CN103469258A - Additive for ultra-thick electrolytic copper foil, preparation method and application - Google Patents
Additive for ultra-thick electrolytic copper foil, preparation method and application Download PDFInfo
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- CN103469258A CN103469258A CN2013103354164A CN201310335416A CN103469258A CN 103469258 A CN103469258 A CN 103469258A CN 2013103354164 A CN2013103354164 A CN 2013103354164A CN 201310335416 A CN201310335416 A CN 201310335416A CN 103469258 A CN103469258 A CN 103469258A
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Abstract
The invention discloses an additive for an ultra-thick electrolytic copper foil. The additive is prepared by polyethylene glycol, silver sulfate and allyl thiourea, wherein a mass ratio of polyethylene glycol to silver sulfate to allyl thiourea is 0.8-1.2 : 1.0-1.1 : 0.6-1.3. The invention also discloses a preparation method and an application of the additive for the ultra-thick electrolytic copper foil. The additive for the electrolytic copper foil can greatly increase the thickness of a prepared electrolytic copper foil, reduce roughness of a rough surface of the electrolytic copper foil, increase crystalline density of grains and increase tensile strength and anti-peeling strength. The surface roughness of the electrolytic copper foil prepared by the additive is 10-20 [mu]m; the thickness is 150-500 [mu]m; a tensile strength at a room temperature is larger than 30 Kg/mm<2>; and elongation rate at the room temperature is higher than 20%.
Description
Technical field
The present invention relates to electrolytic copper foil and manufacture field, be specifically related to a kind of super thick additive for electrolytic copper foil, preparation method and application for the preparation of the high side circuitry plate.
Background technology
Electrolytic copper foil, as the electronics base mateiral, is mainly used in printed-wiring board (PWB) PCB above, and additive plays very large impact to looks state and the weave construction of electrolytic copper foil.At present the additive for the production of electrolytic copper foil has: 1. inorganic additives, such as the inorganic additives containing arsenic, antimony, for strengthening cathodic polarization and suppressing elasticity, intensity, hardness and the level and smooth sense of metal misgrowth to improve Copper Foil; 2. organic additive, such as hydrolyzed animal protein (gelatin) and PEG, for improving Copper Foil hair side peak valley shape.Gelatin or the PEG elongation under normal temperature or high temperature acutely descends, therefore as the degradation that can cause Copper Foil for printed-wiring board (PWB).Along with the development of electronic industry, the high-density of printed wiring and thin narrow circuit, require Copper Foil that high tensile strength, unit elongation and low roughness are arranged especially now, and the additive of Choice and design specific function is just very important.Additive containing arsenic, antimony is poisonous, environment, human body are harmful to, and this type of metal price is high, certainly will cause the Copper Foil cost high.Therefore, at present, additive is mainly towards environmental protection more, cheap future development.And technology can only be accomplished below 200 microns at present, can not meet the demand of high side circuitry plate.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, a kind of additive that can prepare the thick electrolytic copper foil of excess of export is provided, in particular for producing the electrolytic copper foil of 150～500 μ m, its roughness is low, and unit elongation is high, and tensile strength is high, even thickness.
The present invention realizes that the technical scheme that above-mentioned target adopts is:
A kind of super thick additive for electrolytic copper foil, it is made by polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide, and its mass ratio is: polyoxyethylene glycol 0.8-1.2: Sulfuric acid disilver salt 1.0-1.1: the 0.6-1.3 of propenyl thiocarbamide.
A kind of preparation method of described super thick additive for electrolytic copper foil, it comprises the following steps:
(1) be in mass ratio 0.8-1.2: 1.0-1.1: 0.6-1.3, respectively weighing polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide;
(2) polyoxyethylene glycol, Sulfuric acid disilver salt and the propenyl thiocarbamide of the weighing of step (1) institute are joined in the 3L deionized water;
(3) by step (2) gained mixed solution, be placed under the condition of 40-60 ℃, thermostatically heating, and stir 30-70min, polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide are fully dissolved;
(4) by the prepared solution of step (3), be diluted with water to 37L, just obtain super thick additive for electrolytic copper foil.
According to the application of described super thick additive for electrolytic copper foil, super thick electrolytic copper foil for its circuit card that is 150～500 μ m for the preparation of thickness.
The invention has the beneficial effects as follows: electrolytic copper foil additive provided by the present invention, can greatly increase the thickness of the electrolytic copper foil produced, and can lower the crystal density of electrolytic copper foil hair side roughness, increase crystal grain and increase tensile strength, peel strength; Preparation method provided by the invention, easily control, constant product quality, be easy to mass production; Adopt the electrolytic copper foil surface roughness that additive provided by the invention is prepared to be: 10～20 μ m, thickness is: 150～500 μ m, room temperature tensile strength>30Kg/mm
2, normal temperature unit elongation>20%, be the 2-3 of existing similar additive doubly, there is significant advantage.
Embodiment
Embodiment 1: the super thick additive for electrolytic copper foil that the present embodiment provides, and it is made by polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide, and its mass ratio is: described polyoxyethylene glycol 0.8-1.2: Sulfuric acid disilver salt 1.0-1.1: propenyl thiocarbamide 0.6-1.3.
The preparation method of described super thick additive for electrolytic copper foil, it comprises the following steps:
(1) be in mass ratio 0.8-1.2: 1.0-1.1: 0.6-1.3, respectively weighing polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide;
(2) polyoxyethylene glycol, Sulfuric acid disilver salt and the propenyl thiocarbamide of the weighing of step (1) institute are joined in the 3L deionized water;
(3) by step (2) gained mixed solution, be placed under the condition of 40-60 ℃, thermostatically heating, and stir 30-70min, polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide are fully dissolved;
(4) by the prepared solution of step (3), be diluted with water to 37L, just obtain super thick additive for electrolytic copper foil.
The application of described super thick additive for electrolytic copper foil, super thick electrolytic copper foil for its circuit card that is 150～500 μ m for the preparation of thickness.
Through test, the electrolytic copper foil that the additive that adopts the present embodiment to provide is prepared, have following technical characteristic: surfaceness is: 10～20 μ m, thickness is: 150～500 μ m, room temperature tensile strength>30Kg/mm
2, normal temperature unit elongation>20%, be the 2-3 of existing similar additive doubly, there is significant advantage.
Embodiment 2: super thick additive for electrolytic copper foil, preparation method and application that the present embodiment provides, and its component and step are substantially the same manner as Example 1, and its difference is:
The mass ratio of described polyoxyethylene glycol, Sulfuric acid disilver salt, propenyl thiocarbamide is 1: 1: 1;
A kind of preparation method of described super thick additive for electrolytic copper foil, it comprises the following steps:
(1) be in mass ratio 1: 1: 1, respectively weighing polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide;
(2) polyoxyethylene glycol, Sulfuric acid disilver salt and the propenyl thiocarbamide of the weighing of step (1) institute are joined in the 3L deionized water;
(3) by step (2) gained mixed solution, be placed under the condition of 45 ℃, thermostatically heating, and stir 60min, polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide are fully dissolved;
(4) by the prepared solution of step (3), be diluted with water to 37L, just obtain super thick additive for electrolytic copper foil.
According to the application of described super thick additive for electrolytic copper foil, super thick electrolytic copper foil for its circuit card that is 150 μ m for the preparation of thickness.
Embodiment 3: super thick additive for electrolytic copper foil, preparation method and application that the present embodiment provides, and its component and step and embodiment 1,2 are basic identical, and its difference is:
The mass ratio of described polyoxyethylene glycol, Sulfuric acid disilver salt, propenyl thiocarbamide is 0.8: 1.1: 0.6;
A kind of preparation method of described super thick additive for electrolytic copper foil, it comprises the following steps:
(1) be in mass ratio 0.8: 1.1: 0.6, respectively weighing polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide;
(2) polyoxyethylene glycol, Sulfuric acid disilver salt and the propenyl thiocarbamide of the weighing of step (1) institute are joined in the 3L deionized water;
(3) by step (2) gained mixed solution, be placed under the condition of 60 ℃, thermostatically heating, and stir 30min, polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide are fully dissolved;
(4) by the prepared solution of step (3), be diluted with water to 37L, just obtain super thick additive for electrolytic copper foil.
The application of described super thick additive for electrolytic copper foil, super thick electrolytic copper foil for the circuit card that is 500 μ m for the preparation of thickness.
Embodiment 4: super thick additive for electrolytic copper foil, preparation method and application that the present embodiment provides, and its component and step and embodiment 1,2,3 are basic identical, and its difference is:
The mass ratio of described polyoxyethylene glycol, Sulfuric acid disilver salt, propenyl thiocarbamide is 1.2: 1.05: 1.3;
A kind of preparation method of described super thick additive for electrolytic copper foil, it comprises the following steps:
(1) be in mass ratio 1.2: 1.05: 1.3, respectively weighing polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide;
(2) polyoxyethylene glycol, Sulfuric acid disilver salt and the propenyl thiocarbamide of the weighing of step (1) institute are joined in the 3L deionized water;
(3) by step (2) gained mixed solution, be placed under the condition of 40 ℃, thermostatically heating, and stir 70min, polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide are fully dissolved;
(4) by the prepared solution of step (3), be diluted with water to 37L, just obtain super thick additive for electrolytic copper foil.
The application of described super thick additive for electrolytic copper foil, this super thick additive for electrolytic copper foil, for preparing 150～500 super thick electrolytic copper foils for μ m circuit card.
Embodiment 5: the present embodiment provides a kind of super thick additive for electrolytic copper foil, preparation method and application, and its component and step and embodiment 1,2,3,4 are basic identical, and its difference is:
The mass ratio of described polyoxyethylene glycol, Sulfuric acid disilver salt, propenyl thiocarbamide is 0.9: 1: 0.8;
A kind of preparation method of described super thick additive for electrolytic copper foil, it comprises the following steps:
(1) be in mass ratio 0.9: 1: 0.8, respectively weighing polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide;
(2) polyoxyethylene glycol, Sulfuric acid disilver salt and the propenyl thiocarbamide of the weighing of step (1) institute are joined in the 3L deionized water;
(3) by step (2) gained mixed solution, be placed under the condition of 50 ℃, thermostatically heating, and stir 50min, polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide are fully dissolved;
(4) by the prepared solution of step (3), be diluted with water to 37L, just obtain super thick additive for electrolytic copper foil.
The application of described super thick additive for electrolytic copper foil, super thick electrolytic copper foil for its circuit card for the preparation of thickness 200 μ m.
In other embodiments, the mass ratio of described polyoxyethylene glycol, Sulfuric acid disilver salt, propenyl thiocarbamide, and the thickness of prepared Copper Foil can, according to the record of above-described embodiment, be selected according to specific needs suitable numerical value in its scope.
But the foregoing is only better possible embodiments of the present invention; not in order to limit to the scope of the claims of the present invention; therefore other embodiment of step, component and the application put down in writing in all utilization the present invention, and the equivalence of doing variation, all be included in protection scope of the present invention.
Claims (3)
1. a super thick additive for electrolytic copper foil, is characterized in that, it is made by polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide, and its mass ratio is: polyoxyethylene glycol 0.8-1.2: Sulfuric acid disilver salt 1.0-1.1: the 0.6-1.3 of propenyl thiocarbamide.
2. the preparation method of a super thick additive for electrolytic copper foil claimed in claim 1, is characterized in that, it comprises the following steps:
(1) polyoxyethylene glycol in mass ratio: Sulfuric acid disilver salt: the propenyl thiocarbamide is 0.8-1.2: 1.0-1.1: 0.6-1.3, respectively each component of weighing;
(2) polyoxyethylene glycol, Sulfuric acid disilver salt and the propenyl thiocarbamide of the weighing of step (1) institute are joined in the 3L deionized water;
(3) by step (2) gained mixed solution, be placed under the condition of 40-60 ℃, thermostatically heating, and stir 30-70min, polyoxyethylene glycol, Sulfuric acid disilver salt and propenyl thiocarbamide are fully dissolved;
(4) by the prepared solution of step (3), be diluted with water to 37L, just obtain super thick additive for electrolytic copper foil.
3. the application of super thick additive for electrolytic copper foil according to claim 1, is characterized in that, super thick electrolytic copper foil for its circuit card that is 150～500 μ m for the preparation of thickness.
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| CN201310335416.4A CN103469258B (en) | 2013-08-02 | 2013-08-02 | A kind of super thick additive for electrolytic copper foil, preparation method and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110042438A (en) * | 2019-04-24 | 2019-07-23 | 福建清景铜箔有限公司 | The preparation method of electrolytic copper foil |
| CN111690956A (en) * | 2019-03-14 | 2020-09-22 | 长春石油化学股份有限公司 | Electrolytic copper foil with copper scrap resistance |
| CN112839436A (en) * | 2020-12-30 | 2021-05-25 | 广东嘉元科技股份有限公司 | Electrolytic copper foil for high-frequency high-speed printed circuit board and preparation method thereof |
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| JPH11152593A (en) * | 1997-11-14 | 1999-06-08 | Japan Energy Corp | Electrolytic copper foil containing silver |
| CN1854348A (en) * | 2005-04-25 | 2006-11-01 | 联合铜箔(惠州)有限公司 | 210-400 um superthick electrolytic copper foil, its composite process and apparatus |
| CN101935854A (en) * | 2010-09-20 | 2011-01-05 | 东莞华威铜箔科技有限公司 | Preparation method of additive for electrolytic copper foil, product and application thereof |
| CN102766890A (en) * | 2012-06-29 | 2012-11-07 | 宿迁楚霸体育器械有限公司 | Acid copper brightening agent |
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2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11152593A (en) * | 1997-11-14 | 1999-06-08 | Japan Energy Corp | Electrolytic copper foil containing silver |
| CN1854348A (en) * | 2005-04-25 | 2006-11-01 | 联合铜箔(惠州)有限公司 | 210-400 um superthick electrolytic copper foil, its composite process and apparatus |
| CN101935854A (en) * | 2010-09-20 | 2011-01-05 | 东莞华威铜箔科技有限公司 | Preparation method of additive for electrolytic copper foil, product and application thereof |
| CN102766890A (en) * | 2012-06-29 | 2012-11-07 | 宿迁楚霸体育器械有限公司 | Acid copper brightening agent |
Non-Patent Citations (1)
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| 易光斌: ""电解铜箔添加剂配方优化"", 《电镀与涂饰》, vol. 29, no. 11, 30 November 2010 (2010-11-30), pages 26 - 28 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690956A (en) * | 2019-03-14 | 2020-09-22 | 长春石油化学股份有限公司 | Electrolytic copper foil with copper scrap resistance |
| CN111690956B (en) * | 2019-03-14 | 2022-05-10 | 长春石油化学股份有限公司 | Electrolytic copper foil with copper scrap resistance |
| CN110042438A (en) * | 2019-04-24 | 2019-07-23 | 福建清景铜箔有限公司 | The preparation method of electrolytic copper foil |
| CN110042438B (en) * | 2019-04-24 | 2021-02-05 | 福建清景铜箔有限公司 | Method for preparing electrolytic copper foil |
| CN112839436A (en) * | 2020-12-30 | 2021-05-25 | 广东嘉元科技股份有限公司 | Electrolytic copper foil for high-frequency high-speed printed circuit board and preparation method thereof |
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| CN103469258B (en) | 2016-01-06 |
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Effective date of registration: 20221124 Address after: No. 118, Rixin Road, Xuancheng economic and Technological Development Zone, Xuancheng City, Anhui Province Patentee after: ANHUI HUAWEI COPPER FOIL TECHNOLOGY CO.,LTD. Address before: 523,000 Ma Ti Gang Second Industrial Zone, Dalingshan Town, Dongguan City, Guangdong Province Patentee before: DONGGUAN WAHWEI COPPER FOIL TECHNOLOGY Co.,Ltd. |
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