Additive for electrolytic copper foil
By using a combination of brightener, dispersing additive and inhibitor in electrolytic copper foil additives, the apparent improvement agent is prepared, which solves the problems of high internal stress and rough surface of electrolytic copper foil, and achieves the low warpage of electrolytic copper foil , uniform thickness and delicate surface effects improve the quality and grade of electrolytic copper foil.
Patent Information
- Application Number
- CN202411284609.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-13
- Publication Date
- 2024-12-10
AI Technical Summary
Existing electrolytic copper foil additives cannot effectively reduce the internal stress of electrolytic copper foil, resulting in problems such as large warpage, uneven thickness, tear edges and rough surfaces.
Using an additive for electrolytic copper foil consisting of brighteners, dispersing additives, inhibitors and apparent improvement agents, through sodium polydithiodipropane sulfonate, sodium alcohol thiopropane sulfonate, sodium phenyldithiopropane sulfonate The combination of brighteners and dispersion additives such as polyethylene glycol and collagen and inhibitors is combined with specific preparation methods to prepare apparent improvement agents to reduce the internal stress of electrolytic copper foil and improve its surface gloss and thickness uniformity.
Effectively reduce the internal stress of electrolytic copper foil, reduce warpage, ensure thickness uniformity and tear-free edges, improve surface fineness, and improve the quality and grade of electrolytic copper foil.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of electrolytic copper foil, in particular to an additive for electrolytic copper foil. Background Art
[0002] Electrolytic copper foil is formed by the copper ions in the electrolyte deposited on the smooth rotating stainless steel plate (or titanium plate) circular cathode roller. The side of the copper foil close to the cathode roller is called the smooth side, and the other side is called the rough side. Electrolytic copper foil was first used in the construction field. In my country, electrolytic copper foil is the main material for producing copper clad laminates, which are the main materials for making printed circuit boards. Electrolytic copper foil is still the best conductive material for printed circuit boards. Furthermore, electrolytic copper foil can also be used in the fields of shielding of cables and military facilities, conductive busbars for flexible connections, gaskets in the machinery industry, furniture decoration, and polar materials for lithium-ion batteries.
[0003] In the preparation process of electrolytic copper foil, the use of additives plays a vital role in the performance of copper foil. The patent document with application number "CN201310335416.4" discloses an additive for ultra-thick electrolytic copper foil, a preparation method and an application. The electrolytic copper foil additive provided in this patent document can greatly increase the thickness of the manufactured electrolytic copper foil and enhance its mechanical properties (tensile strength, peel strength). However, it cannot effectively reduce the internal stress of the electrolytic copper foil, which makes its warping larger. Furthermore, the electrolytic copper foil product prepared by it has defects such as uneven thickness, torn edges and rough surface. These factors seriously affect the quality and grade of the electrolytic copper foil. Based on this, the present invention provides an additive for electrolytic copper foil to solve the above-mentioned technical problems! Summary of the invention
[0004] The purpose of the present invention is to provide an additive for electrolytic copper foil. The surface improving agent prepared by the present invention can not only effectively improve the stacking phenomenon of copper ions, making the surface of the electrolytic copper foil product more delicate and lustrous, but also effectively reduce the internal stress of the electrolytic copper foil. The surface improving agent used as an important raw material for the additive for electrolytic copper foil can effectively reduce the internal stress of the electrolytic copper foil, thereby obtaining an electrolytic copper foil product with low warping, uniform thickness, no tearing and delicate surface, which effectively guarantees its quality and grade.
[0005] To achieve the above object, the present invention provides the following technical solutions:
[0006] An additive for electrolytic copper foil, the additive for electrolytic copper foil is composed of a brightener, a dispersing aid, an inhibitor and an appearance improver; and the weight ratio of the brightener, the dispersing aid, the inhibitor and the appearance improver is 1:3-5:20-30:2-3.
[0007] Furthermore, the brightener is selected from any one of sodium polydisulfide propane sulfonate, sodium alcoholthiopropane sulfonate, and sodium phenyldisulfide propane sulfonate.
[0008] Furthermore, the inhibitor is collagen, and the weight average molecular weight of the collagen is 6000-10000 g / mol.
[0009] Furthermore, the dispersing aid is polyethylene glycol, and the weight average molecular weight of the polyethylene glycol is 8000-12000 g / mol.
[0010] Furthermore, the preparation method of the surface improving agent comprises the following steps:
[0011] Step 1, adding organic ether to deionized water at a dosage ratio of 0.5 to 1.0 mol / L, and adding 1,3-benzodiazepine in a molar amount of 0.6 to 0.8 times that of the organic ether, mixing and stirring evenly, adding a reaction accelerator in an amount of 1.2 to 1.5% of the organic ether to the resulting mixture, heating to 50 to 70° C. after mechanical stirring evenly, and keeping the reaction at this temperature for 3 to 5 hours;
[0012] Step 2: After the reaction is completed, add hexahydropyridine in a molar amount of 0.7 to 0.9 times that of 1,3-benzodiazepine to the mixture obtained in step 1, mix and stir evenly, raise the temperature to 60 to 75° C., and keep the reaction at this temperature for 5 to 6 hours;
[0013] Step 3: After the reaction is completed, the product components obtained in step 2 are filtered and washed, and then the reaction product obtained after washing is mixed with deionized water of 4 to 6 times its mass, and the modifier is added after mechanical stirring to completely dissolve it. After mixing evenly, the mixture is kept warm at a temperature of 50 to 80°C for 20 to 40 hours. After the reaction is completed, the product components are naturally cooled to room temperature, aged for 5 to 8 hours, and then filtered and washed in turn to obtain the surface improvement agent.
[0014] Furthermore, the organic ether is selected from any one of 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether.
[0015] Furthermore, the preparation method of the reaction promoter is as follows: methylimidazole and butyl bromide are added into a reactor equipped with a reflux condenser at a volume ratio of 1:1.5 to 2.0, and a calcium chloride drying tube is installed on the reflux condenser; after mixing and stirring evenly, the mixture is stirred and reacted at a temperature of 65 to 85°C for 20 to 30 hours. After the reaction is completed, the product is naturally cooled to room temperature, and then transferred to an extraction device, and washed with ethyl acetate 2 to 3 times and then rotary evaporated to remove the ethyl acetate therein; then vacuum dried at a temperature of 60 to 70°C to constant weight; after drying is completed, a saturated aqueous solution of sodium hexafluorophosphate is slowly added thereto, stirred at room temperature for 10 to 15 hours, and then allowed to stand for 10 to 20 minutes, and then the lower organic phase is washed with deionized water until no bromine is detected in the washing liquid, and then vacuum dried to remove residual water to obtain the reaction promoter.
[0016] Furthermore, the modifier is selected from any one of methyl chloride and methyl iodide.
[0017] Furthermore, the sodium hexafluorophosphate and methylimidazole are used in equimolar amounts.
[0018] Compared with the prior art, the present invention has the following beneficial effects:
[0019] In the present invention, methylimidazole and butyl bromide are mixed evenly and then stirred and reacted under heat preservation. After the reaction is completed, the product is washed with ethyl acetate, and then subjected to rotary evaporation and vacuum drying. Then, a saturated aqueous solution of sodium hexafluorophosphate is slowly added to the remaining product, and the product is washed and dried under vacuum after chemical reaction to obtain a reaction accelerator. In addition, an organic ether is added to deionized water and then 1,3-benzodiazepine is added. After mixing and stirring evenly, a reaction accelerator is added to the obtained mixed solution. After heat preservation reaction, hexahydropyridine is added to the obtained mixture. Finally, 1,3-benzodiazepine and methylimidazole react chemically with the organic ether. After the obtained product components are filtered and washed, a modifier is added. After heat preservation reaction, aging, filtering and washing, a surface improvement agent is obtained. The prepared surface improver can not only effectively improve the stacking phenomenon of copper ions, making the surface of the electrolytic copper foil product more delicate and shiny, but also effectively reduce the internal stress of the electrolytic copper foil. It is used as an important raw material for additives for electrolytic copper foil, which can effectively reduce the internal stress of the electrolytic copper foil and obtain electrolytic copper foil products with low warpage. Furthermore, the surface improver and the brightener cooperate with each other, so that the prepared electrolytic copper foil has the advantages of uniform thickness, no tearing, and delicate surface, which effectively guarantees its quality and grade. DETAILED DESCRIPTION
[0020] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0021] Example 1
[0022] An additive for electrolytic copper foil, the additive for electrolytic copper foil is composed of sodium polydipropane sulfonate, a dispersing aid, an inhibitor and a surface improver; and the weight ratio of sodium polydipropane sulfonate, the dispersing aid, the inhibitor and the surface improver is 1:3:20:2; wherein,
[0023] The inhibitor is collagen, and the weight average molecular weight of the collagen is 6000 g / mol.
[0024] The dispersing aid is polyethylene glycol, and the weight average molecular weight of the polyethylene glycol is 8000 g / mol.
[0025] The preparation method of the surface improving agent comprises the following steps:
[0026] Step 1: Add 1,4-butanediol diglycidyl ether to deionized water at a dosage ratio of 0.5 mol / L, and add 1,3-benzodiazepine in a molar amount of 0.6 times that of 1,4-butanediol diglycidyl ether. After mixing and stirring evenly, add a reaction accelerator in an amount of 1.2% by mass to the resulting mixture. After mechanical stirring and uniformity, heat to 50° C. and keep the mixture at this temperature for 3 hours.
[0027] Step 2: After the reaction is completed, add hexahydropyridine in a molar amount of 0.7 times that of 1,3-benzodiazepine to the mixture obtained in step 1, mix and stir evenly, raise the temperature to 60° C., and keep the reaction at this temperature for 5 hours;
[0028] Step 3: After the reaction is completed, the product components obtained in step 2 are filtered and washed, and then the reaction product obtained after washing is mixed with deionized water of 4 times its mass, and after mechanical stirring to completely dissolve it, chlorobenzene is added, and after mixing evenly, the mixture is kept warm at 50°C for 20 hours. After the reaction is completed, the product components are naturally cooled to room temperature, aged for 5 hours, and then filtered and washed in turn to obtain a surface improvement agent.
[0029] The preparation method of the reaction accelerator is as follows: methylimidazole and butyl bromide are added into a reactor equipped with a reflux condenser at a volume ratio of 1:1.5, and a calcium chloride drying tube is installed on the reflux condenser; after mixing and stirring evenly, the mixture is stirred and reacted at a temperature of 65°C for 20 hours, and after the reaction is completed, the product is naturally cooled to room temperature, and then transferred to an extraction device, and washed with ethyl acetate twice and then rotary evaporated to remove the ethyl acetate therein; then vacuum dried at a temperature of 60°C to constant weight; after drying is completed, a saturated aqueous solution of sodium hexafluorophosphate is slowly added thereto, stirred at room temperature for 10 hours and then allowed to stand for 10 minutes, and then the lower organic phase is washed with deionized water until no bromine is detected in the washing liquid, and then the residual water is removed by vacuum drying to obtain the reaction accelerator; wherein, the sodium hexafluorophosphate and methylimidazole are used in equimolar amounts.
[0030] Example 2
[0031] An additive for electrolytic copper foil, the additive for electrolytic copper foil is composed of sodium thiopropane sulfonate, a dispersing aid, an inhibitor and an appearance improver; and the weight ratio of sodium thiopropane sulfonate, the dispersing aid, the inhibitor and the appearance improver is 1:4:25:2.5; wherein,
[0032] The inhibitor is collagen, and the weight average molecular weight of the collagen is 8000 g / mol.
[0033] The dispersing aid is polyethylene glycol, and the weight average molecular weight of the polyethylene glycol is 10000 g / mol.
[0034] The preparation method of the surface improving agent comprises the following steps:
[0035] Step 1, add 1,6-hexanediol diglycidyl ether to deionized water at a dosage ratio of 0.8 mol / L, and add 1,3-benzodiazepine with a molar amount of 0.7 times that of 1,6-hexanediol diglycidyl ether, mix and stir evenly, add 1.3% of the reaction accelerator to the resulting mixture, heat to 60°C after mechanical stirring, and keep the reaction at this temperature for 4 hours;
[0036] Step 2: After the reaction is completed, add hexahydropyridine in a molar amount of 0.8 times that of 1,3-benzodiazepine to the mixture obtained in step 1, mix and stir evenly, raise the temperature to 70° C., and keep the reaction at this temperature for 6 hours;
[0037] Step 3: After the reaction is completed, the product components obtained in step 2 are filtered and washed, and then the reaction product obtained after washing is mixed with deionized water of 5 times its mass, mechanically stirred to make it completely dissolved, and then methyl iodide is added. After mixing evenly, the mixture is kept warm at 60°C for 30 hours. After the reaction is completed, the product components are naturally cooled to room temperature, aged for 6 hours, and then filtered and washed in turn to obtain the surface improving agent.
[0038] The preparation method of the reaction accelerator is as follows: methylimidazole and butyl bromide are added into a reactor equipped with a reflux condenser at a volume ratio of 1:2.0, and a calcium chloride drying tube is installed on the reflux condenser; after mixing and stirring evenly, the mixture is stirred and reacted at a temperature of 75°C for 25 hours, and after the reaction is completed, the product is naturally cooled to room temperature, and then transferred to an extraction device, and washed with ethyl acetate for 3 times and then rotary evaporated to remove the ethyl acetate therein; and then vacuum dried at a temperature of 65°C to constant weight; after drying is completed, a saturated aqueous solution of sodium hexafluorophosphate is slowly added thereto, stirred at room temperature for 12 hours, and then allowed to stand for 15 minutes, and then the lower organic phase is washed with deionized water until no bromine is detected in the washing liquid, and then the residual water is removed by vacuum drying to obtain the reaction accelerator; wherein, the sodium hexafluorophosphate and methylimidazole are used in equimolar amounts.
[0039] Example 3
[0040] An additive for electrolytic copper foil, the additive for electrolytic copper foil is composed of sodium phenyl disulfide propane sulfonate, a dispersing aid, an inhibitor and a surface improver; and the weight ratio of sodium phenyl disulfide propane sulfonate, the dispersing aid, the inhibitor and the surface improver is 1:5:30:3; wherein,
[0041] The inhibitor is collagen, and the weight average molecular weight of the collagen is 10000 g / mol.
[0042] The dispersing aid is polyethylene glycol, and the weight average molecular weight of the polyethylene glycol is 12000 g / mol.
[0043] The preparation method of the surface improving agent comprises the following steps:
[0044] Step 1: Add 1,4-butanediol diglycidyl ether to deionized water at a dosage ratio of 1.0 mol / L, and add 1,3-benzodiazepine in a molar amount of 0.8 times that of 1,4-butanediol diglycidyl ether. After mixing and stirring evenly, add a reaction accelerator in an amount of 1.5% by mass to the resulting mixture. After mechanical stirring and uniformity, heat to 70° C. and keep the mixture at this temperature for 5 hours.
[0045] Step 2: After the reaction is completed, add hexahydropyridine in a molar amount of 0.9 times that of 1,3-benzodiazepine to the mixture obtained in step 1, mix and stir evenly, raise the temperature to 75° C., and keep the reaction at this temperature for 6 hours;
[0046] Step 3: After the reaction is completed, the product components obtained in step 2 are filtered and washed, and then the reaction product obtained after washing is mixed with deionized water of 6 times its mass, and after mechanical stirring to completely dissolve it, chlorobenzene is added, and after mixing evenly, the mixture is kept warm at 80°C for 40 hours. After the reaction is completed, the product components are naturally cooled to room temperature, aged for 8 hours, and then filtered and washed in turn to obtain a surface improvement agent.
[0047] The preparation method of the reaction accelerator is as follows: methylimidazole and butyl bromide are added into a reactor equipped with a reflux condenser at a volume ratio of 1:2.0, and a calcium chloride drying tube is installed on the reflux condenser; after mixing and stirring evenly, the mixture is stirred and reacted at a temperature of 85°C for 30 hours, and after the reaction is completed, the product is naturally cooled to room temperature, and then transferred to an extraction device, and washed with ethyl acetate for 3 times and then rotary evaporated to remove the ethyl acetate therein; and then vacuum dried at a temperature of 70°C to constant weight; after drying is completed, a saturated aqueous solution of sodium hexafluorophosphate is slowly added thereto, stirred at room temperature for 15 hours, and then allowed to stand for 20 minutes, and then the lower organic phase is washed with deionized water until no bromine is detected in the washing liquid, and then the residual water is removed by vacuum drying to obtain the reaction accelerator; wherein, the sodium hexafluorophosphate and methylimidazole are used in equimolar amounts.
[0048] Comparative Example 1: The difference between this embodiment and embodiment 1 is that an equal amount of sodium polydisulfide dipropane sulfonate is used to replace the surface improving agent in this embodiment.
[0049] Comparative Example 2: The difference between this embodiment and embodiment 1 is that an equal amount of sodium thiopropane sulfonate is used in this embodiment to replace the surface improving agent.
[0050] Comparative Example 3: The difference between this embodiment and embodiment 1 is that an equal amount of sodium phenyl disulfide propane sulfonate is used to replace the surface improving agent in this embodiment.
[0051] Performance test: The additive samples for electrolytic copper foil provided in Examples 1 to 3 and Comparative Examples 1 to 3 were mixed with water to prepare an aqueous solution of additive with a concentration of 200 mg / L, and then added to the copper foil at a speed of 50 mL / min. 2+ The concentration is 80g / L, the concentration of H2SO4 is 130g / L, and the concentration of Cl - Add additives for electrolytic copper foil to a 20ppm copper sulfate electrolyte and heat at 50°C and 60m 3 / h, current density 7000A / m2的 Electrodeposition was performed under the conditions to prepare electrolytic copper foil samples. Then the relevant properties of the electrolytic copper foil samples (size 150mm*150mm) prepared in each group were tested, and the test results were recorded in the following table:
[0052] Test items Warpage Is there any tearing phenomenon? Crystallization degree Thickness uniformity Rz / μm Example 1 <4mm none Very delicate excellent 1.0 Example 2 <4mm none Very delicate excellent 1.0 Example 3 <4mm none Very delicate excellent 1.1 Comparative Example 1 <5mm Slightly torn edges Slightly rough good 1.8 Comparative Example 2 <5mm none Slightly rough good 1.7 Comparative Example 3 <5mm Slightly torn edges Slightly rough good 1.9
[0053] By comparing and analyzing the relevant data in the table, it can be seen that the surface improver prepared by the present invention can not only effectively improve the stacking phenomenon of copper ions, making the surface of the electrolytic copper foil product more delicate and shiny, but also effectively reduce the internal stress of the electrolytic copper foil. It is used as an important raw material for the additive of electrolytic copper foil, which can effectively reduce the internal stress of the electrolytic copper foil and obtain the electrolytic copper foil product with low warpage; furthermore, the surface improver and the brightener cooperate with each other, so that the prepared electrolytic copper foil has the advantages of uniform thickness, no tearing edge, and delicate surface, which effectively guarantees its quality and grade. This shows that the additive for electrolytic copper foil provided by the present invention has a broader market prospect and is more suitable for promotion.
[0054] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
[0055] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.
Claims
1. An additive for electrolytic copper foil, characterized in that: The additive for electrolytic copper foil consists of a brightener, a dispersing aid, an inhibitor and a surface improving agent; and the weight ratio of the brightener, the dispersing aid, the inhibitor and the surface improving agent is 1:3-5:20-30:2-3.
2. The additive for electrolytic copper foil according to claim 1, characterized in that: The brightener is selected from any one of sodium polydisulfide propane sulfonate, sodium alcoholthiopropane sulfonate, and sodium phenyldisulfide propane sulfonate.
3. The additive for electrolytic copper foil according to claim 1, characterized in that: The inhibitor is collagen, and the weight average molecular weight of the collagen is 6000-10000 g / mol.
4. The additive for electrolytic copper foil according to claim 1, characterized in that: The dispersing aid is polyethylene glycol, and the weight average molecular weight of the polyethylene glycol is 8000-12000 g / mol.
5. The additive for electrolytic copper foil according to claim 1, characterized in that: The preparation method of the surface improving agent comprises the following steps: Step 1, adding organic ether to deionized water at a dosage ratio of 0.5 to 1.0 mol / L, and adding 1,3-benzodiazepine in a molar amount of 0.6 to 0.8 times that of the organic ether, mixing and stirring evenly, adding a reaction accelerator in an amount of 1.2 to 1.5% of the organic ether to the resulting mixture, heating to 50 to 70° C. after mechanical stirring evenly, and keeping the reaction at this temperature for 3 to 5 hours; Step 2: After the reaction is completed, add hexahydropyridine in a molar amount of 0.7 to 0.9 times that of 1,3-benzodiazepine to the mixture obtained in step 1, mix and stir evenly, raise the temperature to 60 to 75° C., and keep the reaction at this temperature for 5 to 6 hours; Step 3: After the reaction is completed, the product components obtained in step 2 are filtered and washed, and then the reaction product obtained after washing is mixed with deionized water of 4 to 6 times its mass, and the modifier is added after mechanical stirring to completely dissolve it. After mixing evenly, the mixture is kept warm at a temperature of 50 to 80°C for 20 to 40 hours. After the reaction is completed, the product components are naturally cooled to room temperature, aged for 5 to 8 hours, and then filtered and washed in turn to obtain the surface improvement agent.
6. The additive for electrolytic copper foil according to claim 5, characterized in that: The organic ether is selected from any one of 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether.
7. The additive for electrolytic copper foil according to claim 5, characterized in that: The preparation method of the reaction accelerator is as follows: methylimidazole and butyl bromide are added into a reactor equipped with a reflux condenser at a volume ratio of 1:1.5-2.0, and a calcium chloride drying tube is installed on the reflux condenser; after mixing and stirring evenly, stirring and reacting at a temperature of 65-85°C for 20-30h, after the reaction is completed, the product is naturally cooled to room temperature, and then transferred to an extraction device, washed with ethyl acetate 2-3 times, and then rotary evaporated to remove the ethyl acetate therein; Then vacuum dry at a temperature of 60-70°C to constant weight; after drying, slowly add a saturated aqueous solution of sodium hexafluorophosphate thereto, stir at room temperature for 10-15 hours, let stand for 10-20 minutes, then wash the lower organic phase with deionized water until no bromine is detected in the washing liquid, and then remove the residual water by vacuum drying to obtain the reaction accelerator.
8. The additive for electrolytic copper foil according to claim 5, characterized in that: The modifier is selected from any one of methyl chloride and methyl iodide.
9. The additive for electrolytic copper foil according to claim 7, characterized in that: The sodium hexafluorophosphate and methylimidazole were used in equimolar amounts.