CN106757181B - A kind of preparation method of ultra-thin carrier copper foil - Google Patents
A kind of preparation method of ultra-thin carrier copper foil Download PDFInfo
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- CN106757181B CN106757181B CN201611022020.4A CN201611022020A CN106757181B CN 106757181 B CN106757181 B CN 106757181B CN 201611022020 A CN201611022020 A CN 201611022020A CN 106757181 B CN106757181 B CN 106757181B
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- copper foil
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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
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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
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
- C25D1/22—Separating compounds
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Abstract
The present invention relates to a kind of preparation methods of ultra-thin carrier copper foil, the specific steps are as follows: 1) plating solution is prepared, and complexing agent sodium gluconate, potassium bichromate, additive A and additive B are dissolved in water respectively, mixed after clarification, adjusts solution ph；2) carrier foils are immersed in the organic solution of silane coupling agent, absorption forms one layer of organic film；3) carrier foils are put into the plating solution of step 1), one layer of compound chrome plating of Performances of Novel Nano-Porous meter level is electroplated as peeling layer, 2-5 microns of very thin electrolytic copper foils, referred to as ultra-thin carrier copper foil are then electroplated on the peeling layer.This ultra-thin carrier copper foil through high-temperature laminating, be solidificated in insulating substrate after, carrier foils can be completely exfoliated by mechanical means by removing.The peeling layer of the method preparation is very thin, and uniformly, carrier foils can be made to be easy to complete, stable removing, had a good application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of copper foil more particularly to a kind of preparation methods of ultra-thin carrier copper foil, belong to
The manufacturing technology field of copper foil.
Background technique
As electronic product constantly develops to the direction of miniaturization, multifunction, printed wiring board line width and spacing also to
Miniaturization direction is developed, and this requires slimming copper foils used in fine-line to have higher fissility.Especially in recent years
The extensive use for carrying out lithium ion battery provides broader space to the development of ultra-thin carrier copper foil.
Copper foil is thinner, and preparation is more difficult, during preparation, processing and transport extra thin copper foil, often will appear foldover
Or torn edges problem.Currently, most common solution is electrodeposited in extra thin copper foil above thicker carrier foils, before deposition
Respective handling is done to middle layer, it is ensured that carrier foils separate well with extra thin copper foil.
The removing of carrier foils and extra thin copper foil is a great problem faced now.The organic and inorganic two major classes of middle layer,
Organic middle layer poorly conductive, it may appear that absorption content of organics is few easily peelable, and the absorption more poorly conductives of content of organics are asked
Topic；Inorganic intermediate layer refers mainly to alloy-layer, when composite insulating foil being laminated on ground at high temperature, due to peeling layer to carrier foils and
Extra thin copper foil layer permeates, and adhesion strength is larger, causes to be partially stripped or be difficult between carrier foils and extra thin copper foil to shell
From.This requires seek a kind of method of extra thin copper foil manufacture that can stablize removing.
Summary of the invention
The present invention provides a kind of preparation of ultra-thin carrier copper foil for deficiency present in existing extra thin copper foil preparation process
Method.
The technical scheme to solve the above technical problems is that
A kind of preparation method of ultra-thin carrier copper foil, which comprises the steps of:
1) plating solution is prepared: complexing agent sodium gluconate, potassium bichromate, additive A and additive B are dissolved in water respectively, it is clear
Mixing after clear adjusts pH value and obtains plating solution, and the additive A is one of soluble-salt of Zn, Fe, Ni, Co, In, Mo or more
Kind arbitrary proportion mixture, the additive B be piperidines, hydroxyethyl cellulose, sodium thiosulfate, ethanedioic acid, tartaric acid,
One of ammonium chloride or a variety of mixtures；
2) carrier foils are immersed in the organic solution of silane coupling agent, absorption forms one layer of organic film；
3) carrier foils obtained in step 2) are placed in the resulting plating solution of step 1) as cathode, in being electroplated in carrier foils
One layer of evanohm coating as peeling layer, after the extra thin copper foil of 2~5um is electroplated on the peeling layer；
4) hot pressing, solidification, removing: after the resulting copper foil of step 3) is pressed, is solidificated on insulating substrate, pass through machinery
Carrier foils are removed and are removed by method.
Further, the content of complexing agent sodium gluconate is 70-100g/L in plating solution described in step 1), potassium bichromate
Content is 10-20g/L, and the content of additive A is 5-15g/L, and the content of additive B is 2-10g/L, pH value control for 9.5 ±
1。
Further, the content of silane coupling agent is 1-10g/L in organic solution described in step 2), and carrier foils immerse silicon
Time in alkane coupling agent solution is 20s.
Further, the temperature of plating solution is 40-55 DEG C during step 3) plating peeling layer, electroplating time 5s.
Further, it is carried out at a temperature of 180 DEG C being pressed on described in step 4).
The beneficial effects of the present invention are:
1) a kind of peeling layer of NEW TYPE OF COMPOSITE chrome plating as ultra-thin carrier copper foil is had studied, which is to pass through
Inorganic metal ion and organo-functional group are combined together by the mode of plating, and the difficult removing both not combined as pure metal is asked
Topic, also not as the problem of binding force difference between pure organic matter；The compound peeling layer is extremely thin and uniform, ultra-thin after capable of making pressing
Copper foil is easy to remove with carrier foils completely, steadily.
2) the peeling layer good conductivity, easy to operate and at low cost, the industrial production for subsequent ultra-thin carrier copper foil provides
Theoretical foundation.
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment 1:
A kind of preparation method of ultra-thin carrier copper foil, includes the following steps:
1) plating solution is prepared: complexing agent sodium gluconate, potassium bichromate, additive A and additive B are dissolved in water respectively, it is clear
Mixing after clear adjusts pH value and obtains plating solution, wherein additive A is by Ni (NO3)26H2O and Co (NO3)26H2O 2:1 in mass ratio is mixed
The mixture formed is closed, additive B is the mixture being mixed to form by hydroxyethyl cellulose and tartaric acid 1:2 in mass ratio, Portugal
The content of grape sodium saccharate is 70g/L, and the content of potassium bichromate is 15g/L, and the content of additive A is 15g/L, and additive B contains
Amount is 10g/L, and control pH value is 8.5；
2) carrier copper foil of 35 μ m-thicks is immersed to 20s in the Silane coupling agent KH550 solution of 5g/L, absorption, which forms one layer, to be had
Machine film；
3) carrier foils obtained in step 2) are placed in the resulting plating solution of step 1) as cathode, control bath temperature is
45 DEG C, electroplating time 5s, in one layer of evanohm coating being electroplated in carrier foils as peeling layer, after be electroplated 2 on the peeling layer
The extra thin copper foil of~5um；
4) by the resulting copper foil of step 3) after 180 DEG C of pressings, being solidificated on insulating substrate, by mechanical means by carrier
Foil removing removes.
Embodiment 2:
A kind of preparation method of ultra-thin carrier copper foil, includes the following steps:
1) plating solution is prepared: complexing agent sodium gluconate, potassium bichromate, additive A and additive B are dissolved in water respectively, it is clear
Mixing after clear adjusts pH value and obtains plating solution, wherein additive A is by Zn (NO3)26H2O and In (NO3)33:2 in mass ratio mixes shape
At mixture, additive B is the mixture being mixed to form by piperidines and sodium thiosulfate 3:2 in mass ratio, sodium gluconate
Content be 90g/L, the content of potassium bichromate is 10g/L, and the content of additive A is 5g/L, and the content of additive B is 2g/L,
Controlling pH value is 10.5；
2) carrier copper foil of 40 μ m-thicks is immersed to 20s in the Silane coupling agent KH550 solution of 1g/L, absorption, which forms one layer, to be had
Machine film；
3) carrier foils obtained in step 2) are placed in the resulting plating solution of step 1) as cathode, control bath temperature is
40 DEG C, electroplating time 5s, in one layer of evanohm coating being electroplated in carrier foils as peeling layer, after be electroplated 2 on the peeling layer
The extra thin copper foil of~5um；
4) by the resulting copper foil of step 3) after 180 DEG C of pressings, being solidificated on insulating substrate, by mechanical means by carrier
Foil removing removes.
Embodiment 3:
A kind of preparation method of ultra-thin carrier copper foil, includes the following steps:
1) plating solution is prepared: complexing agent sodium gluconate, potassium bichromate, additive A and additive B are dissolved in water respectively, it is clear
Mixing after clear adjusts pH value and obtains plating solution, wherein additive A is by Mo (NO3)35H2O, additive B are by sodium sulfite and chlorination
The mixture that ammonium 3:1 in mass ratio is mixed to form, the content of sodium gluconate are 100g/L, and the content of potassium bichromate is 20g/L,
The content of additive A is 10g/L, and the content of additive B is 6g/L, and control pH value is 10.5；
2) carrier copper foil of 40 μ m-thicks is immersed to 20s in the Silane coupling agent KH550 solution of 1g/L, absorption, which forms one layer, to be had
Machine film；
3) carrier foils obtained in step 2) are placed in the resulting plating solution of step 1) as cathode, control bath temperature is
55 DEG C, electroplating time 5s, in one layer of evanohm coating being electroplated in carrier foils as peeling layer, after be electroplated 2 on the peeling layer
The extra thin copper foil of~5um；
4) by the resulting copper foil of step 3) after 180 DEG C of pressings, being solidificated on insulating substrate, by mechanical means by carrier
Foil removing removes.
Comparative example 1:
Complexing agent sodium gluconate, potassium bichromate are dissolved in water respectively, mixed after clarification, pH value is adjusted as 8.5 and obtains plating solution,
Wherein, the content of sodium gluconate is 70g/L, and the content of potassium bichromate is 15g/L, after the carrier copper foil of 35 μ m-thicks is placed in institute
Cathode is used as in the plating solution obtained, control bath temperature is 45 DEG C, electroplating time 5s, in one layer of chrome plating work of plating in carrier foils
For peeling layer, after the extra thin copper foil of 2~5um is electroplated on the peeling layer；Resulting copper foil is pressed through 180 DEG C, is solidificated in absolutely
After on edge substrate, carrier foils are removed by mechanical means and are removed.
Comparative example 2:
Complexing agent sodium gluconate, potassium bichromate, additive A are dissolved in water respectively, mixed after clarification, adjusting pH value is
10.5 obtain plating solution, wherein additive A is by Zn (NO3)26H2O and Ni (NO3)26H2The mixing that O 3:2 in mass ratio is mixed to form
Object, the content of sodium gluconate are 90g/L, and the content of potassium bichromate is 10g/L, and the content of additive A is 5g/L, after by 40 μm
Thick carrier copper foil is placed in resulting plating solution as cathode, and control bath temperature is 40 DEG C, electroplating time 5s, in carrier foils
One layer of evanohm coating of upper plating as peeling layer, after the extra thin copper foil of 2~5um is electroplated on the peeling layer；By resulting copper
Carrier foils are removed by mechanical means and are removed after 180 DEG C of pressings, being solidificated on insulating substrate by foil.
Comparative example 3:
Complexing agent sodium gluconate, potassium bichromate, additive B are dissolved in water respectively, mixed after clarification, adjusting pH value is
10.5 plating solution, wherein additive B is the mixture being mixed to form by sodium sulfite and ammonium chloride 3:1 in mass ratio, glucose
The content of sour sodium is 90g/L, and the content of potassium bichromate is 10g/L, and the content of additive B is 6g/L, after by the carrier of 40 μ m-thicks
Copper foil is placed in resulting plating solution as cathode, and control bath temperature is 55 DEG C, electroplating time 5s, in one is electroplated in carrier foils
Layer evanohm coating be used as peeling layer, after on the peeling layer plating 2~5um extra thin copper foil；By resulting copper foil through 180 DEG C
After pressing, being solidificated on insulating substrate, carrier foils are removed by mechanical means and are removed.
Test result is as follows for the stripping performance of embodiment 1-3 and comparative example 1-3:
The stripping performance and electric conductivity test data of table 1 embodiment 1-3 and comparative example 1-3
As can be seen from the above table, the compound evanohm peeling layer prepared through the invention, the extra thin copper foil after pressing can be made
It is easy to remove with carrier foils completely, steadily.The peeling layer is the compound peeling layer that inorganic matter and organic matter form, and nanoscale is super
Thin peeling layer does not influence the electric conductivity, easy to operate and at low cost of carrier foils, is the industrial production of subsequent carrier extra thin copper foil
Theoretical foundation is provided.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of preparation method of ultra-thin carrier copper foil, which comprises the steps of:
1) plating solution is prepared: complexing agent sodium gluconate, potassium bichromate, additive A and additive B being dissolved in water respectively, after clarification
Mixing adjusts pH value and obtains plating solution, and the additive A is one of soluble-salt of Zn, Fe, Ni, Co, In, Mo or a variety of
The mixture of arbitrary proportion, the additive B are piperidines, hydroxyethyl cellulose, sodium thiosulfate, ethanedioic acid, tartaric acid, chlorination
One of ammonium or a variety of mixtures, the content of complexing agent sodium gluconate is 70-100g/L, dichromic acid in the plating solution
The content of potassium is 10-20g/L, and the content of additive A is 5-15g/L, and the content of additive B is 2-10g/L, and pH value control is
9.5±1；
2) carrier foils are immersed in the organic solution of silane coupling agent, absorption forms one layer of organic film；
3) carrier foils obtained in step 2) are placed in the resulting plating solution of step 1) as cathode, in one layer of plating in carrier foils
Evanohm coating as peeling layer, after 2~5 μm of extra thin copper foil is electroplated on the peeling layer；
4) hot pressing, solidification, removing: after the resulting copper foil of step 3) is pressed, is solidificated on insulating substrate, pass through mechanical means
Carrier foils are removed and are removed.
2. the preparation method of ultra-thin carrier copper foil according to claim 1, which is characterized in that organic described in step 2)
The content of silane coupling agent is 1-10g/L in solution, and the time that carrier foils immerse in silane coupler solution is 20s.
3. the preparation method of ultra-thin carrier copper foil according to claim 1 or 2, which is characterized in that step 3) plating removing
The temperature of plating solution is 40-55 DEG C during layer, electroplating time 5s.
4. the preparation method of ultra-thin carrier copper foil according to claim 1 or 2, which is characterized in that described in step 4)
It is carried out at a temperature of being pressed on 180 DEG C.
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| CN201611022020.4A CN106757181B (en) | 2016-11-16 | 2016-11-16 | A kind of preparation method of ultra-thin carrier copper foil |
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| CN201611022020.4A CN106757181B (en) | 2016-11-16 | 2016-11-16 | A kind of preparation method of ultra-thin carrier copper foil |
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| CN106757181B true CN106757181B (en) | 2019-04-16 |
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| CN109881221A (en) * | 2019-03-04 | 2019-06-14 | 深圳市汇美新科技有限公司 | A kind of ultrathin film electroplating technology of high fracture elongation |
| CN109930179A (en) * | 2019-04-01 | 2019-06-25 | 深圳市环基实业有限公司 | A kind of production method and its product of extra thin copper foil |
| CN112853408B (en) * | 2020-12-31 | 2021-11-16 | 江西理工大学 | Preparation method of ultrathin carrier-attached copper foil easy to peel and pure in interface |
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| CN104812944A (en) * | 2012-11-20 | 2015-07-29 | Jx日矿日石金属株式会社 | Copper foil with carrier |
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| CN1276997C (en) * | 2002-05-14 | 2006-09-27 | 三井金属鉱业株式会社 | Method for producing electrolytic copper foil with carrier foil for high-temperature heat resistance and electrolytic copper foil produced by the method |
| CN104812944A (en) * | 2012-11-20 | 2015-07-29 | Jx日矿日石金属株式会社 | Copper foil with carrier |
| CN105018973A (en) * | 2014-11-27 | 2015-11-04 | 太仓市金鹿电镀有限公司 | Environment-friendly electroplating liquid and electroplating process |
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Address after: 265400 No.268, Guoda Road, Zhaoyuan City, Yantai City, Shandong Province Patentee after: Shandong Jinbao Electronics Co.,Ltd. Address before: 265400 No. 128, Wenquan Road, Zhaoyuan, Shandong, Yantai Patentee before: SHANDONG JINBAO ELECTRONICS Co.,Ltd. |