 minutes, followed by filtration to obtain polyoxyethylene (15) polyoxypropylene (10 ) 1920 g of butyl ether was obtained.
（めっき処理及びめっき被膜評価）
実施例３では、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及び上述のようにして合成した、ポリオキシエチレン（15）ポリオキシプロピレン（10）ブチルエーテル０．２ｇ／Ｌを加えた硫酸銅めっき浴を用いたこと以外は、実施例１と同様にしてハルセル試験器を用いてめっき処理を行った。
(Plating treatment and plating film evaluation)
In Example 3, as additives, bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, diazotized product of diethyl safranine 50 mg / L, and polyoxyethylene (as described above) ( 15) Plating was performed using a Hull cell tester in the same manner as in Example 1 except that a copper sulfate plating bath to which 0.2 g / L of polyoxypropylene (10) butyl ether was added was used.
その結果、低電流密度部から高電流密度部まで良好な光沢を有する析出物を均一に形成させることができた。また、上述したハルセル試験器に銅板を入れたまま一晩放置した後、同様にしてめっき処理を行った場合でも、最初のめっき処理と同様に良好な光沢を有する析出物を均一に形成させることができた。 As a result, precipitates having good gloss from the low current density part to the high current density part could be uniformly formed. In addition, even if the plating process is performed after leaving the copper plate in the above-described Hull Cell tester overnight, the precipitate having a good gloss should be uniformly formed as in the first plating process. I was able to.
＜実施例４＞
（ブロックポリマーの合成）
気密反応容器に、ｎ−ヘキサノール１０２０ｇ（１０モル）と水酸化カリウム５.６ｇ（０．１モル）を採り、窒素ガス雰囲気下でプロピレンオキサイド２９０ｇ（５モル）を９０〜１３０℃、２〜５ｋｇ／ｃｍ２の加圧下で付加反応させた。プロピレンオキサイドの付加反応終了後、反応容器を冷却し、次にエチレンオキサイド８８０ｇ（２０モル）を加えて、同様の条件で付加反応させた。
<Example 4>
(Synthesis of block polymer)
In an airtight reaction vessel, 1020 g (10 mol) of n-hexanol and 5.6 g (0.1 mol) of potassium hydroxide are taken, and 290 g (5 mol) of propylene oxide is 90 to 130 ° C. and 2 to 5 kg in a nitrogen gas atmosphere. The addition reaction was carried out under a pressure of / cm 2 . After completion of the addition reaction of propylene oxide, the reaction vessel was cooled, and then 880 g (20 mol) of ethylene oxide was added to cause addition reaction under the same conditions.
次に、反応容器に、合成吸着材（キョーワード６００、協和化学工業株式会社製）を５０ｇ添加し、７０℃で３０分攪拌処理後にろ過して、ポリオキシエチレン（20）ポリオキシプロピレン（5）ヘキシルエーテル２１３０ｇを得た。 Next, 50 g of a synthetic adsorbent (KYOWARD 600, manufactured by Kyowa Chemical Industry Co., Ltd.) is added to the reaction vessel, followed by stirring at 70 ° C. for 30 minutes, followed by filtration to obtain polyoxyethylene (20) polyoxypropylene (5 ) 2130 g of hexyl ether was obtained.
（めっき処理及びめっき被膜評価）
実施例４では、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及び上述のようにして合成した、ポリオキシエチレン（20）ポリオキシプロピレン（5）ヘキシルエーテル０．２ｇ／Ｌを加えた硫酸銅めっき浴を用いたこと以外は、実施例１と同様にしてハルセル試験器を用いてめっき処理を行った。
(Plating treatment and plating film evaluation)
In Example 4, as additives, bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, a diazotized product of diethyl safranin 50 mg / L, and polyoxyethylene ( 20) Plating was performed using a Hull cell tester in the same manner as in Example 1 except that a copper sulfate plating bath added with 0.2 g / L of polyoxypropylene (5) hexyl ether was used.
その結果、低電流密度部から高電流密度部まで良好な光沢を有する析出物を均一に形成させることができた。また、上述したハルセル試験器に銅板を入れたまま一晩放置した後、同様にしてめっき処理を行った場合でも、最初のめっき処理と同様に良好な光沢を有する析出物を均一に形成させることができた。 As a result, precipitates having good gloss from the low current density part to the high current density part could be uniformly formed. In addition, even if the plating process is performed after leaving the copper plate in the above-described Hull Cell tester overnight, the precipitate having a good gloss should be uniformly formed as in the first plating process. I was able to.
＜実施例５＞
（ブロックポリマーの合成）
気密反応容器に、２−エチルヘキサノール１３００ｇ（１０モル）と水酸化カリウム５.６ｇ（０．１モル）を採り、窒素ガス雰囲気下でプロピレンオキサイド１７４ｇ（３モル）を９０〜１３０℃、２〜５ｋｇ／ｃｍ２の加圧下で付加反応させた。プロピレンオキサイドの付加反応終了後、反応容器を冷却し、次にエチレンオキサイド１１００ｇ（２５モル）を加えて、同様の条件で付加反応させた。
<Example 5>
(Synthesis of block polymer)
In an airtight reaction vessel, take 1300 g (10 mol) of 2-ethylhexanol and 5.6 g (0.1 mol) of potassium hydroxide, and add 174 g (3 mol) of propylene oxide at 90 to 130 ° C., 2 to 2 in a nitrogen gas atmosphere. The addition reaction was carried out under a pressure of 5 kg / cm 2 . After completion of the addition reaction of propylene oxide, the reaction vessel was cooled, and then 1100 g (25 mol) of ethylene oxide was added to cause addition reaction under the same conditions.
次に、反応容器に、合成吸着材（キョーワード６００、協和化学工業株式会社製）を５０ｇ添加し、７０℃で３０分攪拌処理後にろ過して、ポリオキシエチレン（25）ポリオキシプロピレン（3）２−エチルヘキシルエーテル２５００ｇを得た。 Next, 50 g of a synthetic adsorbent (KYOWARD 600, manufactured by Kyowa Chemical Industry Co., Ltd.) is added to the reaction vessel, followed by stirring at 70 ° C. for 30 minutes, followed by filtration to obtain polyoxyethylene (25) polyoxypropylene (3 ) 2500 g of 2-ethylhexyl ether was obtained.
（めっき処理及びめっき被膜評価）
実施例５では、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及び上述のようにして合成した、ポリオキシエチレン（25）ポリオキシプロピレン（3）２−エチルヘキシルエーテル０．２ｇ／Ｌを加えた硫酸銅めっき浴を用いたこと以外は、実施例１と同様にしてハルセル試験器を用いてめっき処理を行った。
(Plating treatment and plating film evaluation)
In Example 5, as additives, bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, diazotized product of diethyl safranin 50 mg / L, and polyoxyethylene ( 25) Plating was performed using a Hull cell tester in the same manner as in Example 1 except that a copper sulfate plating bath to which 0.2 g / L of polyoxypropylene (3) 2-ethylhexyl ether was added was used.
その結果、低電流密度部から高電流密度部まで良好な光沢を有する析出物を均一に形成させることができた。また、上述したハルセル試験器に銅板を入れたまま一晩放置した後、同様にしてめっき処理を行った場合でも、最初のめっき処理と同様に良好な光沢を有する析出物を均一に形成させることができた。 As a result, precipitates having good gloss from the low current density part to the high current density part could be uniformly formed. In addition, even if the plating process is performed after leaving the copper plate in the above-described Hull Cell tester overnight, the precipitate having a good gloss should be uniformly formed as in the first plating process. I was able to.
＜実施例６＞
（ブロックポリマーの合成）
気密反応容器に、１−ドデカノール１８６０ｇ（１０モル）と水酸化カリウム５.６ｇ（０．１モル）を採り、窒素ガス雰囲気下でプロピレンオキサイド１１６ｇ（２モル）を９０〜１３０℃、２〜５ｋｇ／ｃｍ２の加圧下で付加反応させた。プロピレンオキサイドの付加反応終了後、反応容器を冷却し、次にエチレンオキサイド１３２０ｇ（３０モル）を加えて、同様の条件で付加反応させた。
<Example 6>
(Synthesis of block polymer)
In an airtight reaction vessel, 1860 g (10 mol) of 1-dodecanol and 5.6 g (0.1 mol) of potassium hydroxide are taken, and 116 g (2 mol) of propylene oxide is 90 to 130 ° C. and 2 to 5 kg in a nitrogen gas atmosphere. The addition reaction was carried out under a pressure of / cm 2 . After completion of the addition reaction of propylene oxide, the reaction vessel was cooled, and then 1320 g (30 mol) of ethylene oxide was added to carry out the addition reaction under the same conditions.
次に、反応容器に、合成吸着材（キョーワード６００、協和化学工業株式会社製）を５０ｇ添加し、７０℃で３０分攪拌処理後にろ過して、ポリオキシエチレン（30）ポリオキシプロピレン（2）ドデシルエーテル３２００ｇを得た。 Next, 50 g of a synthetic adsorbent (KYOWARD 600, manufactured by Kyowa Chemical Industry Co., Ltd.) is added to the reaction vessel, followed by stirring at 70 ° C. for 30 minutes, followed by filtration to obtain polyoxyethylene (30) polyoxypropylene (2 ) 3200 g of dodecyl ether was obtained.
（めっき処理及びめっき被膜評価）
実施例６では、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及び上述のようにして合成した、ポリオキシエチレン（30）ポリオキシプロピレン（2）ドデシルエーテル０．２ｇ／Ｌを加えた硫酸銅めっき浴を用いたこと以外は、実施例１と同様にしてハルセル試験器を用いてめっき処理を行った。
(Plating treatment and plating film evaluation)
In Example 6, as additives, bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, diazotized product of diethyl safranin 50 mg / L, and polyoxyethylene ( 30) Plating was performed using a Hull cell tester in the same manner as in Example 1 except that a copper sulfate plating bath to which 0.2 g / L of polyoxypropylene (2) dodecyl ether was added was used.
その結果、低電流密度部から高電流密度部まで良好な光沢を有する析出物を均一に形成させることができた。また、上述したハルセル試験器に銅板を入れたまま一晩放置した後、同様にしてめっき処理を行った場合でも、最初のめっき処理と同様に良好な光沢を有する析出物を均一に形成させることができた。 As a result, precipitates having good gloss from the low current density part to the high current density part could be uniformly formed. In addition, even if the plating process is performed after leaving the copper plate in the above-described Hull Cell tester overnight, the precipitate having a good gloss should be uniformly formed as in the first plating process. I was able to.
＜比較例１＞
（めっき処理及びめっき被膜評価）
比較例１では、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及びポリエチレングリコール０．２ｇ／Ｌを加えた硫酸銅めっき浴を用いたこと以外は、実施例１と同様にしてハルセル試験器を用いてめっき処理を行い、析出形成されためっき被膜の評価を行った。なお、この比較例１並びに下記比較例２及び３においても、銅めっき浴には空気を吹き込んで十分に攪拌を行った。
<Comparative Example 1>
(Plating treatment and plating film evaluation)
In Comparative Example 1, copper sulfate to which bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, diazotized product of diethyl safranin 50 mg / L, and polyethylene glycol 0.2 g / L were added as additives. Except for using a plating bath, the plating treatment was performed using a Hull cell tester in the same manner as in Example 1 to evaluate the deposited plating film. In Comparative Example 1 and Comparative Examples 2 and 3 below, air was blown into the copper plating bath and sufficiently stirred.
その結果、析出物は良好な光沢を有するものであったが、微細なピットや白くもりが生じてしまい、低電流密度部から高電流密度部まで均一な析出物は形成されず、不良な外観のめっき被膜であった。 As a result, the precipitate had a good gloss, but fine pits and white cloudiness occurred, and a uniform precipitate was not formed from the low current density portion to the high current density portion, resulting in a poor appearance. It was a plating film.
＜比較例２＞
（めっき処理及びめっき被膜評価）
比較例２では、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及びポリプロピレングリコール０．２ｇ／Ｌを加えた硫酸銅めっき浴を用いたこと以外は、実施例１と同様にしてハルセル試験器を用いてめっき処理を行い、析出形成されためっき被膜の評価を行った。
<Comparative example 2>
(Plating treatment and plating film evaluation)
In Comparative Example 2, copper sulfate to which bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, diazotized product of diethyl safranin 50 mg / L, and polypropylene glycol 0.2 g / L were added as additives. Except for using a plating bath, the plating treatment was performed using a Hull cell tester in the same manner as in Example 1 to evaluate the deposited plating film.
その結果、析出物は良好な光沢を有するものであったが、微細なピットや白くもりが生じてしまい、低電流密度部から高電流密度部まで均一な析出物は形成されず、不良な外観のめっき被膜であった。 As a result, the precipitate had a good gloss, but fine pits and white cloudiness occurred, and a uniform precipitate was not formed from the low current density portion to the high current density portion, resulting in a poor appearance. It was a plating film.
＜比較例３＞
（めっき処理及びめっき被膜評価）
比較例３では、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及び、ポリプロピレングリコールにエチレンオキサイドを付加して得られたブロックポリマー（Ｈ−（ＥＯ）ａ−（ＰＯ）ｍ−（ＥＯ）ｂ−Ｈ、ｍ＝１７、ｎ＝ａ＋ｂ＝９）０．２ｇ／Ｌを加えた硫酸銅めっき浴を用いたこと以外は、実施例１と同様にしてハルセル試験器を用いてめっき処理を行い、析出形成されためっき被膜の評価を行った。
<Comparative Example 3>
(Plating treatment and plating film evaluation)
In Comparative Example 3, the additive is obtained by adding ethylene oxide to bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, diazotized product of diethyl safranine 50 mg / L, and polypropylene glycol. Other than using a copper sulfate plating bath to which 0.2 g / L of a block polymer (H- (EO) a- (PO) m- (EO) b-H, m = 17, n = a + b = 9) was added. In the same manner as in Example 1, plating treatment was performed using a Hull cell tester, and the deposited plating film was evaluated.
その結果、析出物は良好な光沢を有するものであったが、微細なピットや白くもりが生じてしまい、低電流密度部から高電流密度部まで均一な析出物は形成されず、不良な外観のめっき被膜であった。 As a result, the precipitate had a good gloss, but fine pits and white cloudiness occurred, and a uniform precipitate was not formed from the low current density portion to the high current density portion, resulting in a poor appearance. It was a plating film.
＜比較例４＞
（めっき処理及びめっき被膜評価）
比較例４では、添加剤として、ビス−（ω−スルホプロピル）−ジスルフィド２ナトリウム塩１０ｍｇ／Ｌ、ジエチルサフラニンのジアゾ化処理物５０ｍｇ／Ｌ、及び、ｎ−ブタノールにエチレンオキサイドとプロピレンオキサイドとを同時に付加して得られたランダムポリマー０．２ｇ／Ｌを加えた硫酸銅めっき浴を用いたこと以外は、実施例１と同様にしてハルセル試験器を用いてめっき処理を行い、析出形成されためっき被膜の評価を行った。
<Comparative example 4>
(Plating treatment and plating film evaluation)
In Comparative Example 4, bis- (ω-sulfopropyl) -disulfide disodium salt 10 mg / L, diethylsafranine diazotized product 50 mg / L, and ethylene oxide and propylene oxide as n-butanol were used as additives. Except for using a copper sulfate plating bath to which 0.2 g / L of a random polymer obtained by addition at the same time was used, plating was performed using a Hull cell tester in the same manner as in Example 1 to form a precipitate. The plating film was evaluated.
その結果、析出物は良好な光沢を有するものであったが、ステップ状に変化して析出する段地めっきとなり、低電流密度部ではめっきは析出されず、不良な外観のめっき被膜であった。 As a result, although the deposit had a good gloss, it became a stepped plating that changed into a step shape and deposited, and the plating was not deposited at the low current density portion, and the plating film had a poor appearance. .
Claims (3)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011070667A JP5363523B2 (en) | 2011-03-28 | 2011-03-28 | Additive for electrolytic copper plating and electrolytic copper plating bath |
| CN201280015856.5A CN103443334B (en) | 2011-03-28 | 2012-03-23 | Cathode copper plates application additive and electrolysis electroless copper bath |
| PCT/JP2012/057594 WO2012133225A1 (en) | 2011-03-28 | 2012-03-23 | Electro copper plating additive and electro copper plating bath |
| KR1020137026205A KR101940593B1 (en) | 2011-03-28 | 2012-03-23 | Electro copper plating additive and electro copper plating bath |
| US14/004,011 US20130341199A1 (en) | 2011-03-28 | 2012-03-23 | Electro copper plating additive and electro copper plating bath |
| TW101110579A TWI608130B (en) | 2011-03-28 | 2012-03-27 | Copper Plating Additives and Copper Plating Baths |
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| JP (1) | JP5363523B2 (en) |
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| KR20160090306A (en) * | 2013-11-25 | 2016-07-29 | 엔쏜 인코포레이티드 | Electrodeposition of copper |
| US9809891B2 (en) | 2014-06-30 | 2017-11-07 | Rohm And Haas Electronic Materials Llc | Plating method |
| JP6733314B2 (en) * | 2015-09-29 | 2020-07-29 | 三菱マテリアル株式会社 | High-purity copper electrolytic refining additive and high-purity copper manufacturing method |
| US10988852B2 (en) * | 2015-10-27 | 2021-04-27 | Rohm And Haas Electronic Materials Llc | Method of electroplating copper into a via on a substrate from an acid copper electroplating bath |
| WO2020096906A1 (en) | 2018-11-07 | 2020-05-14 | Coventya, Inc. | Satin copper bath and method of depositing a satin copper layer |
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| US5730854A (en) * | 1996-05-30 | 1998-03-24 | Enthone-Omi, Inc. | Alkoxylated dimercaptans as copper additives and de-polarizing additives |
| JPH1088186A (en) * | 1996-09-17 | 1998-04-07 | Dai Ichi Kogyo Seiyaku Co Ltd | Nonionic surfactant and liquid detergent composition uisng the same |
| US6776893B1 (en) * | 2000-11-20 | 2004-08-17 | Enthone Inc. | Electroplating chemistry for the CU filling of submicron features of VLSI/ULSI interconnect |
| SG144688A1 (en) * | 2001-07-23 | 2008-08-28 | Fujimi Inc | Polishing composition and polishing method employing it |
| EP1422320A1 (en) * | 2002-11-21 | 2004-05-26 | Shipley Company, L.L.C. | Copper electroplating bath |
| JP2005194608A (en) | 2004-01-09 | 2005-07-21 | Asahi Denka Kogyo Kk | Additive for electrolytic copper plating, and electrolytic copper plating bath |
| KR101134610B1 (en) * | 2004-08-18 | 2012-04-09 | 에바라 유지라이토 가부시키가이샤 | Additive for copper plating and process for producing electronic circuit substrate therewith |
| TW200632147A (en) * | 2004-11-12 | 2006-09-16 | ||
| US20070178697A1 (en) * | 2006-02-02 | 2007-08-02 | Enthone Inc. | Copper electrodeposition in microelectronics |
| JP4813213B2 (en) * | 2006-03-07 | 2011-11-09 | 花王株式会社 | Wrinkle removal deodorant composition |
| JP2008222946A (en) * | 2007-03-15 | 2008-09-25 | Seiko Epson Corp | Ink for inkjet recording |
| JP2008222944A (en) * | 2007-03-15 | 2008-09-25 | Seiko Epson Corp | Ink for inkjet recording |
| JP2008297221A (en) | 2007-05-29 | 2008-12-11 | Shinko Electric Ind Co Ltd | Method for producing brightener for plating |
| CA2728411A1 (en) * | 2008-06-18 | 2009-12-23 | Dow Global Technologies Inc. | Cleaning compositions containing mid-range alkoxylates |
| EP2199315B1 (en) * | 2008-12-19 | 2013-12-11 | Basf Se | Composition for metal electroplating comprising leveling agent |
| JP2010255078A (en) * | 2009-04-28 | 2010-11-11 | Adeka Corp | Electrolytic copper plating bath and electrolytic copper plating method |
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| KR20140013021A (en) | 2014-02-04 |
| CN103443334B (en) | 2018-02-06 |
| WO2012133225A1 (en) | 2012-10-04 |
| US20130341199A1 (en) | 2013-12-26 |
| TWI608130B (en) | 2017-12-11 |
| TW201300581A (en) | 2013-01-01 |
| KR101940593B1 (en) | 2019-01-21 |
| CN103443334A (en) | 2013-12-11 |
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