CN108330517B - Plating solution for stripping layer of carrier copper foil and preparation method of stripping layer - Google Patents
Plating solution for stripping layer of carrier copper foil and preparation method of stripping layer Download PDFInfo
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- CN108330517B CN108330517B CN201810072176.6A CN201810072176A CN108330517B CN 108330517 B CN108330517 B CN 108330517B CN 201810072176 A CN201810072176 A CN 201810072176A CN 108330517 B CN108330517 B CN 108330517B
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- stripping layer
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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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- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a plating solution of a carrier copper foil stripping layer and a preparation method of the stripping layer, wherein the plating solution comprises the following components: 20-60 g/L potassium hydrogen tartrate, 8-16 g/L zinc sulfate, 5-20 g/L additive A and 3.0-5.0 pH, wherein the additive A is a mixture prepared by mixing at least one of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltriethoxysilane, 3- (2, 3-glycidoxy) propylmethoxydiethoxysilane or 3- (methacryloyloxy) propyltrimethoxysilane and at least one of potassium thiocyanate, potassium dihydrogen phosphate, sodium acetate or ammonium sulfate according to any proportion. The carrier copper foil stripping layer obtained by adopting the stripping layer plating solution and the stripping layer preparation method provided by the invention is a novel nano-scale composite zinc plating layer, the stripping layer is extremely thin and uniform, and the extremely thin copper foil after pressing can be completely and stably stripped from the carrier foil.
Description
Technical Field
The invention relates to a plating solution for a stripping layer of a carrier copper foil and a preparation method of the stripping layer, belonging to the technical field of preparation of electrolytic copper foils.
Background
With the development of electronic products in the light, thin, short, small, multifunctional and high-added-value directions, the development of high-density interconnection printed circuit boards (HDI PCBs) is promoted, about 90% of mobile phones in the market currently adopt the HDI PCBs as bottom plates, and the main condition for manufacturing the HDI PCBs is that ultrathin electrolytic copper foils are adopted. The thinner the copper foil, the more difficult it is to produce and the more easily it wrinkles and tears during transport. Therefore, the production technology of the extra thin copper foil will become a hot spot for future research.
Currently, the method for preparing the extra thin copper foil is to adopt 18 or 35 micron double-photoelectrolysis copper foil as a carrier foil, firstly form a stripping layer on the carrier foil, and then deposit 2 to 6 micron extra thin copper foil. The electrodeposited extra thin copper foil is thermally pressed and cured on the insulating substrate together with the carrier foil, and the carrier foil is peeled off and removed by a mechanical method.
In the production of an extra thin copper foil, a peeling layer is very important and the peeling layer is mainly classified into: inorganic release layer, organic release layer and composite release layer; the inorganic stripping layer is mainly a metal layer or an alloy layer, and the stripping layer has good conductivity but is difficult to strip; the organic stripping layer is a nitrogen-containing compound, a sulfur-containing compound, carboxylic acid and the like, and Benzotriazole (BTA), Carboxyl Benzotriazole (CBTA) and the like are commonly used, and the stripping layer has the defects of poor conductivity, uneven stripping caused by uneven adsorption of organic matters, easy stripping in some places, difficult stripping in some places and the like. Although many studies have been made, no release layer capable of completely stably releasing has been developed yet.
Disclosure of Invention
The invention provides a plating solution for a stripping layer of a carrier copper foil and a preparation method of the stripping layer, aiming at the defects of the stripping layer in the production process of the existing ultrathin electrolytic copper foil.
The technical scheme for solving the technical problems is as follows:
a plating solution for a stripping layer of a carrier copper foil comprises the following components: 20-60 g/L of potassium hydrogen tartrate, 8-16 g/L of zinc sulfate, 5-20 g/L of an additive A, and the pH value of the additive A is 3.0-5.0, wherein the additive A is a mixture obtained by mixing at least one of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 3- (2, 3-epoxypropoxy) propylmethoxydiethoxysilane or 3- (methacryloyloxy) propyltrimethoxysilane and at least one of potassium thiocyanate, potassium dihydrogen phosphate, sodium acetate or ammonium sulfate according to any proportion.
Further, the paint comprises the following components: 40g/L of potassium hydrogen tartrate, 12g/L of zinc sulfate, 12g/L of additive A12g/L, and the pH value of the additive A is 3.8-4.2.
The method for preparing the carrier copper foil stripping layer by adopting the plating solution of the stripping layer comprises the following steps:
1) preparing a plating solution: respectively dissolving potassium hydrogen tartrate, zinc sulfate and an additive A in water, clarifying and mixing, and controlling the content of each substance in the plating solution as follows: 20-60 g/L of potassium hydrogen tartrate, 8-16 g/L of zinc sulfate, 5-20 g/L of an additive A, and the pH value of a plating solution is 3.0-5.0, wherein the additive A is a mixture obtained by mixing at least one of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 3- (2, 3-epoxypropoxy) propylmethoxydiethoxysilane or 3- (methacryloyloxy) propyltrimethoxysilane and at least one of potassium thiocyanate, potassium dihydrogen phosphate, sodium acetate or ammonium sulfate according to any proportion;
2) electroplating a stripping layer: controlling the temperature of the plating solution to be 25-45 ℃, then placing the carrier copper foil into the plating solution obtained in the step 1), and plating a nano-scale composite zinc plating layer on the carrier copper foil, namely the stripping layer.
After the stripping layer is electroplated on the carrier copper foil by adopting the method, a layer of 2-6 micron ultrathin copper foil is electroplated and deposited, the ultrathin copper foil and the carrier copper foil are hot-pressed and solidified on the insulating substrate, and the carrier copper foil is stripped and removed by a mechanical method to obtain the 2-6 micron ultrathin electrolytic copper foil.
The invention has the beneficial effects that:
1) the carrier copper foil stripping layer obtained by adopting the stripping layer plating solution and the stripping layer preparation method provided by the invention is a novel nano-scale composite zinc plating layer, the stripping layer is extremely thin and uniform, and the extremely thin copper foil after pressing can be completely and stably stripped from the carrier foil;
2) the stripping layer has good conductivity, integrates the advantages of an inorganic stripping layer and an organic stripping layer, has simple operation and low cost, and provides a theoretical basis for the subsequent industrial production of the carrier ultrathin copper foil.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
a plating solution for a stripping layer of a carrier copper foil comprises the following components: the content of potassium hydrogen tartrate is 40g/L, the content of zinc sulfate is 12g/L, the content of additive A is 12g/L, and the mass ratio of additive A to 3- (methacryloyloxy) propyl trimethoxy silane to potassium thiocyanate to potassium dihydrogen phosphate is 1: 5: 5, and the pH value is 3.8-4.2.
The method for preparing the carrier copper foil stripping layer by using the plating solution comprises the following steps: controlling the temperature of the plating solution to be 35 ℃, then placing the carrier copper foil into the plating solution, and electroplating a novel nano-scale composite zinc plating layer as a stripping layer under the action of direct current with the voltage of 20V and the current of 5A for 3s to obtain the stripping layer.
Example 2:
a plating solution for a stripping layer of a carrier copper foil comprises the following components: the content of potassium hydrogen tartrate is 60g/L, the content of zinc sulfate is 16g/L, the content of additive A is 20g/L, and the additive A is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl triethoxy silane and sodium acetate according to the mass ratio of 2: 2: 8, and the pH value is 3.0-3.6.
The method for preparing the carrier copper foil stripping layer by using the plating solution comprises the following steps: controlling the temperature of the plating solution to be 25 ℃, then putting the carrier copper foil into the plating solution, and electroplating a novel nano-scale composite zinc plating layer as a stripping layer under the action of direct current with the voltage of 20V and the current of 5A for 3s to obtain the stripping layer.
Example 3:
a plating solution for a stripping layer of a carrier copper foil comprises the following components: the content of potassium hydrogen tartrate is 20g/L, the content of zinc sulfate is 8g/L, the content of additive A is 5g/L, and the additive A is 3- (2, 3-epoxypropoxy) propyl methoxy diethoxysilane, 3- (methacryloyloxy) propyl trimethoxy silane, sodium acetate and ammonium sulfate according to the mass ratio of 1: 1: 3: 5, and the pH value is 4.5-5.0.
The method for preparing the carrier copper foil stripping layer by using the plating solution comprises the following steps: controlling the temperature of the plating solution to be 45 ℃, then putting the carrier copper foil into the plating solution, and electroplating a novel nano-scale composite zinc plating layer as a stripping layer under the action of direct current with the voltage of 20V and the current of 5A for 5s to obtain the stripping layer.
Comparative example:
the plating solution of the carrier copper foil stripping layer comprises the following components: the content of potassium hydrogen tartrate is 40g/L, the content of zinc sulfate is 12g/L, the pH value of the solution is 3.8-4.2, and the pH value is 3.8-4.2.
Controlling the temperature of the plating solution to be 35 ℃, then placing the carrier copper foil into the plating solution, and electroplating a layer of nano-composite zinc plating layer as a stripping layer under the action of direct current with the voltage of 20V and the current of 5A for 3s to obtain the stripping layer.
To verify the technical effects of the stripping layer plating solution and the stripping layer preparation method provided by the present invention, an ultrathin electrolytic copper foil of 2 to 6 μm was electroplated on the stripping layers obtained in examples 1 to 3 and comparative examples. Then, the extra thin carrier copper foil was laminated and cured on the insulating substrate at a high temperature of 180 ℃ to see whether the carrier copper foil could be completely peeled off by a mechanical method, and the test results are shown in table 1.
TABLE 1 Peel Properties of examples 1-3 and comparative examples
As can be seen from Table 1, the nano-composite zinc stripping layer prepared by the method can ensure that the extremely thin copper foil after being pressed can be easily and completely and stably stripped from the carrier foil. The stripping layer is a composite stripping layer consisting of inorganic matters and organic matters; the stripping layer is extremely thin and uniform, has good conductivity, simple operation and low cost, and provides a theoretical basis for the subsequent industrial production of the carrier extremely thin copper foil.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. The plating solution for the stripping layer of the carrier copper foil is characterized by comprising the following components:
20-60 g/L of potassium hydrogen tartrate, 8-16 g/L of zinc sulfate, 5-20 g/L of an additive A, and the pH value of the additive A is 3.0-5.0, wherein the additive A is a mixture obtained by mixing at least one of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 3- (2, 3-epoxypropoxy) propylmethoxydiethoxysilane or 3- (methacryloyloxy) propyltrimethoxysilane and at least one of potassium thiocyanate, potassium dihydrogen phosphate, sodium acetate or ammonium sulfate according to any proportion.
2. The plating solution of claim 1, comprising the following components: 40g/L of potassium hydrogen tartrate, 12g/L of zinc sulfate, 12g/L of additive A, and the pH value of the additive A is 3.8-4.2.
3. A preparation method of a carrier copper foil stripping layer is characterized by comprising the following steps:
1) preparing a plating solution: respectively dissolving potassium hydrogen tartrate, zinc sulfate and an additive A in water, clarifying and mixing, and controlling the content of each substance in the plating solution as follows: 20-60 g/L of potassium hydrogen tartrate, 8-16 g/L of zinc sulfate, 5-20 g/L of an additive A, and the pH value of a plating solution is 3.0-5.0, wherein the additive A is a mixture obtained by mixing at least one of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 3- (2, 3-epoxypropoxy) propylmethoxydiethoxysilane or 3- (methacryloyloxy) propyltrimethoxysilane and at least one of potassium thiocyanate, potassium dihydrogen phosphate, sodium acetate or ammonium sulfate according to any proportion;
2) electroplating a stripping layer: controlling the temperature of the plating solution to be 25-45 ℃, then placing the carrier copper foil into the plating solution obtained in the step 1), and plating a nano-scale composite zinc plating layer on the carrier copper foil, namely the stripping layer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810072176.6A CN108330517B (en) | 2018-01-25 | 2018-01-25 | Plating solution for stripping layer of carrier copper foil and preparation method of stripping layer |
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| CN201810072176.6A CN108330517B (en) | 2018-01-25 | 2018-01-25 | Plating solution for stripping layer of carrier copper foil and preparation method of stripping layer |
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| CN108330517A CN108330517A (en) | 2018-07-27 |
| CN108330517B true CN108330517B (en) | 2019-12-24 |
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| CN112226790B (en) * | 2020-10-19 | 2022-04-22 | 九江德福科技股份有限公司 | Production method of ultrathin high-strength electronic copper foil |
| CN112795964B (en) * | 2020-12-07 | 2021-11-19 | 安徽铜冠铜箔集团股份有限公司 | Ultrathin strippable composite copper foil and preparation method thereof |
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| CN101906630A (en) * | 2010-08-03 | 2010-12-08 | 山东金宝电子股份有限公司 | Black surface treatment process of electrolytic copper foil |
| CN104099061A (en) * | 2014-07-09 | 2014-10-15 | 山东金宝电子股份有限公司 | Preparation method of electrolytic copper foil surface treating agent |
| CN104943273A (en) * | 2014-03-26 | 2015-09-30 | Jx日矿日石金属株式会社 | Lamination body formed by platelike carrier made of resin and metal layer |
| CN106257969A (en) * | 2015-06-17 | 2016-12-28 | Ｊｘ金属株式会社 | The Copper Foil of appendix body, laminate, the manufacture method of printed wiring board and the manufacture method of e-machine |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG101924A1 (en) * | 1998-10-19 | 2004-02-27 | Mitsui Mining & Smelting Co | Composite material used in making printed wiring boards |
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| CN101906630A (en) * | 2010-08-03 | 2010-12-08 | 山东金宝电子股份有限公司 | Black surface treatment process of electrolytic copper foil |
| CN104943273A (en) * | 2014-03-26 | 2015-09-30 | Jx日矿日石金属株式会社 | Lamination body formed by platelike carrier made of resin and metal layer |
| CN104099061A (en) * | 2014-07-09 | 2014-10-15 | 山东金宝电子股份有限公司 | Preparation method of electrolytic copper foil surface treating agent |
| CN106257969A (en) * | 2015-06-17 | 2016-12-28 | Ｊｘ金属株式会社 | The Copper Foil of appendix body, laminate, the manufacture method of printed wiring board and the manufacture method of e-machine |
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