阅读说明：本技术 一种高强度电子铜箔制备方法 (Preparation method of high-strength electronic copper foil ) 是由 金荣涛 杨红光 王小东 于 2020-12-08 设计创作，主要内容包括：本发明公开了一种高强度电子铜箔制备方法,包括以下步骤：步骤S1,将铜杆、铜线、氯化物用硫酸溶解成水溶液,作为主电解液,所述主电解液中铜、硫酸的含量分别为60-100g/L、70-160g/L、0-25mg/L；步骤S2,向主电解液中放入添加剂,所述添加剂包含A剂、B剂、C剂,且浓度分别为3-50mg/L、5-80 mg/L、1-20mg/L,步骤S3,在温度为35-65℃、流量为45m-50～3/h、电流密度为2000-8200A/m～2的条件下,对放有添加剂的主电解液进行电解；步骤S4：主电解液电解在阴极上电沉积厚9-105um。本发明提供一种高强度电子铜箔制备方法,这种制备方法生产的电子铜箔,具有抗拉强度高、延伸率高,厚度均匀的优点,可满足超高密度印刷线路板的发展需要。(The invention discloses a preparation method of a high-strength electronic copper foil, which comprises the following steps: step S1, dissolving a copper rod, a copper wire and chloride into aqueous solution by using sulfuric acid to serve as main electrolyte, wherein the contents of copper and sulfuric acid in the main electrolyte are respectively 60-100g/L, 70-160g/L and 0-25 mg/L; step S2, adding additives into the main electrolyte, wherein the additives comprise an agent A, an agent B and an agent C, and the concentrations are 3-50mg/L, 5-80 mg/L and 1-20mg/L respectively, and step S3, the temperature is 35-65 ℃, and the flow rate is 45m-50 3 Current density of 2000-8200A/m 2 Under the condition of (1), electrolyzing the main electrolyte with the additive; step S4: the main electrolyte electrolysis electrodeposits 9-105um thick on the cathode. The invention provides a preparation method of a high-strength electronic copper foil, and the electronic copper foil produced by the preparation method has the advantages of high tensile strength, high elongation and uniform thickness, and can meet the development requirement of an ultrahigh-density printed circuit board.)

1. The preparation method of the high-strength electronic copper foil is characterized by comprising the following steps of:

step S1, dissolving a copper rod, a copper wire and chloride into aqueous solution by using sulfuric acid to serve as main electrolyte, wherein the contents of copper and sulfuric acid in the main electrolyte are respectively 60-100g/L, 70-160g/L and 0-25 mg/L;

step S2, adding additives into the main electrolyte, wherein the additives comprise an agent A, an agent B and an agent C, the concentrations of the agent A, the agent B and the agent C are respectively 3-50mg/L, 5-80 mg/L and 1-20mg/L, the agent A at least contains one of thiazolidinethione (H1), fatty amine ethoxy sulfonate (AESS), sodium mercapto imidazole propanesulfonate (MESS) and azooxazine dye (MDD), the agent B at least contains one of sodium polydithio-dipropyl sulfonate (SPS), 3-mercapto-1-propane sodium sulfonate (MPS), sodium mercaptopropane sulfonate (HP), dimethyl formamido sulfonate (TPS), thia-imidan dithio-propane sulfonic acid (SH 110) and 2-mercapto benzimidazole, the agent C at least contains one of polyethylene glycol (P) and Sodium Dodecyl Benzene Sulfonate (SDBS);

step S3, the temperature is 35-65 ℃, and the flow rate is 45m-50³Current density of 2000-8200A/m²Under the condition of (1), electrolyzing the main electrolyte with the additive;

step S4: and (3) electrolyzing the main electrolyte to electrodeposit 9-105um on the cathode to obtain the high-strength electronic copper foil.

Technical Field

The invention relates to the technical field of electrolytic copper foil, in particular to a preparation method of a high-strength electronic copper foil.

Background

With the development and the continuous upgrading of the technology, the printed circuit board gradually develops towards the direction of high density, small aperture, large capacity, light weight and thinness, so that the conductive circuit made of the electrolytic copper foil is thinner and thinner, the working temperature is higher and higher, the manufacturing process is more and more complex, and the tension borne by the copper foil is larger and larger. The traditional electrolytic copper foil has tensile strength below 450MPa, and is difficult to meet the development requirement of the ultrahigh-density printed circuit board.

Disclosure of Invention

Aiming at the problems in the related art, the invention provides a preparation method of a high-strength electronic copper foil, which solves the problem that the existing electrolytic copper foil is low in tensile strength.

In order to achieve the technical purpose, the technical scheme of the invention is as follows:

the preparation method of the high-strength electronic copper foil comprises the following steps:

step S1, dissolving a copper rod, a copper wire and chloride into aqueous solution by using sulfuric acid to serve as main electrolyte, wherein the contents of copper and sulfuric acid in the main electrolyte are respectively 60-100g/L, 70-160g/L and 0-25 mg/L;

step S2, adding additives into the main electrolyte, wherein the additives comprise an agent A, an agent B and an agent C, the concentrations of the agent A, the agent B and the agent C are respectively 3-50mg/L, 5-80 mg/L and 1-20mg/L, the agent A at least contains one of thiazolidinethione (H1), fatty amine ethoxy sulfonate (AESS), sodium mercapto imidazole propanesulfonate (MESS) and azooxazine dye (MDD), the agent B at least contains one of sodium polydithio-dipropyl sulfonate (SPS), 3-mercapto-1-propane sodium sulfonate (MPS), sodium mercaptopropane sulfonate (HP), dimethyl formamido sulfonate (TPS), thia-imidan dithio-propane sulfonic acid (SH 110) and 2-mercapto benzimidazole, the agent C at least contains one of polyethylene glycol (P) and Sodium Dodecyl Benzene Sulfonate (SDBS);

step S3, the temperature is 35-65 ℃, and the flow rate is 45m-50³Current density of 2000-8200A/m²Under the condition of (1), electrolyzing the main electrolyte with the additive;

step S4: and (3) electrolyzing the main electrolyte to electrodeposit 9-105um on the cathode to obtain the high-strength electronic copper foil.

The invention has the beneficial effects that: the preparation method of the high-strength electronic copper foil obtains the electronic copper foil with compact and uniform crystal form and excellent mechanical property through the synergistic action of various additives, has the advantages of high tensile strength, high elongation and uniform thickness, and can meet the development requirement of an ultrahigh-density printed circuit board.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.

The first embodiment is as follows:

the preparation method of the high-strength electronic copper foil provided by the embodiment of the invention comprises the following steps:

step S1, dissolving a copper rod and a copper wire into aqueous solution by using sulfuric acid to serve as main electrolyte, wherein the contents of copper and sulfuric acid in the main electrolyte are respectively 80g/L and 100 g/L;

step S2, adding additives into the main electrolyte, wherein the additives comprise an agent A, an agent B and an agent C,

the agent A is 5mg/l thiazolidinethione, the agent B is 8mg/l 3-mercapto-1-propane sodium sulfonate, and the agent C is 10mg/l polyethylene glycol;

step S3, the temperature is 55 ℃, the flow rate is 50³H, current density 3000A/m²Under the condition of (1), electrolyzing the main electrolyte with the additive;

step S4: and (3) electrolyzing the main electrolyte to electrodeposit the thickness of 9um on the cathode to obtain the high-strength electronic copper foil.

Example two:

the preparation method of the high-strength electronic copper foil provided by the embodiment of the invention comprises the following steps:

step S1, dissolving a copper rod and a copper wire into aqueous solution by using sulfuric acid to serve as main electrolyte, wherein the contents of copper and sulfuric acid in the main electrolyte are respectively 95g/L and 120 g/L;

step S2, adding additives into the main electrolyte, wherein the additives comprise an agent A, an agent B and an agent C,

the agent A is 5mg/l thiazolidinethione, the agent B is 8mg/l 3-mercapto-1-propane sodium sulfonate, and the agent C is 10mg/l polyethylene glycol;

step S3, the temperature is 55 ℃, the flow rate is 50³H, current density 3000A/m²Under the condition of (1), electrolyzing the main electrolyte with the additive;

step S4: and (3) electrolyzing the main electrolyte to electrodeposit the thickness of 12um on the cathode to obtain the high-strength electronic copper foil.

Example three:

the preparation method of the high-strength electronic copper foil provided by the embodiment of the invention comprises the following steps:

step S1, dissolving a copper rod, a copper wire and chloride into aqueous solution by using sulfuric acid to serve as main electrolyte, wherein the contents of copper, sulfuric acid and chlorine in the main electrolyte are respectively 80g/L, 100g/L and 25 mg/L;

step S2, adding additives into the main electrolyte, wherein the additives comprise an agent A, an agent B and an agent C,

the agent A is 18mg/l of fatty amine ethoxy sulfonate, the agent B is 20mg/l of sodium polydithio-dipropyl sulfonate and 2-mercaptobenzimidazole, and the agent C is 10mg/l of sodium dodecyl benzene sulfonate;

step S3, the temperature is 55 ℃, the flow rate is 45³H, current density 5600A/m²Under the condition of (1), electrolyzing the main electrolyte with the additive;

step S4: and (3) electrolyzing the main electrolyte to electrodeposit the thickness of 9um on the cathode to obtain the high-strength electronic copper foil.

Example four:

the preparation method of the high-strength electronic copper foil provided by the embodiment of the invention comprises the following steps:

step S1, dissolving a copper rod, a copper wire and chloride into aqueous solution by using sulfuric acid to serve as main electrolyte, wherein the contents of copper, sulfuric acid and chlorine in the main electrolyte are respectively 95g/L, 130g/L and 25 mg/L;

step S2, adding additives into the main electrolyte, wherein the additives comprise an agent A, an agent B and an agent C,

the agent A is 18mg/l of mercaptoimidazole sodium propanesulfonate, the agent B is 20mg/l of polydithio-dipropyl sodium sulfonate, and the agent C is 10mg/l of dodecyl benzene sodium sulfonate;

step S3, the temperature is 55 ℃, the flow rate is 45³H, current density of 7200A/m²Under the condition of (1), electrolyzing the main electrolyte with the additive;

step S4: and (3) electrolyzing the main electrolyte to electrodeposit the thickness of 15um on the cathode to obtain the high-strength electronic copper foil.

Example five:

the preparation method of the high-strength electronic copper foil provided by the embodiment of the invention comprises the following steps:

step S1, dissolving a copper rod, a copper wire and chloride into aqueous solution by using sulfuric acid to serve as main electrolyte, wherein the contents of copper, sulfuric acid and chlorine in the main electrolyte are respectively 80g/L, 100g/L and 22 mg/L;

step S2, adding additives into the main electrolyte, wherein the additives comprise an agent A, an agent B and an agent C,

the agent A is 15mg/l fatty amine ethoxy sulfonate, the agent B is 12mg/l sodium polydithio dipropyl sulfonate, and the agent C is 16mg/l polyethylene glycol;

step S3, the temperature is 50 ℃, and the flow rate is 50³H, current density 4500A/m²Under the condition of (1), electrolyzing the main electrolyte with the additive;

step S4: and (3) electrolyzing the main electrolyte to electrodeposit on the cathode to the thickness of 35um to obtain the high-strength electronic copper foil.

Example six:

the preparation method of the high-strength electronic copper foil provided by the embodiment of the invention comprises the following steps:

step S1, dissolving a copper rod, a copper wire and chloride into aqueous solution by using sulfuric acid to serve as main electrolyte, wherein the contents of copper, sulfuric acid and chlorine in the main electrolyte are respectively 80g/L, 100g/L and 22 mg/L;

step S2, adding additives into the main electrolyte, wherein the additives comprise an agent A, an agent B and an agent C,

the agent A is 18mg/l of mercaptoimidazole sodium propanesulfonate, the agent B is 20mg/l of polydithio-dipropyl sodium sulfonate, and the agent C is 10mg/l of dodecyl benzene sodium sulfonate;

step S3, the temperature is 50 ℃, the flow rate is 45³H, current density 5600A/m²Under the condition of (1), electrolyzing the main electrolyte with the additive;

step S4: and (3) electrolyzing the main electrolyte to electrodeposit the thickness of 70um on the cathode to obtain the high-strength electronic copper foil.

The six examples were tested separately and included the following steps:

step S41, taking out the high-strength electronic copper foil in the step S4, selecting a copper foil sample which is smooth and has no distortion wrinkles, and cutting the copper foil sample into 5 pieces of 254mmX12.7mm samples;

step S42, weighing and recording the weight, wherein the accurate value of the weighed sample is 0.001g, the average thickness value and the average sectional area of the section are calculated, and the density of the electronic copper foil is 8.909g/cm³The calculation formula is as follows:

average thickness (um) = specimen weight (g)/specimen area (cm)²) x copper foil Density (g/cm)³）；

Average cross-sectional area (cm)²) = sample weight (g)/sample length (cm) x copper foil density (g/cm)³）；

Step S43, measuring the experimental data, if the tensile testing instrument is equipped with an area compensator, measuring the average sectional area by using the dial of the tensile testing instrument, if not, calculating the tensile strength by using the sectional area, wherein the calculation formula is as follows:

tensile strength (MPa) = load force for breaking the sample/average cross-sectional area;

and step S44, carrying out high-temperature test on the selected copper foil sample.

In this embodiment, in the step S44, the specific steps of the high temperature test are as follows:

s441, heating the high-temperature box to 180 ℃, opening the high-temperature box, clamping the copper foil sample between tension clamps, and staying for 5min, wherein the maximum time of the temperature is not more than 10 min;

s442, closing the high-temperature box, and controlling the temperature of the sample by using the thermocouple to be maintained at a set value;

s443, the tensile strength of the copper foil at 180 ℃ is tested, and the average value and the elongation of 5 copper foil samples are calculated.

The results of the performance test of the high-strength electronic copper foil are shown as follows:

physical Properties	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Thickness (um)	9	12	9	15	35	70
Tensile strength (MPa)	710	625	685	718	825	748
							Tensile strength after baking (MPa)	485	430	450	460	430	480
Elongation (%)	6.8	5.6	6.8	9.1	7.8	5.6

In summary, the tensile strength at room temperature is not less than 700Mpa, the tensile strength at 180 ℃ is not less than 450Mpa, and the elongation is greater than 5.0% as measured by the electronic circuit copper foil manufactured in the examples, and the high-strength electronic circuit copper foil can be formed by adopting any known peel strength enhancing and oxidation resisting surface treatment process.

It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.