WO2023178826A1 - Additif de placage de cuivre, solution de placage de cuivre et leur utilisation - Google Patents

Additif de placage de cuivre, solution de placage de cuivre et leur utilisation Download PDF

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Publication number
WO2023178826A1
WO2023178826A1 PCT/CN2022/094709 CN2022094709W WO2023178826A1 WO 2023178826 A1 WO2023178826 A1 WO 2023178826A1 CN 2022094709 W CN2022094709 W CN 2022094709W WO 2023178826 A1 WO2023178826 A1 WO 2023178826A1
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WO
WIPO (PCT)
Prior art keywords
copper plating
copper
plating liquid
additive
potassium salt
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Application number
PCT/CN2022/094709
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English (en)
Chinese (zh)
Inventor
刘国春
李学法
张国平
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江阴纳力新材料科技有限公司
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Priority to PCT/CN2023/083344 priority Critical patent/WO2023179704A1/fr
Publication of WO2023178826A1 publication Critical patent/WO2023178826A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/22—Electroplating combined with mechanical treatment during the deposition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of copper plating, and in particular to a copper plating additive, a copper plating liquid and their application.
  • Brush plating also known as metal pen plating, rapid electroplating, and brush plating, uses electrochemical methods to use a plating pen soaked in plating solution as the anode to discharge and crystallize metal ions on the surface of the negative electrode (workpiece) to form a metal coating. process.
  • the brush copper plating process is mainly used in fields with high conductivity requirements such as electronics, power, aerospace, etc. It is especially of high practical value for local plating and repair of plating layers.
  • the relative movement speed of the cathode and the anode is fast, so a higher current density is allowed to be used (several times to dozens of times greater than the current density used in tank plating).
  • the copper ion content in the plating solution of the copper plating process is brushed. High, so the plating speed is extremely fast (5 to 10 times faster than tank plating).
  • the object of the present invention is to provide a copper plating additive that has a fast plating speed and can greatly improve the uniformity, brightness and fullness of the plating layer.
  • a copper plating additive includes 1,4-cyclohexanedione monoethylene glycol ketal, phthalimide potassium salt and amino polyol compound.
  • the mass ratio of the 1,4-cyclohexanedione monoethylene glycol ketal, phthalimide potassium salt and amino polyol compound is (0.6 ⁇ 1.0): (1.2 ⁇ 2.0): (1.8 ⁇ 3.0).
  • the mass ratio of the 1,4-cyclohexanedione monoethylene glycol ketal, phthalimide potassium salt and amino polyol compound is (0.8 ⁇ 1.0): (1.5 ⁇ 2.0): (2.0 ⁇ 3.0).
  • the aminopolyol compound is 3-amino-1,2-propanediol.
  • the present invention also provides a copper plating liquid, which includes the copper plating additive as mentioned above.
  • the copper plating solution further includes water, copper sulfate, sulfuric acid and chloride ions.
  • each liter of the copper plating solution includes water and the following components:
  • the copper plating solution further includes a brightener, a surfactant and a leveling agent.
  • the brightener is selected from one or more of ethylene thiourea, benzimidazole and fatty amine ethoxysulfonate.
  • the surfactant is selected from one or both of sodium dodecyl sulfonate and sodium polydisulfide propane sulfonate.
  • the leveling agent is selected from one or more of polyethylene glycol, 1,4-butynediol and polyethyleneimine alkyl salt.
  • each liter of the copper plating liquid contains water and the following components:
  • each liter of the copper plating liquid contains water and the following components:
  • the invention also provides a method for plating copper on the surface of a substrate, which is characterized in that it includes the following steps:
  • the base material is contacted with the copper plating liquid as described above to perform copper plating treatment.
  • the process parameters of copper plating include:
  • the plating temperature is 35°C ⁇ 45°C
  • the plating time is 1min ⁇ 2min
  • the working voltage is 2V ⁇ 7V.
  • the copper plating additive provided by the invention includes 1,4-cyclohexanedione monoethylene glycol ketal, phthalimide potassium salt and amino polyol compound.
  • 1,4-cyclohexanedione monoethylene glycol ketal can significantly improve the brightness of the brushed copper layer
  • phthalimide potassium salt can effectively improve the brightness of 1,4-cyclohexanedione monoethylene glycol ketal.
  • the dissolution efficiency of the ketal can also refine the grains, level them, and improve the uniformity and thickness of the coating.
  • the amino polyol compound can greatly change the hue of the copper layer, making it more vivid.
  • this copper plating additive has the advantages of environmental protection, non-toxicity, low cost, etc., and is suitable for mass industrial production.
  • the copper plating additive of the present invention When the copper plating additive of the present invention is added to the copper plating liquid, a very small amount of addition can greatly improve the thickness, brightness and whiteness of the plating layer without changing the stability of the original copper plating liquid and the performance of the original copper plating layer.
  • Figure 1(a) is a copper plating picture of Example 1
  • Figure 1(b) is a copper plating picture of Example 2
  • Figure 1(c) is a copper plating picture of Example 3.
  • the invention provides a copper plating additive that can greatly improve the thickness, brightness and whiteness of the plating layer.
  • a copper plating additive includes 1,4-cyclohexanedione monoethylene glycol ketal, phthalimide potassium salt and amino polyol compound.
  • 1,4-cyclohexanedione monoethylene glycol ketal can significantly improve the brightness of the brushed copper layer, and phthalimide potassium salt can effectively improve the brightness of 1,4-cyclohexanedione monoethylene glycol ketal.
  • the dissolution efficiency of the ketal can also refine the grains, level them, and improve the uniformity and thickness of the coating.
  • the amino polyol compound can greatly change the hue of the copper layer, making it more vivid.
  • this copper plating additive has the advantages of environmental protection, non-toxicity, low cost, etc., and is suitable for mass industrial production.
  • the mass ratio of the 1,4-cyclohexanedione monoethylene glycol ketal, phthalimide potassium salt and amino polyol compound is (0.6 ⁇ 1.0): (1.2 ⁇ 2.0): (1.8 ⁇ 3.0), including but not limited to 0.6:1.2:1.8, 0.6:1.2:1.9, 0.6:1.2:2.0, 0.6:1.2:2.1, 0.6:1.2:2.2, 0.6:1.2:2.3, 0.6: 1.2: 2.4, 0.6: 1.2: 2.5, 0.6: 1.2: 2.6, 0.6: 1.2: 2.7, 0.6: 1.2: 2.8, 0.6: 1.2: 2.9, 0.6: 1.2: 3.0, 0.6: 1.5: 1.8, 0.6: 1.5: 1.9, 0.6: 1.5: 2.0, 0.6: 1.5: 2.1, 0.6: 1.5: 2.2, 0.6: 1.5: 2.3, 0.6: 1.5: 2.4, 0.6: 1.5: 2.5, 0.6: 1.5: 2.6, 0.6: 1.5: 2.7, 0.6: 1.5: 2.8, 0.6
  • the mass ratio of the 1,4-cyclohexanedione monoethylene glycol ketal, phthalimide potassium salt and amino polyol compound is (0.8 ⁇ 1.0): (1.5 ⁇ 2.0): (2.0 ⁇ 3.0). Further preferably, the mass ratio of the 1,4-cyclohexanedione monoethylene glycol ketal, phthalimide potassium salt and amino polyol compound is 1.0:2.0:3.0.
  • the aminopolyol compound is 3-amino-1,2-propanediol.
  • the present invention also provides a copper plating liquid, which includes the copper plating additive as described above.
  • the copper plating solution further includes water, copper sulfate, sulfuric acid and chloride ions.
  • each liter of the copper plating solution includes water and the following components:
  • the copper plating solution further includes a brightener, a surfactant and a leveling agent.
  • the brightener is selected from one or more of ethylene thiourea, benzimidazole and fatty amine ethoxysulfonate.
  • the surfactant is selected from one or both of sodium dodecyl sulfonate and sodium polydisulfide propane sulfonate.
  • the leveling agent is selected from one or more of polyethylene glycol, 1,4-butynediol and polyethyleneimine alkyl salt.
  • each liter of the copper plating liquid contains water and the following components:
  • each liter of the copper plating liquid contains water and the following components:
  • the invention also provides a method for plating copper on the surface of a substrate, which is characterized in that it includes the following steps:
  • the base material is contacted with the copper plating liquid as described above to perform copper plating treatment.
  • the process parameters of copper plating include:
  • the plating temperature is 35°C ⁇ 45°C
  • the plating time is 1min ⁇ 2min
  • the working voltage is 2V ⁇ 7V.
  • the copper plating process is brush plating copper plating process.
  • the substrate is made of plastic. Further, the base material is a plastic film. Further, during the copper plating process, the relative movement speed of the substrate relative to the brush plating tank is 3 m/min to 10 m/min.
  • composition of the copper plating additive per liter is as follows:
  • each liter of the copper plating liquid consists of water and the following components:
  • step 2) prepare copper plating additive: Use step 2) to weigh phthalimide potassium salt and slowly add it to the 1,4-cyclohexanedione monoethylene glycol ketal solution in step 1), stir thoroughly to dissolve and mix. Then slowly add the 3-amino-1,2-propanediol solution prepared in step 3), then adjust the volume to 1L with deionized water, and continue stirring until the mixture is evenly mixed.
  • the thickness of the copper plating layer of the brush-plated workpiece after adding the additives of this embodiment is 3.52 ⁇ m, and the appearance is delicate and bright copper color, see Figure 1(a).
  • the thickness of the copper plating layer of the brush-plated workpiece without adding the additives of this embodiment is 1.06 ⁇ m, and the appearance is rough crystalline and matte pig liver color.
  • composition of the copper plating additive per liter is as follows:
  • each liter of the copper plating liquid consists of water and the following components:
  • step 2) prepare copper plating additive: Use step 2) to weigh phthalimide potassium salt and slowly add it to the 1,4-cyclohexanedione monoethylene glycol ketal solution in step 1), stir thoroughly to dissolve and mix. Then slowly add the 3-amino-1,2-propanediol solution prepared in step 3), then adjust the volume to 1L with deionized water, and continue stirring until the mixture is evenly mixed.
  • the thickness of the copper plating layer of the brush-plated workpiece after adding the additives of this embodiment is 3.14 ⁇ m, and the appearance is delicate and bright copper color, see Figure 1(b).
  • the thickness of the copper plating layer of the brush-plated workpiece without adding the additives of this embodiment is 0.98 ⁇ m, and the appearance is rough crystalline and matte pig liver color.
  • composition of the copper plating additive per liter is as follows:
  • each liter of the copper plating liquid consists of water and the following components:
  • step 2) Prepare copper plating additive: Use step 2) to weigh phthalimide potassium salt and slowly add it to the 1,4-cyclohexanedione monoethylene glycol ketal solution in step 1), stir thoroughly to dissolve and mix. Then slowly add the 3-amino-1,2-propanediol solution prepared in step 3), then adjust the volume to 1L with deionized water, and continue stirring to mix evenly.
  • the thickness of the copper plating layer of the brush-plated workpiece after adding the additives of this embodiment is 3.21 ⁇ m, and the appearance is delicate and bright copper color, see Figure 1(c).
  • the thickness of the copper plating layer of the brush-plated workpiece without adding the additives of this embodiment is 1.05 ⁇ m, and the appearance is rough crystalline and matte pig liver color.
  • composition of the copper plating additive per liter is as follows:
  • each liter of the copper plating liquid consists of water and the following components:
  • step 2) prepare copper plating additive: Use step 2) to weigh phthalimide potassium salt and slowly add it to the 1,4-cyclohexanedione monoethylene glycol ketal solution in step 1), stir thoroughly to dissolve and mix. Then slowly add the 3-amino-1,2-propanediol solution prepared in step 3), then adjust the volume to 1L with deionized water, and continue stirring until the mixture is evenly mixed.
  • the thickness of the copper plating layer of the brush-plated workpiece after adding the additives of this embodiment is 3.31 ⁇ m, and the appearance is delicate and bright copper color.
  • the thickness of the copper plating layer of the brush-plated workpiece without adding the additives of this embodiment is 1.02 ⁇ m, and the appearance is rough crystalline and matte pig liver color.
  • composition of the copper plating additive per liter is as follows:
  • each liter of the copper plating liquid consists of water and the following components:
  • step 2) prepare copper plating additive: Use step 2) to weigh phthalimide potassium salt and slowly add it to the 1,4-cyclohexanedione monoethylene glycol ketal solution in step 1), stir thoroughly to dissolve and mix. Then slowly add the 3-amino-1,2-propanediol solution prepared in step 3), then adjust the volume to 1L with deionized water, and continue stirring until the mixture is evenly mixed.
  • the thickness of the copper plating layer of the brush-plated workpiece after adding the additives of this embodiment is 3.36 ⁇ m, and the appearance is delicate and bright copper color.
  • the thickness of the copper plating layer of the brush-plated workpiece without adding the additives of this embodiment is 1.34 ⁇ m, and the appearance is rough crystalline and matte pig liver color.

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

Abstract

La présente invention concerne un additif de placage de cuivre, une solution de placage de cuivre et leur utilisation. L'additif de placage de cuivre comprend du 1,4-cyclohexanedione monoéthylène acétal, un sel de phtalimide de potassium et un composé aminopolyol. Le 1,4-cyclohexanedione monoéthylène acétal peut améliorer significativement la luminosité d'une couche de cuivre plaquée à la brosse ; le sel de phtalimide de potassium peut améliorer efficacement l'efficacité de dissolution du 1,4-cyclohexanedione monoéthylène acétal, et dans le même temps, joue un rôle dans l'affinage des grains cristallins, l'aplatissement et l'amélioration de l'uniformité et de l'épaisseur d'une couche plaquée ; et le composé aminopolyol peut modifier considérablement la tonalité chromatique de la couche de cuivre pour rendre la couche de cuivre plus brillante. De plus, l'additif de placage de cuivre présente les avantages d'être respectueux de l'environnement, de ne pas présenter de toxicité, d'avoir un coût faible et similaire, et est approprié pour une production industrielle à grande échelle. Lorsque l'additif de placage de cuivre est ajouté à une solution de placage de cuivre, une petite quantité ajoutée peut améliorer considérablement l'épaisseur, la luminosité et la saturation de la couche plaquée tout en ne modifiant pas la stabilité d'une solution de placage de cuivre d'origine ou les performances d'une couche plaquée de cuivre d'origine.
PCT/CN2022/094709 2022-03-25 2022-05-24 Additif de placage de cuivre, solution de placage de cuivre et leur utilisation WO2023178826A1 (fr)

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WO2023179704A1 (fr) * 2022-03-25 2023-09-28 Jiangyin Nanopore Innovative Materials Technology Ltd Compositions d'additif de placage de cuivre, solutions de placage de cuivre et leurs utilisations

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US4310392A (en) * 1979-12-31 1982-01-12 Bell Telephone Laboratories, Incorporated Electrolytic plating
CN105887144A (zh) * 2016-06-21 2016-08-24 广东光华科技股份有限公司 电镀铜镀液及其电镀铜工艺
CN111945192A (zh) * 2020-08-11 2020-11-17 深圳市创智成功科技有限公司 用于hdi板和载板的盲孔填孔电镀铜溶液
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