WO2022141709A1 - Electrolytic copper foil for high-frequency high-speed printed circuit board, and preparation method therefor - Google Patents

Electrolytic copper foil for high-frequency high-speed printed circuit board, and preparation method therefor Download PDF

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Publication number
WO2022141709A1
WO2022141709A1 PCT/CN2021/073865 CN2021073865W WO2022141709A1 WO 2022141709 A1 WO2022141709 A1 WO 2022141709A1 CN 2021073865 W CN2021073865 W CN 2021073865W WO 2022141709 A1 WO2022141709 A1 WO 2022141709A1
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Prior art keywords
copper foil
electrolytic copper
printed circuit
frequency
speed printed
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PCT/CN2021/073865
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French (fr)
Chinese (zh)
Inventor
王崇华
庄伟雄
钟孟捷
王俊锋
廖平元
刘少华
温丙台
郭志航
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广东嘉元科技股份有限公司
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Priority to JP2022508794A priority Critical patent/JP2023512132A/en
Publication of WO2022141709A1 publication Critical patent/WO2022141709A1/en

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal

Definitions

  • the present invention relates to the field of electrolytic copper foils, and more particularly, to an electrolytic copper foil for high-frequency and high-speed printed circuit boards and a preparation method thereof.
  • electrolytic copper foil acts as a nerve center.
  • the loss and transmission rate of the transmission signal are directly related to the performance of electronic products.
  • the size, uniformity and roughness peak of the rough surface of the copper foil directly determine the loss and transmission rate in the signal.
  • Electrolytic copper foil must meet high-frequency and high-speed performance during signal transmission, and it is necessary to improve the performance of copper foil. Substrates made of many existing materials have relatively large dielectric loss in the actual use process, and the attenuation of high-frequency signals is also serious when used for high-frequency transmission.
  • the adhesive force of the copper foil and the related inert resin after lamination is reduced.
  • the first aspect of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards, which includes a green foil layer and a surface treatment layer; the thickness of the electrolytic copper foil is 12-35 ⁇ m, deviation of weight per unit area ⁇ 5%, tensile strength at 25°C ⁇ 300N/mm 2 , elongation at 25°C ⁇ 6.0%, peel strength at 25°C ⁇ 1.0Kg/cm, rough surface Rz ⁇ 3.0 ⁇ m.
  • the green foil layer is obtained by electrolysis in an electrolyte containing copper ions, and the electrolyte includes 50-100g/L copper ions, 100-160g/L sulfuric acid, 150-300g /L additive.
  • the additive includes a grain refiner and a leveling agent, and the concentration ratio thereof is 1:(10-25).
  • the grain refiner is selected from the group consisting of sodium polydithiodipropanesulfonate, polyethylene glycol, ethylene thiourea, 3-mercapto-1-propanesulfonate, Sodium 4-[[2-(Acetylamino)ethyl]dithio]-1-butanesulfinate, thiazolidinethione, thiamine disulfide, 2-substituted hydrazono-1,3- One or more of dithiolane and 2-mercaptobenzimidazole.
  • the leveling agent is selected from one or more of nitrogen-containing leveling agents, polyether leveling agents, and quaternary ammonium salt leveling agents.
  • the nitrogen-containing leveling agent is selected from one or more of gelatin, aminopyridine, pyridine, aliphatic amine ethoxysulfonate, and bipyridine.
  • the weight-average molecular weight of the gelatin is 50,000-60,000.
  • the polyether leveling agent is selected from one or more of polyethylene glycol, hydroxyethyl cellulose, and hydroxyethyl methyl cellulose.
  • the weight average molecular weight of the quaternary ammonium salt leveling agent is 3000-5000, and the viscosity at 25°C is 10-30 mpa.s.
  • a second aspect of the present invention provides a method for preparing the electrolytic copper foil for the high-frequency and high-speed printed circuit board, comprising the following steps:
  • the present invention has the following beneficial effects:
  • the electrolytic copper foil for high-frequency and high-speed printed circuit boards of the present invention is simple in raw material, non-toxic and harmless, safe and environmentally friendly, its weight deviation per unit area is less than 5.0%, and at the same time, it has excellent tensile strength, elongation and peel strength, In addition, the electrolytic copper foil does not oxidize or discolor when baked at 200°C for 30 minutes, and at the same time, it can meet the requirements of high information flow circuit boards and adapt to the development of today's 5G era.
  • the invention provides an electrolytic copper foil for the high-frequency and high-speed printed circuit board, which comprises a raw foil layer and a surface treatment layer; the thickness of the electrolytic copper foil is 12-35 ⁇ m, the weight deviation per unit area is less than 5.0%, Tensile strength at 25°C ⁇ 300N/mm 2 , elongation at 25°C ⁇ 6.0%, peel strength at 25°C ⁇ 1.0Kg/cm, rough surface Rz ⁇ 3.0 ⁇ m.
  • the green foil layer is obtained by electrolysis in an electrolyte containing copper ions.
  • the electrolyte includes 50-100 g/L copper ions, 100-160 g/L sulfuric acid, and 150-300 g/L additives.
  • the electrolyte includes 80 g/L copper ions, 126 g/L sulfuric acid, and 236 g/L additives.
  • the solvent of the electrolyte of the present invention is deionized water.
  • the source of the copper ions in the present invention is not particularly limited, and those skilled in the art can make routine selections.
  • the source of the copper ions is copper sulfate pentahydrate.
  • copper sulfate pentahydrate as the main component of the green foil layer in the present application, participates in the electrode process.
  • the concentration of copper sulfate pentahydrate is too high, the dispersibility of copper ions is poor, and the anhydrous If the concentration of copper sulfate is too low, the copper foil layer of the high current layer may be scorched.
  • sulfuric acid is used as an inorganic acid to participate in the electrode process.
  • the copper ion concentration is 50-100 g/L, the decomposition of copper sulfate pentahydrate can be accelerated, and copper precipitation is rapid.
  • the additive includes a grain refiner and a leveling agent in a concentration ratio of 1:(10-25).
  • the concentration ratio of the grain refiner and the leveling agent is 1:15.
  • the grain refiner is selected from the group consisting of sodium polydithiodipropanesulfonate, polyethylene glycol, ethylenethiourea, 3-mercapto-1-propanesulfonate, 4-[[ 2-(Acetylamino)ethyl]dithio]-1-butanesulfinic acid sodium, thiazolidinethione, thiamine disulfide compound, 2-substituted hydrazono-1,3-dithioheterocycle One or more of pentane and 2-mercaptobenzimidazole.
  • the grain refiner is sodium polydisulfide dipropane sulfonate.
  • the leveling agent is selected from one or more of nitrogen-containing leveling agents, polyether leveling agents, and quaternary ammonium salt leveling agents.
  • the nitrogen-containing leveling agent is selected from one or more of gelatin, aminopyridine, pyridine, aliphatic amine ethoxysulfonate, and bipyridine.
  • the nitrogen-containing leveling agent is gelatin.
  • the weight average molecular weight of the gelatin is 50000-60000.
  • the polyether leveling agent is selected from one or more of polyethylene glycol, hydroxyethyl cellulose, and hydroxyethyl methyl cellulose.
  • the polyether leveling agent is hydroxyethyl cellulose.
  • the leveling agent includes gelatin and hydroxyethyl cellulose.
  • the weight ratio of the gelatin to the hydroxyethyl cellulose is (2-6): 1; more preferably, the weight ratio of the gelatin to the hydroxyethyl cellulose is 5:1.
  • the leveling agent further includes a quaternary ammonium salt leveling agent.
  • the weight ratio of the quaternary ammonium salt leveling agent and hydroxyethyl cellulose is (0.8-2.5): 1; more preferably, the quaternary ammonium salt leveling agent and hydroxyethyl cellulose The weight ratio is 1.2:1.
  • the quaternary ammonium salt leveling agent is a quaternary ammonium salt copolymerized with alkyl dimethyl ammonium chloride and sulfur dioxide.
  • the gelatin and hydroxyethyl cellulose molecules with a weight average molecular weight of 50000-60000 contain macromolecular chains structure, after the interaction between them forms hydrogen bonds, while the macromolecular chain structure is deposited on the bump, part of its flexible molecular chain blocks the concave site, hindering the deposition of copper ions in the concave, while the quaternary ammonium salt Leveling agents, especially quaternary ammonium salts copolymerized with alkyl dimethyl ammonium chloride and sulfur dioxide, may hinder the interaction between gelatin molecules with a weight average molecular weight of 50,000-60,000 and hydroxyethyl cellulose on the one hand in the electroplating bath On the other hand, it plays the role of electrolyte and affects the deposition and distribution of copper ions, which increases the flatness of the surface of the green foil and provides a basis for the subsequent surface treatment process.
  • the weight average molecular weight of the quaternary ammonium salt copolymerized with alkyl dimethyl ammonium chloride and sulfur dioxide is 3000-5000, and the viscosity at 25° C. is 10-30 mpa.s.
  • the weight-average molecular weight of the quaternary ammonium salt copolymerized with alkyl dimethyl ammonium chloride and sulfur dioxide is 4000, and the viscosity at 25° C. is 20 mpa.s.
  • the extension of the electrolytic copper foil can be significantly improved rate, its value is greater than ⁇ 6.0%.
  • the molar substitution of the hydroxyethyl cellulose is 1.8-2.0.
  • the applicant unexpectedly found that when the molar substitution degree of hydroxyethyl cellulose is 1.8-2.0, the elongation, folding resistance and stress can be improved. The applicant believes that the possible reason is that the molar substitution degree is 1.8-2.0. 2.0, the hydroxyethyl cellulose can be adsorbed at the corners of the concave surface, inhibiting the deposition of copper ions at the corners of the concave surface, and avoiding the internal stress defect caused by the formation of pinholes.
  • the second aspect of the present invention provides a preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board, which comprises the following steps:
  • the preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board includes the following steps:
  • electrolyte 80g/L copper ion, 126g/L sulfuric acid, 236g/L additive are mixed to obtain electrolyte;
  • the surface treatment in the present invention is not particularly limited, and can be listed as acid treatment stage, roughening treatment stage, curing treatment stage, heat-resistant layer treatment stage, anti-oxidation treatment stage, silane coupling agent treatment stage, etc.
  • the specific treatment methods Without particular limitation, those skilled in the art can make routine choices.
  • Embodiment 1 of the present invention provides an electrolytic copper foil for a high-frequency and high-speed printed circuit board, which is composed of a green foil layer and a surface treatment layer.
  • the green foil layer is obtained by electrolysis in an electrolyte containing copper ions.
  • the electrolyte is 50g/L copper ions, 100g/L sulfuric acid, and 150g/L additives.
  • the source of the copper ions is copper sulfate pentahydrate.
  • the additive is a grain refiner and a leveling agent, the concentration ratio of which is 1:10; the grain refiner is sodium polydisulfide dipropane sulfonate; the leveling agent is gelatin, hydroxyethyl
  • the weight ratio of quaternary ammonium salt and hydroxyethyl cellulose is 0.8:1; the weight average molecular weight of the gelatin is 50000-60000; the weight average molecular weight of the quaternary ammonium salt copolymerized with the alkyl dimethyl ammonium chloride and sulfur dioxide
  • the molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0, and the model is HEC-15000.
  • the preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board is as follows:
  • electrolyte 50g/L copper ion, 100g/L sulfuric acid, 150g/L additive are mixed to obtain electrolyte;
  • Embodiment 2 of the present invention provides an electrolytic copper foil for a high-frequency and high-speed printed circuit board, which is composed of a green foil layer and a surface treatment layer.
  • the green foil layer is obtained by electrolysis in an electrolyte containing copper ions.
  • the electrolyte is 100g/L copper ions, 160g/L sulfuric acid, and 300g/L additives.
  • the source of the copper ions is copper sulfate pentahydrate.
  • the additive is a grain refiner and a leveling agent, and its concentration ratio is 1:25; the grain refiner is sodium polydisulfide dipropane sulfonate; the leveling agent is gelatin, hydroxyethyl
  • the weight ratio of quaternary ammonium salt and hydroxyethyl cellulose is 2.5:1; the weight-average molecular weight of the gelatin is 50,000-60,000; the weight-average molecular weight of the quaternary ammonium salt copolymerized with the alkyl dimethyl ammonium chloride and sulfur dioxide
  • the molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0, and the model is HEC-15000.
  • the preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board is as follows:
  • Embodiment 3 of the present invention provides an electrolytic copper foil for a high-frequency and high-speed printed circuit board, which is composed of a green foil layer and a surface treatment layer.
  • the green foil layer is obtained by electrolysis in an electrolyte containing copper ions.
  • the electrolyte is 80g/L copper ions, 126g/L sulfuric acid, and 236g/L additives.
  • the source of the copper ions is copper sulfate pentahydrate.
  • the additive is a grain refiner and a leveling agent, and the concentration ratio is 1:15; the grain refiner is sodium polydisulfide dipropane sulfonate; the leveling agent is gelatin, hydroxyethyl
  • the weight ratio of quaternary ammonium salt and hydroxyethyl cellulose is 1.2:1; the weight-average molecular weight of the gelatin is 50,000-60,000; the weight-average molecular weight of the quaternary ammonium salt copolymerized with the alkyl dimethyl ammonium chloride and sulfur dioxide
  • the molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0, and the model is HEC-15000.
  • the preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board is as follows:
  • electrolyte 50g/L copper ion, 100g/L sulfuric acid, 150g/L additive are mixed to obtain electrolyte;
  • Embodiment 4 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards.
  • the weight ratio is 5:1
  • the weight average molecular weight of the gelatin is 50000-60000
  • the molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0
  • the model is HEC-15000.
  • Embodiment 5 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards.
  • the weight average molecular weight of the quaternary ammonium salt is 5000, and the viscosity at 25°C is 7mpa.s.
  • Embodiment 6 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards. 2.8.
  • Embodiment 7 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards, the specific implementation of which is the same as that of embodiment 3, except that the grain refiner is thiazolidinethione.
  • Embodiment 8 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards, the specific implementation of which is the same as that of Embodiment 3, except that the leveling agent is The quaternary ammonium salt copolymerized with dimethyl ammonium chloride and sulfur dioxide, the weight ratio of the quaternary ammonium salt copolymerized with dimethyl ammonium chloride and sulfur dioxide and hydroxyethyl cellulose is 1.2:1; The weight-average molecular weight of the quaternary ammonium salt copolymerized with methyl ammonium chloride and sulfur dioxide is 4000, and the viscosity at 25° C. is 20 mpa.s; the molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0, and the model is HEC-15000.
  • Weight per unit area deviation the weight per unit area of the electrolytic copper foil for high-frequency and high-speed printed circuit boards obtained in Examples 1-8 was tested according to the GB/T 5230-1995 standard, and each embodiment was tested 10 times, and calculated For the deviation of weight per unit area, the deviation of weight per unit area is less than 5.0%, which is regarded as excellent; the deviation of weight per unit area is 5.0-7.0%, which is regarded as good; the deviation of weight per unit area is more than 7.0%, which is regarded as poor.
  • Roughness of rough surface The roughness of the electrolytic copper foils for high-frequency and high-speed printed circuit boards obtained in Examples 1 to 8 was tested according to the GB/T 5230-1995 standard. Microscopic roughness (Rz) was tested, where Rz was the difference between the average of the 5 largest profile peak heights and the average of the 5 largest profile valley depths within the sampling length. Among them, the roughness Rz ⁇ 2.5 ⁇ m obtained by the test is regarded as excellent, the roughness Rz of the roughness Rz of 2-5-3.0 ⁇ m is regarded as qualified, and the roughness of the roughness Rz>3.0 ⁇ m is regarded as unqualified.
  • Elongation The elongation of the electrolytic copper foil for high-frequency and high-speed printed circuit boards provided in Examples 1-8 was tested according to the GB/T 5230-1995 standard, and the test temperature was 25°C. Elongation ⁇ 6%, recorded as qualified, otherwise recorded as unqualified.
  • Anti-peeling strength The anti-peeling strength of the electrolytic copper foils for high-frequency and high-speed printed circuit boards provided in Examples 1-8 was tested according to the GB/T 5230-1995 standard, and the test temperature was 25°C. Anti-peel strength ⁇ 1.0Kg/cm, denoted as first-class, anti-peel strength of 0.7-1Kg/cm (excluding 1Kg/cm), denoted as second-class, anti-peel strength less than 0.7Kg/cm, denoted as third-class.

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Abstract

An electrolytic copper foil for a high-frequency high-speed printed circuit board, and a preparation method therefor. The electrolytic copper foil for a high-frequency high-speed printed circuit board comprises a raw foil layer and a surface treated layer; the electrolytic copper foil has a thickness of 12-35 μm, a unit area weight deviation < 5.0%, a tensile strength at 25 °C ≥ 300 N/mm2, an elongation at 25 °C ≥ 6.0%, an anti-peel strength at 25 °C ≥ 1.0 Kg/cm, and a surface roughness Rz ≤ 3.0 μm. The electrolytic copper foil for a high-frequency high-speed printed circuit board has basic raw materials, is non-toxic, harmless, safe, and eco-friendly, has a unit area weight deviation less than 5.0%, and also has uniquely advantageous tensile strength, elongation, and anti-peel strength; additionally, the electrolytic copper foil baked for 30 minutes at 200 °C does not oxidize or change color, is able to satisfy a requirement for a high information traffic circuit board, and is adaptive to present 5G-era development.

Description

一种高频高速印制电路板用电解铜箔及其制备方法Electrolytic copper foil for high frequency and high speed printed circuit board and preparation method thereof 技术领域technical field
本发明涉及电解铜箔领域，更具体地，本发明涉及一种高频高速印制电路板用电解铜箔及其制备方法。The present invention relates to the field of electrolytic copper foils, and more particularly, to an electrolytic copper foil for high-frequency and high-speed printed circuit boards and a preparation method thereof.
背景技术Background technique
随着科技的发展，5G时代已经到来，PCB产品作为高频、高速通讯天线发射与基站信息接受转化的载体，发挥着极其重要的作用。电解铜箔作为元器件的沟通桥梁，起到神经中枢的作用，在传输信号上的损耗与传输速率，直接关系到电子产品的性能。而铜箔毛面晶核大小，均匀性，粗糙峰值，直接决定了信号中损耗与传输速率。电解铜箔在信号转输时要符合高频高速性能，必然要提高铜箔的各项性能。现有的很多材料制成的基板，在实际使用过程中介电损耗较大，并且用于高频传输时候高频信号的衰减也比较严重。同时，随着铜箔表面粗糙度的一再降低，铜箔与相关的惰性树脂压合后的粘合力降低。With the development of science and technology, the 5G era has come, and PCB products play an extremely important role as the carrier of high-frequency and high-speed communication antenna transmission and base station information reception and transformation. As a communication bridge for components, electrolytic copper foil acts as a nerve center. The loss and transmission rate of the transmission signal are directly related to the performance of electronic products. The size, uniformity and roughness peak of the rough surface of the copper foil directly determine the loss and transmission rate in the signal. Electrolytic copper foil must meet high-frequency and high-speed performance during signal transmission, and it is necessary to improve the performance of copper foil. Substrates made of many existing materials have relatively large dielectric loss in the actual use process, and the attenuation of high-frequency signals is also serious when used for high-frequency transmission. At the same time, with the repeated reduction of the surface roughness of the copper foil, the adhesive force of the copper foil and the related inert resin after lamination is reduced.
发明内容SUMMARY OF THE INVENTION
针对现有技术中存在的一些问题，本发明第一个方面提供了一种高频高速印制电路板用电解铜箔，其包括生箔层和表面处理层；所述电解铜箔的厚度为12-35μm，单位面积重量偏差＜5％，在25℃的抗拉强度≥300N/mm 2，在25℃的延伸率≥6.0％，在25℃抗剥离强度≥1.0Kg/cm，毛面Rz≤3.0μm。 In view of some problems existing in the prior art, the first aspect of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards, which includes a green foil layer and a surface treatment layer; the thickness of the electrolytic copper foil is 12-35μm, deviation of weight per unit area <5%, tensile strength at 25℃≥300N/mm 2 , elongation at 25℃≥6.0%, peel strength at 25℃≥1.0Kg/cm, rough surface Rz ≤3.0μm.
作为本发明的一种优选的技术方案，所述生箔层由在含铜离子电解液中电解得到，所述电解液包括50-100g/L铜离子、100-160g/L硫酸、150-300g/L添加剂。As a preferred technical solution of the present invention, the green foil layer is obtained by electrolysis in an electrolyte containing copper ions, and the electrolyte includes 50-100g/L copper ions, 100-160g/L sulfuric acid, 150-300g /L additive.
作为本发明的一种优选的技术方案，所述添加剂包括晶粒细化剂和整平剂，其浓度比为1：(10-25)。As a preferred technical solution of the present invention, the additive includes a grain refiner and a leveling agent, and the concentration ratio thereof is 1:(10-25).
作为本发明的一种优选的技术方案，所述晶粒细化剂选自聚二硫二丙烷磺酸钠、聚乙二醇、乙撑硫脲、3-巯基-1-丙磺酸盐、4-[[2-(乙酰氨基)乙基]二硫代]-1-丁烷亚磺酸钠、四氢噻唑硫酮、硫胺二硫化合物、2-取代亚肼基-1,3-二硫杂环戊烷、2-巯基苯并咪唑中一种或多种。As a preferred technical solution of the present invention, the grain refiner is selected from the group consisting of sodium polydithiodipropanesulfonate, polyethylene glycol, ethylene thiourea, 3-mercapto-1-propanesulfonate, Sodium 4-[[2-(Acetylamino)ethyl]dithio]-1-butanesulfinate, thiazolidinethione, thiamine disulfide, 2-substituted hydrazono-1,3- One or more of dithiolane and 2-mercaptobenzimidazole.
作为本发明的一种优选的技术方案，所述整平剂选自含氮类整平剂、聚醚类 整平剂、季铵盐类整平剂中一种或多种。As a preferred technical solution of the present invention, the leveling agent is selected from one or more of nitrogen-containing leveling agents, polyether leveling agents, and quaternary ammonium salt leveling agents.
作为本发明的一种优选的技术方案，所述含氮类整平剂选自明胶、氨基吡啶、吡啶、脂肪胺乙氧基磺化物、联吡啶中一种或多种。As a preferred technical solution of the present invention, the nitrogen-containing leveling agent is selected from one or more of gelatin, aminopyridine, pyridine, aliphatic amine ethoxysulfonate, and bipyridine.
作为本发明的一种优选的技术方案，所述明胶的重均分子量为50000-60000。As a preferred technical solution of the present invention, the weight-average molecular weight of the gelatin is 50,000-60,000.
作为本发明的一种优选的技术方案，所述聚醚类整平剂选自聚乙二醇、羟乙基纤维素、羟乙基甲基纤维素中一种或多种。As a preferred technical solution of the present invention, the polyether leveling agent is selected from one or more of polyethylene glycol, hydroxyethyl cellulose, and hydroxyethyl methyl cellulose.
作为本发明的一种优选的技术方案，所述季铵盐类整平剂的重均分子量为3000-5000，在25℃粘度为10-30mpa.s。As a preferred technical solution of the present invention, the weight average molecular weight of the quaternary ammonium salt leveling agent is 3000-5000, and the viscosity at 25°C is 10-30 mpa.s.
本发明第二个方面提供了一种所述高频高速印制电路板用电解铜箔的制备方法，包括下面步骤：A second aspect of the present invention provides a method for preparing the electrolytic copper foil for the high-frequency and high-speed printed circuit board, comprising the following steps:
(1)电解液的配置：将50-100g/L铜离子、100-160g/L硫酸、150-300g/L添加剂混合得到电解液；(1) Configuration of electrolyte: mix 50-100g/L copper ions, 100-160g/L sulfuric acid, and 150-300g/L additives to obtain electrolyte;
(2)生箔的制备：通直流电，在电流密度3000-11000A/m 2条件下，阴极析出铜箔，剥离，得到生箔； (2) Preparation of green foil: direct current is applied, and under the condition of current density of 3000-11000A/m 2 , copper foil is precipitated at the cathode, and peeled off to obtain green foil;
(3)表面处理：对步骤(2)中制备的生箔进行表面处理。(3) Surface treatment: The green foil prepared in step (2) is subjected to surface treatment.
本发明与现有技术相比具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明所述高频高速印制电路板用电解铜箔原料简单，无毒无害，安全环保，其单位面积重量偏差小于5.0％，同时具有优异的抗拉强度、延伸率以及抗剥离强度，此外，该电解铜箔在200℃烘烤30min不氧化、不变色，同时能够满足高信息流量电路板的要求，适应如今5G时代的发展。The electrolytic copper foil for high-frequency and high-speed printed circuit boards of the present invention is simple in raw material, non-toxic and harmless, safe and environmentally friendly, its weight deviation per unit area is less than 5.0%, and at the same time, it has excellent tensile strength, elongation and peel strength, In addition, the electrolytic copper foil does not oxidize or discolor when baked at 200°C for 30 minutes, and at the same time, it can meet the requirements of high information flow circuit boards and adapt to the development of today's 5G era.
具体实施方式Detailed ways
本发明提供了一种所述高频高速印制电路板用电解铜箔，其包括生箔层和表面处理层；所述电解铜箔的厚度为12-35μm，单位面积重量偏差＜5.0％，在25℃的抗拉强度≥300N/mm 2，在25℃的延伸率≥6.0％，在25℃抗剥离强度≥1.0Kg/cm，毛面Rz≤3.0μm。 The invention provides an electrolytic copper foil for the high-frequency and high-speed printed circuit board, which comprises a raw foil layer and a surface treatment layer; the thickness of the electrolytic copper foil is 12-35 μm, the weight deviation per unit area is less than 5.0%, Tensile strength at 25℃≥300N/mm 2 , elongation at 25℃≥6.0%, peel strength at 25℃≥1.0Kg/cm, rough surface Rz≤3.0μm.
在一种实施方式中，所述生箔层由在含铜离子电解液中电解得到。In one embodiment, the green foil layer is obtained by electrolysis in an electrolyte containing copper ions.
在一种实施方式中，所述电解液包括50-100g/L铜离子、100-160g/L硫酸、150-300g/L添加剂。In one embodiment, the electrolyte includes 50-100 g/L copper ions, 100-160 g/L sulfuric acid, and 150-300 g/L additives.
优选的，所述电解液包括80g/L铜离子、126g/L硫酸、236g/L添加剂。Preferably, the electrolyte includes 80 g/L copper ions, 126 g/L sulfuric acid, and 236 g/L additives.
本发明所述电解液的溶剂为去离子水。The solvent of the electrolyte of the present invention is deionized water.
铜离子Copper ions
本发明所述铜离子的来源不作特别限定，本领域技术人员可作常规选择。The source of the copper ions in the present invention is not particularly limited, and those skilled in the art can make routine selections.
在一种实施方式中，所述铜离子的来源为五水硫酸铜。In one embodiment, the source of the copper ions is copper sulfate pentahydrate.
本发明中五水硫酸铜作为本申请中生箔层的主要成分，参与电极过程，在本申请生箔层的制备过程中，五水硫酸铜浓度过高，铜离子的分散能力差，无水硫酸铜的浓度过低，高电流层的铜箔层出现烧焦的现象。In the present invention, copper sulfate pentahydrate, as the main component of the green foil layer in the present application, participates in the electrode process. During the preparation process of the green foil layer in the present application, the concentration of copper sulfate pentahydrate is too high, the dispersibility of copper ions is poor, and the anhydrous If the concentration of copper sulfate is too low, the copper foil layer of the high current layer may be scorched.
硫酸sulfuric acid
本申请中使用硫酸作为无机酸，参与电极过程，当铜离子浓度在50-100g/L时，能够加快促进五水硫酸铜的分解，析铜迅速。In this application, sulfuric acid is used as an inorganic acid to participate in the electrode process. When the copper ion concentration is 50-100 g/L, the decomposition of copper sulfate pentahydrate can be accelerated, and copper precipitation is rapid.
添加剂additive
在一种实施方式中，所述添加剂包括晶粒细化剂和整平剂，其浓度比为1：(10-25)。In one embodiment, the additive includes a grain refiner and a leveling agent in a concentration ratio of 1:(10-25).
优选的，所述晶粒细化剂和整平剂的浓度比为1：15。Preferably, the concentration ratio of the grain refiner and the leveling agent is 1:15.
在一种实施方式中，所述晶粒细化剂选自聚二硫二丙烷磺酸钠、聚乙二醇、乙撑硫脲、3-巯基-1-丙磺酸盐、4-[[2-(乙酰氨基)乙基]二硫代]-1-丁烷亚磺酸钠、四氢噻唑硫酮、硫胺二硫化合物、2-取代亚肼基-1,3-二硫杂环戊烷、2-巯基苯并咪唑中一种或多种。In one embodiment, the grain refiner is selected from the group consisting of sodium polydithiodipropanesulfonate, polyethylene glycol, ethylenethiourea, 3-mercapto-1-propanesulfonate, 4-[[ 2-(Acetylamino)ethyl]dithio]-1-butanesulfinic acid sodium, thiazolidinethione, thiamine disulfide compound, 2-substituted hydrazono-1,3-dithioheterocycle One or more of pentane and 2-mercaptobenzimidazole.
优选的，所述晶粒细化剂为聚二硫二丙烷磺酸钠。Preferably, the grain refiner is sodium polydisulfide dipropane sulfonate.
在一种实施方式中，所述整平剂选自含氮类整平剂、聚醚类整平剂、季铵盐类整平剂中一种或多种。In one embodiment, the leveling agent is selected from one or more of nitrogen-containing leveling agents, polyether leveling agents, and quaternary ammonium salt leveling agents.
优选的，所述含氮类整平剂选自明胶、氨基吡啶、吡啶、脂肪胺乙氧基磺化物、联吡啶中一种或多种。Preferably, the nitrogen-containing leveling agent is selected from one or more of gelatin, aminopyridine, pyridine, aliphatic amine ethoxysulfonate, and bipyridine.
在一种实施方式中，所述含氮类整平剂为明胶。In one embodiment, the nitrogen-containing leveling agent is gelatin.
优选的，所述明胶的重均分子量为50000-60000。Preferably, the weight average molecular weight of the gelatin is 50000-60000.
在一种实施方式中，所述聚醚类整平剂选自聚乙二醇、羟乙基纤维素、羟乙基甲基纤维素中一种或多种。In one embodiment, the polyether leveling agent is selected from one or more of polyethylene glycol, hydroxyethyl cellulose, and hydroxyethyl methyl cellulose.
优选的，所述聚醚类整平剂为羟乙基纤维素。Preferably, the polyether leveling agent is hydroxyethyl cellulose.
在一种实施方式中，所述整平剂包括明胶和羟乙基纤维素。In one embodiment, the leveling agent includes gelatin and hydroxyethyl cellulose.
优选的，所述明胶和羟乙基纤维素的重量比为(2-6)：1；更优选的，所述明胶和羟乙基纤维素的重量比为5：1。Preferably, the weight ratio of the gelatin to the hydroxyethyl cellulose is (2-6): 1; more preferably, the weight ratio of the gelatin to the hydroxyethyl cellulose is 5:1.
在一种实施方式中，所述整平剂还包括季铵盐类整平剂。In one embodiment, the leveling agent further includes a quaternary ammonium salt leveling agent.
优选的，所述季铵盐类整平剂和羟乙基纤维素的重量比为(0.8-2.5)：1；更优选的，所述季铵盐类整平剂和羟乙基纤维素的重量比为1.2：1。Preferably, the weight ratio of the quaternary ammonium salt leveling agent and hydroxyethyl cellulose is (0.8-2.5): 1; more preferably, the quaternary ammonium salt leveling agent and hydroxyethyl cellulose The weight ratio is 1.2:1.
在一种实施方式中，所述季铵盐类整平剂为烷基二甲基氯化铵与二氧化硫共聚的季铵盐。In one embodiment, the quaternary ammonium salt leveling agent is a quaternary ammonium salt copolymerized with alkyl dimethyl ammonium chloride and sulfur dioxide.
本申请人在实验中发现，当使用重均分子量为50000-60000的明胶和羟乙基纤维素共同使用时，其得到的电解铜箔毛面粗糙度Rz相对比较大，难达到毛面粗糙度Rz＜3.0μm，而本申请人意外的发现，当整平剂还包括季铵盐类整平剂，且季铵盐类整平剂和羟乙基纤维素的重量比为(0.8-2.5)：1时，可以将电解铜箔毛面粗糙度Rz＜3.0μm，甚至更低，本申请人认为可能的原因是重均分子量为50000-60000的明胶和羟乙基纤维素分子含有大分子链结构，其之间相互作用形成氢键后，其大分子链结构在沉积在凸点的同时，其柔性分子链一部分遮挡凹处位点，阻碍铜离子在凹处的沉积，而季铵盐类整平剂，特别是烷基二甲基氯化铵与二氧化硫共聚的季铵盐可能在电镀液中一方面阻碍重均分子量为50000-60000的明胶分子和羟乙基纤维素之间的相互作用，另一方面其发挥电解质作用，影响铜离子的沉积分布，使得生箔表面的平整度增加，在后续的表面处理过程提供了基础。The applicant found in experiments that when gelatin with a weight average molecular weight of 50,000-60,000 and hydroxyethyl cellulose are used together, the roughness Rz of the resulting electrolytic copper foil is relatively large, and it is difficult to achieve the roughness of the rough surface. Rz<3.0μm, and the applicant unexpectedly found that when the leveling agent also includes quaternary ammonium salt leveling agent, and the weight ratio of quaternary ammonium salt leveling agent and hydroxyethyl cellulose is (0.8-2.5) : 1, the rough surface roughness Rz of the electrolytic copper foil can be less than 3.0 μm, or even lower. The applicant believes that the possible reason is that the gelatin and hydroxyethyl cellulose molecules with a weight average molecular weight of 50000-60000 contain macromolecular chains structure, after the interaction between them forms hydrogen bonds, while the macromolecular chain structure is deposited on the bump, part of its flexible molecular chain blocks the concave site, hindering the deposition of copper ions in the concave, while the quaternary ammonium salt Leveling agents, especially quaternary ammonium salts copolymerized with alkyl dimethyl ammonium chloride and sulfur dioxide, may hinder the interaction between gelatin molecules with a weight average molecular weight of 50,000-60,000 and hydroxyethyl cellulose on the one hand in the electroplating bath On the other hand, it plays the role of electrolyte and affects the deposition and distribution of copper ions, which increases the flatness of the surface of the green foil and provides a basis for the subsequent surface treatment process.
在一种实施方式中，所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐的重均分子量为3000-5000，在25℃粘度为10-30mpa.s。In one embodiment, the weight average molecular weight of the quaternary ammonium salt copolymerized with alkyl dimethyl ammonium chloride and sulfur dioxide is 3000-5000, and the viscosity at 25° C. is 10-30 mpa.s.
优选的，所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐的重均分子量为4000，在25℃粘度为20mpa.s。Preferably, the weight-average molecular weight of the quaternary ammonium salt copolymerized with alkyl dimethyl ammonium chloride and sulfur dioxide is 4000, and the viscosity at 25° C. is 20 mpa.s.
本申请人意外的发现，当所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐的重均分子量为4000，在25℃粘度为20mpa.s时，可以显著提高电解铜箔的延伸率，其值大于≥6.0％。The applicant unexpectedly found that when the weight-average molecular weight of the quaternary ammonium salt copolymerized with alkyldimethylammonium chloride and sulfur dioxide is 4000 and the viscosity at 25°C is 20mpa.s, the extension of the electrolytic copper foil can be significantly improved rate, its value is greater than ≥ 6.0%.
在一种实施方式中，所述羟乙基纤维素的摩尔取代度为1.8-2.0。In one embodiment, the molar substitution of the hydroxyethyl cellulose is 1.8-2.0.
当纤维素醚形成侧向分歧的醚时，平均每个失水葡萄糖单元上所结合的取代醚基总量用摩尔取代度(molar degree of substitution,MS)表示。When cellulose ethers form laterally branched ethers, the average total amount of substituted ether groups bound to each anhydroglucose unit is expressed as molar degree of substitution (MS).
本申请人意外的发现，当羟乙基纤维素的摩尔取代度为1.8-2.0时，可以提高延伸率、耐折性及降低应力，本申请人认为可能的原因是，摩尔取代度为1.8-2.0时，该羟乙基纤维素能够吸附在凹面的拐角处，抑制凹处的拐角处铜离子的沉积，避免形成针孔导致的内应力缺陷。The applicant unexpectedly found that when the molar substitution degree of hydroxyethyl cellulose is 1.8-2.0, the elongation, folding resistance and stress can be improved. The applicant believes that the possible reason is that the molar substitution degree is 1.8-2.0. 2.0, the hydroxyethyl cellulose can be adsorbed at the corners of the concave surface, inhibiting the deposition of copper ions at the corners of the concave surface, and avoiding the internal stress defect caused by the formation of pinholes.
本发明第二个方面提供了一种所述高频高速印制电路板用电解铜箔的制备方法，其包括下面步骤：The second aspect of the present invention provides a preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board, which comprises the following steps:
(1)电解液的配置：将50-100g/L铜离子、100-160g/L硫酸、150-300g/L添加剂混合得到电解液；(1) Configuration of electrolyte: mix 50-100g/L copper ions, 100-160g/L sulfuric acid, and 150-300g/L additives to obtain electrolyte;
(2)生箔的制备：通直流电，在电流密度3000-11000A/m 2条件下，阴极析出铜箔，剥离，得到生箔； (2) Preparation of green foil: direct current is applied, and under the condition of current density of 3000-11000A/m 2 , copper foil is precipitated at the cathode, and peeled off to obtain green foil;
(3)表面处理：对步骤(2)中制备的生箔进行表面处理。(3) Surface treatment: The green foil prepared in step (2) is subjected to surface treatment.
在一种实施方式中，所述高频高速印制电路板用电解铜箔的制备方法，其包括下面步骤：In one embodiment, the preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board includes the following steps:
(1)电解液的配置：将80g/L铜离子、126g/L硫酸、236g/L添加剂混合得到电解液；(1) configuration of electrolyte: 80g/L copper ion, 126g/L sulfuric acid, 236g/L additive are mixed to obtain electrolyte;
(2)生箔的制备：通直流电，在电流密度8000A/m 2条件下，阴极析出铜箔，剥离，得到生箔； (2) Preparation of green foil: direct current is applied, and under the condition of current density of 8000A/m 2 , copper foil is precipitated at the cathode, and peeled off to obtain green foil;
(3)表面处理：对步骤(2)中制备的生箔进行表面处理。(3) Surface treatment: The green foil prepared in step (2) is subjected to surface treatment.
本发明所述表面处理不作特别限定，可以列举的有酸处理阶段、粗化处理阶段、固化处理阶段、耐热层处理阶段、防氧化处理阶段、硅烷偶联剂处理阶段等，其具体处理方式不作特别限制，本领域技术人员可作常规选择。The surface treatment in the present invention is not particularly limited, and can be listed as acid treatment stage, roughening treatment stage, curing treatment stage, heat-resistant layer treatment stage, anti-oxidation treatment stage, silane coupling agent treatment stage, etc. The specific treatment methods Without particular limitation, those skilled in the art can make routine choices.
实施例Example
在下文中，通过实施例对本发明进行更详细地描述，但应理解，这些实施例仅仅是示例的而非限制性的。如果没有其它说明，下面实施例所用原料都是市售的。Hereinafter, the present invention will be described in more detail by means of examples, but it should be understood that these examples are merely illustrative and not restrictive. Unless otherwise stated, the raw materials used in the following examples are all commercially available.
实施例1Example 1
本发明的实施例1提供了一种高频高速印制电路板用电解铜箔，其由生箔层和表面处理层构成。Embodiment 1 of the present invention provides an electrolytic copper foil for a high-frequency and high-speed printed circuit board, which is composed of a green foil layer and a surface treatment layer.
所述生箔层由在含铜离子电解液中电解得到。The green foil layer is obtained by electrolysis in an electrolyte containing copper ions.
所述电解液为50g/L铜离子、100g/L硫酸、150g/L添加剂。The electrolyte is 50g/L copper ions, 100g/L sulfuric acid, and 150g/L additives.
所述铜离子的来源为五水硫酸铜。The source of the copper ions is copper sulfate pentahydrate.
所述添加剂为晶粒细化剂和整平剂，其浓度比为1：10；所述晶粒细化剂为聚二硫二丙烷磺酸钠；所述整平剂为明胶、羟乙基纤维素、烷基二甲基氯化铵与二氧化硫共聚的季铵盐，所述明胶和羟乙基纤维素的重量比为2：1，所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐和羟乙基纤维素的重量比为0.8：1；所述明胶的重均分子量为50000-60000；所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐的重均分子量为4000，在25℃粘度为20mpa.s；所述羟乙基纤维素的摩尔取代度为1.8-2.0，型号为HEC-15000。The additive is a grain refiner and a leveling agent, the concentration ratio of which is 1:10; the grain refiner is sodium polydisulfide dipropane sulfonate; the leveling agent is gelatin, hydroxyethyl The quaternary ammonium salt copolymerized with cellulose, alkyl dimethyl ammonium chloride and sulfur dioxide, the weight ratio of the gelatin and hydroxyethyl cellulose is 2:1, the copolymer of the alkyl dimethyl ammonium chloride and sulfur dioxide The weight ratio of quaternary ammonium salt and hydroxyethyl cellulose is 0.8:1; the weight average molecular weight of the gelatin is 50000-60000; the weight average molecular weight of the quaternary ammonium salt copolymerized with the alkyl dimethyl ammonium chloride and sulfur dioxide The molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0, and the model is HEC-15000.
所述高频高速印制电路板用电解铜箔的制备方法，如下：The preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board is as follows:
(1)电解液的配置：将50g/L铜离子、100g/L硫酸、150g/L添加剂混合得到电解液；(1) configuration of electrolyte: 50g/L copper ion, 100g/L sulfuric acid, 150g/L additive are mixed to obtain electrolyte;
(2)生箔的制备：通直流电，在电流密度8000A/m 2条件下，阴极析出铜箔，剥离，得到生箔； (2) Preparation of green foil: direct current is applied, and under the condition of current density of 8000A/m 2 , copper foil is precipitated at the cathode, and peeled off to obtain green foil;
(3)表面处理：对步骤(2)中制备的生箔进行硫酸酸化处理、粗化处理、锌-铬防氧化处理、3-缩水甘油醚氧基丙基三甲氧基硅烷处理。(3) Surface treatment: sulfuric acid acidification treatment, roughening treatment, zinc-chromium anti-oxidation treatment, and 3-glycidyloxypropyltrimethoxysilane treatment are performed on the raw foil prepared in step (2).
实施例2Example 2
本发明的实施例2提供了一种高频高速印制电路板用电解铜箔，其由生箔层和表面处理层构成。Embodiment 2 of the present invention provides an electrolytic copper foil for a high-frequency and high-speed printed circuit board, which is composed of a green foil layer and a surface treatment layer.
所述生箔层由在含铜离子电解液中电解得到。The green foil layer is obtained by electrolysis in an electrolyte containing copper ions.
所述电解液为100g/L铜离子、160g/L硫酸、300g/L添加剂。The electrolyte is 100g/L copper ions, 160g/L sulfuric acid, and 300g/L additives.
所述铜离子的来源为五水硫酸铜。The source of the copper ions is copper sulfate pentahydrate.
所述添加剂为晶粒细化剂和整平剂，其浓度比为1：25；所述晶粒细化剂为聚二硫二丙烷磺酸钠；所述整平剂为明胶、羟乙基纤维素、烷基二甲基氯化铵与二氧化硫共聚的季铵盐，所述明胶和羟乙基纤维素的重量比为6：1，所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐和羟乙基纤维素的重量比为2.5：1；所述明胶的重均分子量为50000-60000；所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐的重均分子量为4000，在25℃粘度为20mpa.s；所述羟乙基纤维素的摩尔取代度为1.8-2.0，型号为HEC-15000。The additive is a grain refiner and a leveling agent, and its concentration ratio is 1:25; the grain refiner is sodium polydisulfide dipropane sulfonate; the leveling agent is gelatin, hydroxyethyl The quaternary ammonium salt copolymerized with cellulose, alkyl dimethyl ammonium chloride and sulfur dioxide, the weight ratio of the gelatin and hydroxyethyl cellulose is 6:1, the copolymer of the alkyl dimethyl ammonium chloride and sulfur dioxide The weight ratio of quaternary ammonium salt and hydroxyethyl cellulose is 2.5:1; the weight-average molecular weight of the gelatin is 50,000-60,000; the weight-average molecular weight of the quaternary ammonium salt copolymerized with the alkyl dimethyl ammonium chloride and sulfur dioxide The molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0, and the model is HEC-15000.
所述高频高速印制电路板用电解铜箔的制备方法，如下：The preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board is as follows:
(1)电解液的配置：将100g/L铜离子、160g/L硫酸、300g/L添加剂混合得到电解液；(1) configuration of electrolyte: 100g/L copper ion, 160g/L sulfuric acid, 300g/L additive are mixed to obtain electrolyte;
(2)生箔的制备：通直流电，在电流密度8000A/m 2条件下，阴极析出铜箔，剥离，得到生箔； (2) Preparation of green foil: direct current is applied, and under the condition of current density of 8000A/m 2 , copper foil is precipitated at the cathode, and peeled off to obtain green foil;
(3)表面处理：对步骤(2)中制备的生箔进行硫酸酸化处理、粗化处理、锌-铬防氧化处理、3-缩水甘油醚氧基丙基三甲氧基硅烷处理。(3) Surface treatment: sulfuric acid acidification treatment, roughening treatment, zinc-chromium anti-oxidation treatment, and 3-glycidyloxypropyltrimethoxysilane treatment are performed on the raw foil prepared in step (2).
实施例3Example 3
本发明的实施例3提供了一种高频高速印制电路板用电解铜箔，其由生箔层和表面处理层构成。Embodiment 3 of the present invention provides an electrolytic copper foil for a high-frequency and high-speed printed circuit board, which is composed of a green foil layer and a surface treatment layer.
所述生箔层由在含铜离子电解液中电解得到。The green foil layer is obtained by electrolysis in an electrolyte containing copper ions.
所述电解液为80g/L铜离子、126g/L硫酸、236g/L添加剂。The electrolyte is 80g/L copper ions, 126g/L sulfuric acid, and 236g/L additives.
所述铜离子的来源为五水硫酸铜。The source of the copper ions is copper sulfate pentahydrate.
所述添加剂为晶粒细化剂和整平剂，其浓度比为1：15；所述晶粒细化剂为聚二硫二丙烷磺酸钠；所述整平剂为明胶、羟乙基纤维素、烷基二甲基氯化铵与二氧化硫共聚的季铵盐，所述明胶和羟乙基纤维素的重量比为5：1，所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐和羟乙基纤维素的重量比为1.2：1；所述明胶的重均分子量为50000-60000；所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐的重均分子量为4000，在25℃粘度为20mpa.s；所述羟乙基纤维素的摩尔取代度为1.8-2.0，型号为HEC-15000。The additive is a grain refiner and a leveling agent, and the concentration ratio is 1:15; the grain refiner is sodium polydisulfide dipropane sulfonate; the leveling agent is gelatin, hydroxyethyl The quaternary ammonium salt of cellulose, alkyl dimethyl ammonium chloride and sulfur dioxide copolymerization, the weight ratio of the gelatin and hydroxyethyl cellulose is 5:1, the alkyl dimethyl ammonium chloride and sulfur dioxide copolymerization The weight ratio of quaternary ammonium salt and hydroxyethyl cellulose is 1.2:1; the weight-average molecular weight of the gelatin is 50,000-60,000; the weight-average molecular weight of the quaternary ammonium salt copolymerized with the alkyl dimethyl ammonium chloride and sulfur dioxide The molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0, and the model is HEC-15000.
所述高频高速印制电路板用电解铜箔的制备方法，如下：The preparation method of the electrolytic copper foil for the high-frequency and high-speed printed circuit board is as follows:
(1)电解液的配置：将50g/L铜离子、100g/L硫酸、150g/L添加剂混合得到电解液；(1) configuration of electrolyte: 50g/L copper ion, 100g/L sulfuric acid, 150g/L additive are mixed to obtain electrolyte;
(2)生箔的制备：通直流电，在电流密度8000A/m 2条件下，阴极析出铜箔，剥离，得到生箔； (2) Preparation of green foil: direct current is applied, and under the condition of current density of 8000A/m 2 , copper foil is precipitated at the cathode, and peeled off to obtain green foil;
(3)表面处理：对步骤(2)中制备的生箔进行硫酸酸化处理、粗化处理、锌-铬防氧化处理、3-缩水甘油醚氧基丙基三甲氧基硅烷处理。(3) Surface treatment: sulfuric acid acidification treatment, roughening treatment, zinc-chromium anti-oxidation treatment, and 3-glycidyloxypropyltrimethoxysilane treatment are performed on the raw foil prepared in step (2).
实施例4Example 4
本发明的实施例4提供了一种高频高速印制电路板用电解铜箔，其具体实施 方式同实施例3，不同之处在于，所述整平剂为明胶和羟乙基纤维素，其重量比为5：1，所述明胶的重均分子量为50000-60000，所述羟乙基纤维素的摩尔取代度为1.8-2.0，型号为HEC-15000。Embodiment 4 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards. The weight ratio is 5:1, the weight average molecular weight of the gelatin is 50000-60000, the molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0, and the model is HEC-15000.
所述高频高速印制电路板用电解铜箔的制备方法其具体实施方式同实施例3。The specific implementation of the method for preparing the electrolytic copper foil for high-frequency and high-speed printed circuit boards is the same as that in Example 3.
实施例5Example 5
本发明的实施例5提供了一种高频高速印制电路板用电解铜箔，其具体实施方式同实施例3，不同之处在于，所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐的重均分子量为5000，在25℃粘度为7mpa.s。Embodiment 5 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards. The weight average molecular weight of the quaternary ammonium salt is 5000, and the viscosity at 25°C is 7mpa.s.
所述高频高速印制电路板用电解铜箔的制备方法其具体实施方式同实施例3。The specific implementation of the method for preparing the electrolytic copper foil for high-frequency and high-speed printed circuit boards is the same as that in Example 3.
实施例6Example 6
本发明的实施例6提供了一种高频高速印制电路板用电解铜箔，其具体实施方式同实施例3，不同之处在于，所述羟乙基纤维素的摩尔取代度为2.2-2.8。Embodiment 6 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards. 2.8.
所述高频高速印制电路板用电解铜箔的制备方法其具体实施方式同实施例3。The specific implementation of the method for preparing the electrolytic copper foil for high-frequency and high-speed printed circuit boards is the same as that in Example 3.
实施例7Example 7
本发明的实施例7提供了一种高频高速印制电路板用电解铜箔，其具体实施方式同实施例3，不同之处在于，所述晶粒细化剂为四氢噻唑硫酮。Embodiment 7 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards, the specific implementation of which is the same as that of embodiment 3, except that the grain refiner is thiazolidinethione.
所述高频高速印制电路板用电解铜箔的制备方法其具体实施方式同实施例3。The specific implementation of the method for preparing the electrolytic copper foil for high-frequency and high-speed printed circuit boards is the same as that in Example 3.
实施例8Example 8
本发明的实施例8提供了一种高频高速印制电路板用电解铜箔，其具体实施方式同实施例3，不同之处在于，所述整平剂为羟乙基纤维素、烷基二甲基氯化铵与二氧化硫共聚的季铵盐，所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐和羟乙基纤维素的重量比为1.2：1；所述烷基二甲基氯化铵与二氧化硫共聚的季铵盐的重均分子量为4000，在25℃粘度为20mpa.s；所述羟乙基纤维素的摩尔取代度为1.8-2.0，型号为HEC-15000。Embodiment 8 of the present invention provides an electrolytic copper foil for high-frequency and high-speed printed circuit boards, the specific implementation of which is the same as that of Embodiment 3, except that the leveling agent is The quaternary ammonium salt copolymerized with dimethyl ammonium chloride and sulfur dioxide, the weight ratio of the quaternary ammonium salt copolymerized with dimethyl ammonium chloride and sulfur dioxide and hydroxyethyl cellulose is 1.2:1; The weight-average molecular weight of the quaternary ammonium salt copolymerized with methyl ammonium chloride and sulfur dioxide is 4000, and the viscosity at 25° C. is 20 mpa.s; the molar substitution degree of the hydroxyethyl cellulose is 1.8-2.0, and the model is HEC-15000.
所述高频高速印制电路板用电解铜箔的制备方法其具体实施方式同实施例 3。The specific implementation of the method for preparing the electrolytic copper foil for high-frequency and high-speed printed circuit boards is the same as that in Example 3.
性能评估performance evaluation
1.单位面积重量偏差：将实施例1-8得到的高频高速印制电路板用电解铜箔的单位面积重量按照GB/T 5230-1995标准进行测试，每个实施例测试10次，计算单位面积重量偏差，单位面积重量偏差<5.0％，记为优；单位面积重量偏差为5.0-7.0％，记为良；单位面积重量偏差>7.0％记为差。1. Weight per unit area deviation: the weight per unit area of the electrolytic copper foil for high-frequency and high-speed printed circuit boards obtained in Examples 1-8 was tested according to the GB/T 5230-1995 standard, and each embodiment was tested 10 times, and calculated For the deviation of weight per unit area, the deviation of weight per unit area is less than 5.0%, which is regarded as excellent; the deviation of weight per unit area is 5.0-7.0%, which is regarded as good; the deviation of weight per unit area is more than 7.0%, which is regarded as poor.
2.毛面粗糙度：将实施例1～8得到的高频高速印制电路板用电解铜箔的粗糙度按照GB/T 5230-1995标准进行测试。测试微观不平度(Rz)，Rz为在取样长度内5个最大的轮廓峰高的平均值与5个最大的轮廓谷深的平均值之差。其中，测试得到的毛面粗糙度Rz＜2.5μm记为优，毛面粗糙度Rz为2-5-3.0μm记为合格，毛面粗糙度Rz＞3.0μm记为不合格。2. Roughness of rough surface: The roughness of the electrolytic copper foils for high-frequency and high-speed printed circuit boards obtained in Examples 1 to 8 was tested according to the GB/T 5230-1995 standard. Microscopic roughness (Rz) was tested, where Rz was the difference between the average of the 5 largest profile peak heights and the average of the 5 largest profile valley depths within the sampling length. Among them, the roughness Rz<2.5μm obtained by the test is regarded as excellent, the roughness Rz of the roughness Rz of 2-5-3.0μm is regarded as qualified, and the roughness of the roughness Rz>3.0μm is regarded as unqualified.
3.延伸率：将实施例1-8提供的高频高速印制电路板用电解铜箔的延伸率按照GB/T 5230-1995标准进行测试，测试温度为25℃。延伸率≥6％，记为合格，否则记为不合格。3. Elongation: The elongation of the electrolytic copper foil for high-frequency and high-speed printed circuit boards provided in Examples 1-8 was tested according to the GB/T 5230-1995 standard, and the test temperature was 25°C. Elongation ≥ 6%, recorded as qualified, otherwise recorded as unqualified.
4.抗剥离强度：将实施例1-8提供的高频高速印制电路板用电解铜箔的抗剥离强度按照GB/T 5230-1995标准进行测试，测试温度为25℃。抗剥离强度≥1.0Kg/cm，记为一级，抗剥离强度为0.7-1Kg/cm(不包括1Kg/cm)，记为二级，抗剥离强度小于0.7Kg/cm，记为三级。4. Anti-peeling strength: The anti-peeling strength of the electrolytic copper foils for high-frequency and high-speed printed circuit boards provided in Examples 1-8 was tested according to the GB/T 5230-1995 standard, and the test temperature was 25°C. Anti-peel strength ≥ 1.0Kg/cm, denoted as first-class, anti-peel strength of 0.7-1Kg/cm (excluding 1Kg/cm), denoted as second-class, anti-peel strength less than 0.7Kg/cm, denoted as third-class.
表1Table 1
   单位面积重量偏差Weight per unit area deviation 毛面粗糙度RzRoughness Rz 延伸率Elongation 抗剥离强度peel strength
实施例1Example 1 优excellent 优excellent 合格qualified 一级Level 1
实施例2Example 2 优excellent 优excellent 合格qualified 一级Level 1
实施例3Example 3 优excellent 优excellent 合格qualified 一级Level 1
实施例4Example 4 差Difference 不合格Failed 不合格Failed 三级Level 3
实施例5Example 5 良good 合格qualified 不合格Failed 二级secondary
实施例6Example 6 良good 不合格Failed 不合格Failed 三级Level 3
实施例7Example 7 良good 不合格Failed 不合格Failed 二级secondary
实施例8Example 8 差Difference 合格qualified 不合格Failed 三级Level 3
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数 值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。The foregoing examples are illustrative only and serve to explain some of the features of the methods described herein. The appended claims are intended to claim the broadest conceivable scope and the embodiments presented herein are merely illustrative of selected implementations according to a combination of all possible embodiments. Accordingly, it is the applicant's intention that the appended claims not be limited by the selection of examples that characterize the invention. Some numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be construed, where possible, to be covered by the appended claims.

Claims (10)

  1. 一种高频高速印制电路板用电解铜箔，其特征在于，其包括生箔层和表面处理层；所述电解铜箔的厚度为12-35μm，单位面积重量偏差＜5％，在25℃的抗拉强度≥300N/mm 2，在25℃的延伸率≥6.0％，在25℃抗剥离强度≥1.0Kg/cm，毛面Rz≤3.0μm。 An electrolytic copper foil for high-frequency and high-speed printed circuit boards, characterized in that it comprises a raw foil layer and a surface treatment layer; the thickness of the electrolytic copper foil is 12-35 μm, the weight deviation per unit area is less than 5%, and the thickness of the electrolytic copper foil is less than 5%. Tensile strength at ℃≥300N/mm 2 , elongation at 25℃≥6.0%, peel strength at 25℃≥1.0Kg/cm, rough surface Rz≤3.0μm.
  2. 根据权利要求1所述高频高速印制电路板用电解铜箔，其特征在于，所述生箔层由在含铜离子电解液中电解得到，所述电解液包括50-100g/L铜离子、100-160g/L硫酸、150-300g/L添加剂。The electrolytic copper foil for high-frequency and high-speed printed circuit boards according to claim 1, wherein the green foil layer is obtained by electrolysis in an electrolyte containing copper ions, and the electrolyte includes 50-100 g/L copper ions , 100-160g/L sulfuric acid, 150-300g/L additives.
  3. 根据权利要求2所述高频高速印制电路板用电解铜箔，其特征在于，所述添加剂包括晶粒细化剂和整平剂，其浓度比为1：(10-25)。The electrolytic copper foil for high-frequency and high-speed printed circuit boards according to claim 2, wherein the additive comprises a grain refiner and a leveling agent, and the concentration ratio thereof is 1:(10-25).
  4. 根据权利要求3所述高频高速印制电路板用电解铜箔，其特征在于，所述晶粒细化剂选自聚二硫二丙烷磺酸钠、聚乙二醇、乙撑硫脲、3-巯基-1-丙磺酸盐、4-[[2-(乙酰氨基)乙基]二硫代]-1-丁烷亚磺酸钠、四氢噻唑硫酮、硫胺二硫化合物、2-取代亚肼基-1,3-二硫杂环戊烷、2-巯基苯并咪唑中一种或多种。The electrolytic copper foil for high-frequency and high-speed printed circuit boards according to claim 3, wherein the grain refiner is selected from the group consisting of sodium polydisulfide dipropane sulfonate, polyethylene glycol, ethylene thiourea, 3-Mercapto-1-propanesulfonate, 4-[[2-(acetylamino)ethyl]dithio]-1-butanesulfinate sodium, thiazolidinethione, thiamine disulfide compound, One or more of 2-substituted hydrazono-1,3-dithiolane and 2-mercaptobenzimidazole.
  5. 根据权利要求3所述高频高速印制电路板用电解铜箔，其特征在于，所述整平剂选自含氮类整平剂、聚醚类整平剂、季铵盐类整平剂中一种或多种。The electrolytic copper foil for high-frequency and high-speed printed circuit boards according to claim 3, wherein the leveling agent is selected from nitrogen-containing leveling agents, polyether leveling agents, and quaternary ammonium salt leveling agents one or more of them.
  6. 根据权利要求5所述高频高速印制电路板用电解铜箔，其特征在于，所述含氮类整平剂选自明胶、氨基吡啶、吡啶、脂肪胺乙氧基磺化物、联吡啶中一种或多种。The electrolytic copper foil for high-frequency and high-speed printed circuit boards according to claim 5, wherein the nitrogen-containing leveling agent is selected from the group consisting of gelatin, aminopyridine, pyridine, fatty amine ethoxysulfonate, and bipyridine one or more.
  7. 根据权利要求6所述高频高速印制电路板用电解铜箔，其特征在于，所述明胶的重均分子量为50000-60000。The electrolytic copper foil for high-frequency and high-speed printed circuit boards according to claim 6, wherein the weight-average molecular weight of the gelatin is 50,000-60,000.
  8. 根据权利要求5所述高频高速印制电路板用电解铜箔，其特征在于，所述聚醚类整平剂选自聚乙二醇、羟乙基纤维素、羟乙基甲基纤维素中一种或多种。The electrolytic copper foil for high-frequency and high-speed printed circuit boards according to claim 5, wherein the polyether leveling agent is selected from the group consisting of polyethylene glycol, hydroxyethyl cellulose, and hydroxyethyl methyl cellulose one or more of them.
  9. 根据权利要求5-8任一项所述高频高速印制电路板用电解铜箔，其特征在于，所述季铵盐类整平剂的重均分子量为3000-5000，在25℃粘度为10-30mpa.s。The electrolytic copper foil for high-frequency and high-speed printed circuit boards according to any one of claims 5-8, wherein the weight-average molecular weight of the quaternary ammonium salt leveling agent is 3000-5000, and the viscosity at 25°C is 3000-5000. 10-30mpa.s.
  10. 一种根据权利要求2-9任一项所述高频高速印制电路板用电解铜箔的制备方法，其特征在于，包括下面步骤：A preparation method of electrolytic copper foil for high-frequency and high-speed printed circuit boards according to any one of claims 2-9, characterized in that, comprising the following steps:
    (1)电解液的配置：将50-100g/L铜离子、100-160g/L硫酸、150-300g/L添加剂混合得到电解液；(1) Configuration of electrolyte: mix 50-100g/L copper ions, 100-160g/L sulfuric acid, and 150-300g/L additives to obtain electrolyte;
    (2)生箔的制备：通直流电，在电流密度3000-11000A/m 2条件下，阴极析 出铜箔，剥离，得到生箔； (2) Preparation of green foil: direct current is applied, and under the condition of current density of 3000-11000A/m 2 , copper foil is precipitated at the cathode, and peeled off to obtain green foil;
    (3)表面处理：对步骤(2)中制备的生箔进行表面处理。(3) Surface treatment: The green foil prepared in step (2) is subjected to surface treatment.
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