CN114032586A - Electrolyte for improving uniformity of M-surface particles of electrolytic copper foil, production process and product - Google Patents
Electrolyte for improving uniformity of M-surface particles of electrolytic copper foil, production process and product Download PDFInfo
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- CN114032586A CN114032586A CN202111334773.XA CN202111334773A CN114032586A CN 114032586 A CN114032586 A CN 114032586A CN 202111334773 A CN202111334773 A CN 202111334773A CN 114032586 A CN114032586 A CN 114032586A
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- 239000002245 particle Substances 0.000 title claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011889 copper foil Substances 0.000 title claims abstract description 55
- 239000003792 electrolyte Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000005498 polishing Methods 0.000 claims abstract description 62
- 108010010803 Gelatin Proteins 0.000 claims abstract description 28
- 229920000159 gelatin Polymers 0.000 claims abstract description 28
- 239000008273 gelatin Substances 0.000 claims abstract description 28
- 235000019322 gelatine Nutrition 0.000 claims abstract description 28
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 25
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 25
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 25
- 239000011888 foil Substances 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 5
- 230000001680 brushing effect Effects 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 description 27
- 230000000996 additive effect Effects 0.000 description 25
- 239000007788 liquid Substances 0.000 description 16
- 238000004381 surface treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000007714 electro crystallization reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Classifications
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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
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B29/00—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
- B24B29/005—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents using brushes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B29/00—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
- B24B29/02—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents designed for particular workpieces
- B24B29/04—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents designed for particular workpieces for rotationally symmetrical workpieces, e.g. ball-, cylinder- or cone-shaped workpieces
-
- 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
Abstract
The invention discloses an electrolyte for improving the uniformity of M-surface particles of an electrolytic copper foil, which comprises copper sulfate, sulfuric acid, pure water and chloride ions, wherein the concentration of the copper ions is 65g/L to 90 g/L; the concentration of the sulfuric acid is 80g/L to 120 g/L; the concentration of the chloride ions is 10mg/L to 30 mg/L; the concentration of the hydroxyethyl cellulose is 7mg/L to 15 mg/L; the invention also discloses a production process for improving the uniformity of the M-surface particles of the electrolytic copper foil by using the electrolyte, which comprises the following steps: polishing the cathode roller on line, and brushing off partial oxide layer and attached impurities on the surface of the cathode roller; adding a mixed solution of hydroxyethyl cellulose and gelatin; electrolyzing the raw foil to obtain a target product; the electrolytic copper foil obtained by the invention reduces MRz and improves the anti-peeling strength.
Description
Technical Field
The invention relates to the technical field of electrolytic copper foil, in particular to electrolyte for improving the uniformity of M-surface particles of electrolytic copper foil, a production process and a product.
Background
The electrolytic copper foil is formed by separating out copper ions in a copper sulfate electrolytic bath by electrolysis on a circular cathode roll by a special electrolytic machine, and the initial product is a rough foil. The rough foil close to the surface of the cathode roller is the smooth surface of the foil, and is generally called an S surface; the other surface of the matte foil has a crystal structure in an uneven shape, and is the matte surface of the foil, which is generally called an M-surface.
The electrolytic copper foil is one of raw materials for manufacturing a Copper Clad Laminate (CCL) and a Printed Circuit Board (PCB), and is widely used in various electronic information devices including signal base stations, servers, mobile devices, and the like. Along with the updating iteration of electronic products, the production capacity of the domestic electronic circuit copper foil is increased year by year. The manufacturing of the electrolytic copper foil has extremely strict requirements on production equipment, process technology and workshop environment, and product defects such as pinholes, overproof MRz, low peeling strength and the like are easily caused by slight ring joint error.
The residual copper is a problem which is easily encountered in the PCB processing process, and is greatly related to the processing layer structure of the copper foil and the M-surface structure of the raw foil. The M-surface particles of the raw foil of the copper foil are uneven in size and too large in part, so that after surface treatment, the PCB is difficult to completely etch large particles, and residual copper is generated. After the occurrence of the residual copper, the residual copper is concentrated in the dense area of the circuit board, which can cause short circuit of the circuit and seriously affect the quality of the printed circuit board.
Disclosure of Invention
The invention aims to provide the electrolyte for improving the uniformity of M-surface particles of the electrolytic copper foil.
In order to solve the technical problem, the technical scheme of the invention is as follows: an electrolyte for improving the uniformity of particles on the M surface of an electrolytic copper foil comprises copper sulfate, sulfuric acid, pure water and chloride ions, wherein the concentration of the copper ions is 65g/L to 90 g/L; the concentration of the sulfuric acid is 80g/L to 120 g/L; the concentration of the chloride ions is 10mg/L to 30 mg/L;
the concentration of the hydroxyethyl cellulose is 7mg/L to 15 mg/L; the concentration of gelatin is 5mg/L to 10 mg/L.
Preferably, the molecular weight of gelatin is 20000-30000.
Preferably, the hydroxyethyl cellulose and the gelatin are uniformly stirred and mixed in pure water at 40-70 ℃, and the total concentration of the hydroxyethyl cellulose and the gelatin is 10-20 mg/L.
The invention aims to provide a production process for improving the uniformity of M-surface particles of an electrolytic copper foil.
In order to solve the technical problem, the technical scheme of the invention is as follows: the production process for improving the uniformity of the M-surface particles of the electrolytic copper foil by using the electrolyte provided by the invention comprises the following steps:
polishing the cathode roller on line, and brushing off partial oxide layer and attached impurities on the surface of the cathode roller;
adding a mixed solution of hydroxyethyl cellulose and gelatin;
and electrolyzing the raw foil to obtain the target product.
Preferably, the temperature of the supernatant is 40-52 deg.C, and the flow rate of the supernatant is 20m3H to 30m3H is used as the reference value. When the temperature of the upper liquid is lower than 40 ℃, obvious concentration polarization is easy to appear, and mottling appears on the M surface of the copper foil; when the temperature of the upper liquid is higher than 52 ℃, the electrochemical polarization is weaker, and the adsorption effect of the additive is weaker, so that the copper foil has less nucleation, coarse grains and poorer leveling property in the electro-crystallization process, and the situations of higher MRz and more large particles on the M surface appear. When the liquid feeding flow is lower than 20m3The concentration polarization is serious, the M surface of the copper foil has mottling and the basis weight uniformity is poor, and the requirement of 70A/M cannot be met2Production requirements for current density; when the upper liquid flow is higher than 30m3The amount of micro impurities entering the electroplating bath in unit time is increased, and the probability of impurities in a copper foil crystal nucleus is increased in the electrodeposition process, so that the lattice structure of the copper foil is abnormal, and large particles are easily formed.
Preferably, the current density of the electrolytically generated foil is 60A/m2To 80A/m2。
Preferably, the polishing brush is used for online polishing, and the number of the polishing brush is 1200# -2000 #.
Preferably, silicon carbide particles are used as the abrasive particles to be attached to the polishing brush, and the particle diameter of the silicon carbide particles is 15 μm to 50 μm.
Preferably, the rotation speed of the polishing brush for online polishing is 200-250 r/min, the swing speed of the polishing brush is 100-150 r/min, the polishing current is 2.5A, the rotation speed of the cathode roller is 1m/min, and the polishing time is 1-1.5 h. The ratio range of the swing speed to the rotating speed of the linear polishing brush is 1 (0.4-0.75). According to the invention, different polishing conditions and different polishing effects on the roll surface of the cathode roll result in different oxidation degrees of the roll surface of the cathode roll, and the growth uniformity of copper ions in the electrodeposition process can be influenced.
The invention aims to provide an electrolytic copper foil, which is prepared by the method and can improve the uniformity of M-surface particles.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the electrolyte has the advantages of less component variety of used additives, low concentration in the electrolyte, low production cost and convenience for optimizing the concentration of the used additives; the additive slowly changes in the using process and can ensure the stable physical property of the copper foil;
the concentration of chloride ions in the electrolyte is 10-30 mg/L; when the concentration of chloride ions is lower than 10mg/L, the copper foil is easy to have the problems of high warping and pin hole increase, meanwhile, the leveling capability is weak, and the number of large particles on the M surface is large; when the chloride ion is higher than 30mg/L, MRz is easily too high and rapid oxidation of the cathode roller occurs, which is not beneficial to the improvement of yield;
the additive hydroxyethyl cellulose is added into an electrolytic bath, and the concentration of the additive hydroxyethyl cellulose in the electrolyte is 7-15 mg/L. When the concentration of the additive is lower than 7mg/L, the dispersing effect is weaker, and the effect of reducing large particles is poorer; when the concentration of the additive is higher than 15mg/L, the additive has stronger interaction with the gelatin, and the leveling effect of the gelatin is weakened.
The gelatin additive is added into an electrolytic cell, and the concentration of the gelatin additive in the electrolyte is 5-10 mg/L. When the concentration of the additive is lower than 5mg/L, the leveling property is poor, and the number of large particles on the M surface is large; when the concentration of the additive is higher than 10mg/L, the additive components are easily mixed in the plating layer, so that the tensile strength and the elongation of the copper foil are low, the inhibiting effect is weakened, and the leveling property is poor.
2. The electrolytic copper foil is prepared by adopting the electrolyte and the production process, the cathode roller is subjected to online polishing, namely a polishing brush is used for removing partial oxide layers and attached impurities on the surface of the cathode roller, so that the surface lines of the cathode roller are fine, uniform, smooth and clean, the copper foil is favorably and uniformly electrodeposited on the surface of the cathode roller, and the uniformity of M-surface particles and the uniformity of transverse MRz and longitudinal MRz are improved;
3. the copper foil obtained by the invention has high uniformity of M-surface particles and large particle density less than 5/cm2(ii) a MRz is low, and the uniformity of MRz in the transverse direction and the longitudinal direction is high, MRz of 35-micron copper foil is 3.5-4.5 microns, and the deviation of MRz in the transverse direction and the longitudinal direction is less than 5%;
the 35-micron copper foil prepared by the invention has good uniformity of M-surface particles, and the peel strength can reach more than 2.0N/mm after surface treatment.
Thereby achieving the above object of the present invention.
Drawings
FIG. 1 is an SEM photograph of the M-side of an electrodeposited copper foil obtained in example 1 of the present invention;
FIG. 2 is an SEM photograph of the M-side of the electrodeposited copper foil obtained in example 2 of the present invention;
FIG. 3 is an SEM photograph of the M-side of the electrodeposited copper foil obtained in example 3 of the present invention;
FIG. 4 is an SEM photograph of the M-side of the electrolytic copper foil obtained in comparative example 1;
FIG. 5 is an SEM photograph of the M-side of the electrolytic copper foil obtained in comparative example 2;
FIG. 6 is an SEM photograph of the M-side of the electrodeposited copper foil obtained in comparative example 3.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The embodiment discloses an electrolyte for improving the uniformity of M-surface particles of an electrolytic copper foil and a production process thereof, which comprises the following steps,
(1) adding copper wire, sulfuric acid and pure water into a copper dissolving tank, and introducing air to generate copper sulfate electrolyte
(2) Regulating the concentration of copper ions in the electrolyte to be 65g/L and the concentration of sulfuric acid to be 80g/L in a low-level tank; the concentration of the chloride ions in the electrolyte is 10mg/L,
(3) in an additive preparation system, 10g/L additive hydroxyethyl cellulose and 20000-30000 gelatin are prepared at 40 ℃ under heat preservation, are uniformly stirred for 1h and then are continuously added into an electrolytic cell, the concentration of the hydroxyethyl cellulose in the electrolyte is kept to be 7mg/L and the concentration of the gelatin in the electrolyte is kept to be 5mg/L,
(4) regulating the temperature of the upper liquid to 40 ℃ by a plate heat exchanger, and regulating the flow of the upper liquid to 20m by an electromagnetic flowmeter and a ball valve3/h，
(5) And (3) carrying out online polishing on the cathode roller by using a 1200# polishing brush, wherein the rotating speed of the polishing brush is 150 revolutions per minute, the swing speed of the polishing brush is 100 times per minute, the polishing current is 2.5A, the rotating speed of the cathode roller is 1m/min, and the polishing time is 1-1.5 h.
(6) Setting the production current density to 60A/dm2The cathode roller rotation speed was set according to the thickness of 35 μm.
(7) And (4) shooting an SEM after the electrolysis is finished, and performing rough curing and anti-oxidation treatment on the SEM in a surface treatment machine.
The 35 μm green foil prepared in this example, as shown in FIG. 1, was observed to have a uniform particle size under SEM observation and a large particle density of 13 particles/cm2The M-plane roughness Rz was 3.69 μ M, the variation in the transverse direction MRz was 6.3%, and the variation in the longitudinal direction MRz was 5.9%, and after surface treatment, the peel strength was 2.07N/mm.
Example 2
The embodiment discloses an electrolyte production process for improving the uniformity of M-surface particles of an electrolytic copper foil, which comprises the following steps,
(1) the concentration of copper ions in the electrolyte is 80g/L, and the concentration of sulfuric acid is 100 g/L; the concentration of chloride ions in the electrolyte is 20 mg/L;
(2) in an additive preparation system, preparing additive hydroxyethyl cellulose with the concentration of 15g/L and gelatin with the molecular weight of 20000-30000 at the temperature of 55 ℃, uniformly stirring for 1h, and continuously adding into an electrolytic cell, wherein the concentration of the hydroxyethyl cellulose in the electrolyte is 10mg/L, and the concentration of the gelatin in the electrolyte is 8 mg/L;
(3) regulating the temperature of the upper liquid by a plate heat exchanger to be kept at 46 ℃, and regulating the flow of the upper liquid to be 25m by using an electromagnetic flowmeter and a ball valve3/h，
And (3) carrying out online polishing on the cathode roller by using a 1500# polishing brush, wherein the rotating speed of the polishing brush is 200 revolutions per minute, the swing speed of the polishing brush is 125 times per minute, the polishing current is 3.0A, the rotating speed of the cathode roller is 1.5 m/min, and the polishing time is 1-1.5 h.
Setting the production current density to 70A/dm2The cathode roll rotation speed was set according to the thickness of 35 μm
The rest of the procedure was the same as in example 1.
The 35 μm green foil prepared in this example, as shown in FIG. 2, was observed to have a uniform particle size under SEM and a large particle density of 6 particles/cm2The M-plane roughness Rz was 3.34 μ M, the variation in the transverse direction MRz was 2.3%, and the variation in the longitudinal direction MRz was 2.6%, and after surface treatment, the peel strength was 2.19N/M.
Example 3
The embodiment discloses an additive for improving the uniformity of M-surface particles of an electrolytic copper foil and a production process thereof, which comprises the following steps,
(1) the concentration of copper ions in the electrolyte is 90g/L, and the concentration of sulfuric acid is 120 g/L; the concentration of the chloride ions in the electrolyte is 30mg/L,
(2) in an additive preparation system, 20g/L additive hydroxyethyl cellulose and 20000-30000 molecular weight gelatin are prepared at 70 ℃ under heat preservation, the mixture is uniformly stirred for 1h and then continuously added into an electrolytic cell, the concentration of the hydroxyethyl cellulose in the electrolyte is 15mg/L, the concentration of the gelatin in the electrolyte is 10mg/L,
(3) regulating the temperature of the upper liquid to 50 ℃ by a plate heat exchanger, and regulating the flow of the upper liquid to 25m by using an electromagnetic flowmeter and a ball valve3/h，
And (3) carrying out online polishing on the cathode roller by using a 2000# polishing brush, wherein the rotating speed of the polishing brush is 250 revolutions per minute, the swing speed of the polishing brush is 150 times per minute, the polishing current is 3.5A, the rotating speed of the cathode roller is 1.5 m/min, and the polishing time is 1-1.5 h.
Setting the production current density to 70A/dm2According to 35μ m thickness setting cathode roll rotation speed the remaining steps were the same as in example 1.
The prepared 35 mu m green foil has uniform particle size observed under SEM and large particle density of 9 particles/cm2The M-plane roughness Rz was 3.87 μ M, the variation in the transverse direction MRz was 6.1%, the variation in the longitudinal direction MRz was 6.5%, and the peel strength after the surface treatment was 2.15N/M.
Comparative example 1
The production process of the electrolytic copper foil comprises the following steps:
(1) the concentration of copper ions in the electrolyte is 90g/L, and the concentration of sulfuric acid is 120 g/L; the concentration of the chloride ions in the electrolyte is 20mg/L,
(2) in an additive preparation system, 20g/L additive hydroxyethyl cellulose and 20mg/L gelatin with molecular weight of 20000-30000 are prepared at 70 ℃ under the condition of heat preservation, uniformly stirred for 1h and then continuously added into an electrolytic cell, the concentration of the hydroxyethyl cellulose in the electrolyte is 25mg/L, the concentration of the gelatin in the electrolyte is 20mg/L,
(3) regulating the temperature of the upper liquid to 56 ℃ by a plate heat exchanger, and regulating the flow of the upper liquid to 60m by using an electromagnetic flowmeter and a ball valve3/h，
And (3) carrying out online polishing on the cathode roller by using a No. 1000 polishing brush, wherein the rotating speed of the polishing brush is 100 revolutions per minute, the swing speed of the polishing brush is 100 times per minute, the polishing current is 2.0A, the rotating speed of the cathode roller is 1.5 m/min, and the polishing time is 1-1.5 h.
Setting the production current density to 70A/dm2The cathode roll rotation speed was set according to the thickness of 35 μm
The rest of the procedure was the same as in example 1.
The prepared 35 mu m green foil has poor uniformity of particle size observed under SEM and large particle density of 69 particles/cm2The M-plane roughness Rz was 6.29 μ M, the variation in the transverse direction MRz was 12.3%, the variation in the longitudinal direction MRz was 13.8%, and the peel strength after the surface treatment was 1.87N/M.
Comparative example 2
The production process of the electrolytic copper foil comprises the following steps:
(1) the concentration of copper ions in the electrolyte is 60g/L, and the concentration of sulfuric acid is 140 g/L; the concentration of the chloride ions in the electrolyte is 5mg/L,
(2) in an additive preparation system, 10g/L additive hydroxyethyl cellulose and 20000-30000 molecular weight gelatin are prepared at 70 ℃ under heat preservation, the mixture is uniformly stirred for 1h and then continuously added into an electrolytic cell, the concentration of the hydroxyethyl cellulose in the electrolyte is 3mg/L, the concentration of the gelatin in the electrolyte is 2mg/L,
(3) the temperature of the upper liquid is adjusted by a plate heat exchanger to be kept at 38 ℃, and the flow of the upper liquid is adjusted to be 50m by an electromagnetic flowmeter and a ball valve3/h，
And (3) carrying out online polishing on the cathode roller by using a No. 1000 polishing brush, wherein the rotating speed of the polishing brush is 280 revolutions per minute, the swing speed of the polishing brush is 80 times per minute, the polishing current is 3.0A, the rotating speed of the cathode roller is 1.5 m/min, and the polishing time is 1-1.5 h.
Setting the production current density to 60A/dm2The cathode roll rotation speed was set according to the thickness of 35 μm
The rest of the procedure was the same as in example 1.
The prepared 35 mu m green foil has poor uniformity of particle size observed under SEM and large particle density of 41 particles/cm2The M-plane roughness Rz was 5.37 μ M, the variation from MRz in the transverse direction was 13.1%, the variation from MRz in the longitudinal direction was 9.5%, and the peel strength after the surface treatment was 1.76N/M.
Comparative example 3
The production process of the electrolytic copper foil comprises the following steps:
(1) the concentration of copper ions in the electrolyte is 100g/L, and the concentration of sulfuric acid is 120 g/L; the concentration of the chloride ions in the electrolyte is 50 mg/L,
(2) in an additive preparation system, 20g/L additive hydroxyethyl cellulose and 20000-30000 gelatin are prepared at 70 ℃ under heat preservation, and are uniformly stirred for 1h and then are continuously added into an electrolytic cell, wherein the concentration of the hydroxyethyl cellulose in the electrolyte is 20mg/L, the concentration of the gelatin in the electrolyte is 30mg/L,
(3) the temperature of the upper liquid is adjusted by a plate heat exchanger to be kept at 60 ℃, the flow of the upper liquid is adjusted to be 10m3/h by an electromagnetic flowmeter and a ball valve,
and (3) carrying out online polishing on the cathode roller by using a 1500# polishing brush, wherein the rotating speed of the polishing brush is 60 revolutions per minute, the swing speed of the polishing brush is 50 times per minute, the polishing current is 3.7A, the rotating speed of the cathode roller is 1.5 m/min, and the polishing time is 1-1.5 h.
Setting the production current density to 90A/dm2The remaining steps of setting the rotation speed of the cathode roll according to the thickness of 35 μm were the same as in example 1.
The prepared 35-micron green foil has large-area mottle on the M surface, uneven particle size observed under SEM and large particle density of 58 particles/cm2The M-plane roughness Rz was 7.15 μ M, the variation in transverse MRz was 14.1%, the variation in longitudinal MRz was 16.5%, and the peel strength after surface treatment was 2.08N/M.
TABLE 1 Process parameters and properties of electrolytic copper foil obtained in examples 1 to 3 and comparative examples 1 to 3
As can be seen from FIGS. 1 to 6 and Table 1, the uniformity of the particles of examples 1 to 3 of the present invention is superior to that of comparative examples 1 to 3, and the density of large particles on the M-side of the electrodeposited copper foil obtained by the present invention is 15 particles/cm, as compared with comparative examples 1 to 32MRz are all between 3 and 4 mu m, and both the transverse deviation and the longitudinal deviation of MRz are less than 7 percent; after surface treatment, the anti-peeling strength can reach more than 2.0N/mm, the risk of residual copper can be greatly reduced, and the method is very suitable for being used in the PCB with low line loss.
The calculation method of the transverse or longitudinal MRz deviation of the copper foil is as follows:
lateral or longitudinal MRz deviation = (mrz (max) -mrz (min))/mrz (max).
The statistical mode of the large particles in the invention is as follows:
taking 9 samples of the full-width copper foil at the same position at the left, middle and right, taking SEM pictures under 250 times, counting the number of large particles, and converting into 1cm according to the area proportion2The number of large internal particles, normal particle size 13-15 μm, and large particle size 20-26 μm.
MRz has strong relation with the signal transmission of the circuit board, according to the principle of skin effect, the lower the copper foil MRz, the smaller the circuit board DK, Df, and the smaller the loss of signal transmission. The peel strength is closely related to the uniformity of the particle size of the M-side of the green foil, and is also greatly related to the uniformity of MRz, and the more uniform the particle size of the M-side of the green foil is and the smaller the MRz deviation is, the higher and uniform the peel strength of the copper foil after surface treatment is. Generally, MRz and peel strength show a tendency of this trade-off, and it can be seen from table 1 and fig. 1 to 3 that the electrolytic copper foil obtained by the present invention has a reduced MRz and improved peel strength by improving the uniformity of particles on the M-side of the green foil.
Claims (10)
1. The electrolyte for improving the uniformity of the particles on the M surface of the electrolytic copper foil contains copper sulfate, sulfuric acid, pure water and chloride ions, and is characterized in that:
the concentration of copper ions is 65g/L to 90 g/L;
the concentration of the sulfuric acid is 80g/L to 120 g/L;
the concentration of the chloride ions is 10mg/L to 30 mg/L;
the concentration of the hydroxyethyl cellulose is 7mg/L to 15 mg/L;
the concentration of gelatin is 5mg/L to 10 mg/L.
2. The electrolyte for improving the uniformity of particles on the M surface of an electrolytic copper foil according to claim 1, wherein: the molecular weight of gelatin is 20000-30000.
3. The electrolyte for improving the uniformity of particles on the M surface of an electrolytic copper foil according to claim 1, wherein: the hydroxyethyl cellulose and the gelatin are stirred and mixed evenly in pure water at 40 ℃ to 70 ℃, and the total concentration of the hydroxyethyl cellulose and the gelatin is 10g/L to 20 g/L.
4. A production process for improving the uniformity of M-side particles of an electrolytic copper foil by using the electrolyte according to any one of claims 1 to 3, characterized by comprising the following steps:
the method comprises the following steps:
polishing the cathode roller on line, and brushing off partial oxide layer and attached impurities on the surface of the cathode roller;
adding a mixed solution of hydroxyethyl cellulose and gelatin;
and electrolyzing the raw foil to obtain the target product.
5. The production process according to claim 4, wherein: adding the mixture of hydroxyethyl cellulose and gelatin at a temperature of 40-52 deg.C and a flow rate of 20m3H to 30m3/h。
6. The production process according to claim 4, wherein: the current density of the electrolytic green foil is 60A/m2To 80A/m2。
7. The production process according to claim 4, wherein: the polishing brush is used for on-line polishing, and the number of the polishing brush is 1200# -2000 #.
8. The production process according to claim 7, wherein: the abrasive particles attached to the polishing brush are silicon carbide particles having a particle diameter of 15 to 50 μm.
9. The production process according to claim 7, wherein: the rotation speed of a polishing brush for online polishing is 200-250 r/min, the swing speed of the polishing brush is 100-150 r/min, the polishing current is 2.5A, the rotation speed of a cathode roller is 1m/min, and the polishing time is 1-1.5 h.
10. An electrolytic copper foil produced by the production process as claimed in any one of claims 4 to 9.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215646A (en) * | 1992-05-06 | 1993-06-01 | Circuit Foil Usa, Inc. | Low profile copper foil and process and apparatus for making bondable metal foils |
| JP2004035932A (en) * | 2002-07-02 | 2004-02-05 | Mitsui Mining & Smelting Co Ltd | Method of producing electrolytic copper foil |
| US20040104118A1 (en) * | 2002-11-29 | 2004-06-03 | Lg Cable Ltd. | Method for manufacturing very low roughness electrodeposited copper foil and electrodeposited copper foil manufactured thereby |
| KR20050046837A (en) * | 2003-11-14 | 2005-05-19 | 엘에스전선 주식회사 | Very low profile copper foil with high strength and manufacturing method thereof |
| JP2006299320A (en) * | 2005-04-19 | 2006-11-02 | Ls Cable Ltd | High strength low roughness copper foil and method of manufacturing the same |
| CN1995469A (en) * | 2006-11-28 | 2007-07-11 | 招远金宝电子有限公司 | High temperature high ductibility electrolytic copper foil production process |
| RU2006126952A (en) * | 2006-07-24 | 2008-01-27 | Борис Александрович Коновалов (RU) | METHOD FOR PRODUCING COPPER LOW PROFILE FOIL AND LOW PROFILE FOIL OBTAINED USING THIS METHOD |
| CN102181889A (en) * | 2011-04-08 | 2011-09-14 | 联合铜箔(惠州)有限公司 | Additive for electrolytic copper foil, electrolytic copper foil manufacturing process and electrolytic copper foil |
| CN103397352A (en) * | 2013-07-31 | 2013-11-20 | 联合铜箔(惠州)有限公司 | Process for producing lower-outline super-thick electrolytic copper foil with thickness more than or equal to 210 micrometers |
| CN104762642A (en) * | 2015-03-31 | 2015-07-08 | 灵宝华鑫铜箔有限责任公司 | Production process of electrolytic copper foil with low warping degree |
-
2021
- 2021-11-11 CN CN202111334773.XA patent/CN114032586A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215646A (en) * | 1992-05-06 | 1993-06-01 | Circuit Foil Usa, Inc. | Low profile copper foil and process and apparatus for making bondable metal foils |
| JP2004035932A (en) * | 2002-07-02 | 2004-02-05 | Mitsui Mining & Smelting Co Ltd | Method of producing electrolytic copper foil |
| US20040104118A1 (en) * | 2002-11-29 | 2004-06-03 | Lg Cable Ltd. | Method for manufacturing very low roughness electrodeposited copper foil and electrodeposited copper foil manufactured thereby |
| KR20050046837A (en) * | 2003-11-14 | 2005-05-19 | 엘에스전선 주식회사 | Very low profile copper foil with high strength and manufacturing method thereof |
| JP2006299320A (en) * | 2005-04-19 | 2006-11-02 | Ls Cable Ltd | High strength low roughness copper foil and method of manufacturing the same |
| RU2006126952A (en) * | 2006-07-24 | 2008-01-27 | Борис Александрович Коновалов (RU) | METHOD FOR PRODUCING COPPER LOW PROFILE FOIL AND LOW PROFILE FOIL OBTAINED USING THIS METHOD |
| CN1995469A (en) * | 2006-11-28 | 2007-07-11 | 招远金宝电子有限公司 | High temperature high ductibility electrolytic copper foil production process |
| CN102181889A (en) * | 2011-04-08 | 2011-09-14 | 联合铜箔(惠州)有限公司 | Additive for electrolytic copper foil, electrolytic copper foil manufacturing process and electrolytic copper foil |
| CN103397352A (en) * | 2013-07-31 | 2013-11-20 | 联合铜箔(惠州)有限公司 | Process for producing lower-outline super-thick electrolytic copper foil with thickness more than or equal to 210 micrometers |
| CN104762642A (en) * | 2015-03-31 | 2015-07-08 | 灵宝华鑫铜箔有限责任公司 | Production process of electrolytic copper foil with low warping degree |
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