CN109763152A - A kind of production technology of 6 μm of double low warpage additive for electrolytic copper foil of light and the electrolytic copper foil - Google Patents
A kind of production technology of 6 μm of double low warpage additive for electrolytic copper foil of light and the electrolytic copper foil Download PDFInfo
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- CN109763152A CN109763152A CN201910247097.9A CN201910247097A CN109763152A CN 109763152 A CN109763152 A CN 109763152A CN 201910247097 A CN201910247097 A CN 201910247097A CN 109763152 A CN109763152 A CN 109763152A
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Abstract
The present invention is to further decrease the warpage issues of 6 μm of electrolytic copper foils, there is provided a kind of 6 μm of double light low warpage additive for electrolytic copper foil, the KH-5 aqueous solution that the additive is 2-6g/L by concentration, the sodium polydithio-dipropyl sulfonate aqueous solution composition that the low molecule glue solution and concentration that concentration is 4-8g/L are 4-8g/L, and when electro-deposition generates copper foil, it is 50-100mL/min that the aqueous solution of three kinds of components of additive presses KH-5 respectively, low molecule glue is 50-100mL/min, sodium polydithio-dipropyl sulfonate is that the flow of 100-150mL/min is added in copper sulfate electrolyte, and the upper flow quantity of copper sulfate electrolyte is 40-60m3/h.The depth of camber of present invention copper foil produced is reduced to 5mm or less.
Description
Technical field
The invention belongs to electrolytic copper foil technical fields, and in particular to a kind of low warpage additive for electrolytic copper foil of 6 μm of double light
And the production technology of the electrolytic copper foil.
Background technique
Electrolytic copper foil is one of important foundation material of electronics industry, is widely used in electronics industry.With electric car
The fast development of industry, copper foil is as new energy dynamic lithium battery cathode proprietary material, and demand is increasing, to its quality
Requirement be also continuously improved.For ultrathin electrolytic copper foil, warpage is most common and most ignorable defect, and serious
Under the influence of tourist family use, the process mainly influenced be coating, with the reduction of copper thickness, the warpage issues of copper foil are gradually
It aggravates, 6 μm of copper foils are especially prominent.
Applied patent CN105002524A discloses a kind of use 6 μm of low warpages of Additive Production to applicant in the past
The technique of electrolytic copper foil, the additive are the aqueous solution containing brightener SPS, polyethylene glycol, thiocarbamide and Cl-, and in additive
SPS concentration be 6-17g/l, Polyethylene glycol 2-15g/l, thiourea concentration 4-15g/l, Cl- concentration be 15~
25ppm.Although the patent can reduce 6 μm of electrolytic copper foil depth of camber of gained to 12mm hereinafter, solving to a certain extent
The warpage issues of extra thin copper foil, but effect is limited.
Summary of the invention
The present invention is to further decrease the warpage issues of 6 μm of electrolytic copper foils, provides a kind of 6 μm of double light low warpage electrolytic copper foil
5mm or less is reduced to the depth of camber of additive, copper foil produced.
The present invention adopts the following technical scheme:
A kind of low warpage additive for electrolytic copper foil of 6 μm of double light, the additive by the KH-5 aqueous solution that concentration is 2-6g/L,
The sodium polydithio-dipropyl sulfonate aqueous solution composition that the low molecule glue solution and concentration that concentration is 4-8g/L are 4-8g/L, and
When electro-deposition generates copper foil, it is 50-100mL/min, low molecule glue that the aqueous solution of three kinds of components of additive presses KH-5 respectively
For 50-100mL/min, sodium polydithio-dipropyl sulfonate is added in copper sulfate electrolyte for the flow of 100-150mL/min, and
The upper flow quantity of copper sulfate electrolyte is 40-60m3/h。
Preferably, the low molecule glue is collagen of the molecular weight less than 3000.
Preferably, from Shenzhen An Difa Science and Technology Ltd., name of product is copper foil additive KH-5 for the KH-5 purchase,
Network address is http://www.szadfkg.com/pro01/05373.html.
Utilize the technique of the low warpage additive for electrolytic copper foil production electrolytic copper foil of above-mentioned 6 μm pairs of light, first adjusting sulfuric acid
Copper ion concentration in copper electrolyte is 70-100g/L, H2SO4Concentration is 80-130g/L, chlorine ion concentration 25-45ppm, sulphur
Sour copper electrolyte temperature is 45-55 DEG C, and the additive is added by the flow, then under the upper flow quantity, electric current
Density is 4000-6000A/m2Under conditions of, electro-deposition is carried out using foil machine, to generate the low warpage electricity of described 6 μm pairs of light
Solve copper foil.
Preferably, when electro-deposition, current density 4000-6000A/m2。
Beneficial effects of the present invention are as follows:
Electrolytic copper foil hair side roughness RZ of the invention at 2.0 μm hereinafter, with a thickness of 5 μm -7 μm, tensile strength 350MPa with
On, elongation percentage is 8% or more, and on the basis of the above excellent comprehensive performance, the present invention further solves sticking up for electrolytic copper foil
Qu Wenti.
It has been investigated that additive of the invention can effectively promote the consistency and hardness of copper foil, to help to drop
The depth of camber of low copper foil makes warpage be down to 5mm hereinafter, technical value added is high, conducive to the competitiveness for promoting enterprise.Therefore and now
Some technologies are compared, and using the present invention, the warpage of copper foil can be further substantially reduced, and improve the matter of extra thin copper foil product
Amount, furthermore in process of production, apparent by adjusting low molecule glue and the controllable foliation face of sodium polydithio-dipropyl sulfonate, operation letter
It is single.
Detailed description of the invention
Fig. 1 is to prepare face × 500 times copper foil M SEM photograph using embodiment 1；
Fig. 2 is to prepare face × 500 times copper foil M SEM photograph using embodiment 2；
Fig. 3 is to prepare face × 500 times copper foil M SEM photograph using embodiment 3；
Remarks: double light copper foils of the present invention divide M(maos) face and S(light) face, the one side close to cathode roll is the face S, another side M
Unlike face and standard foil, there is brightness in the face M of double light copper foils of the invention, and the face standard foil M is without brightness.
Specific embodiment
In order to keep technical purpose of the invention, technical scheme and beneficial effects clearer, with reference to the accompanying drawing and specifically
Embodiment is further illustrated technical solution of the present invention.
In production practice, following each embodiments can buy KH-5 described in KH-5(to obtain preferable production effect
From Shenzhen An Difa Science and Technology Ltd.), low molecule glue and sodium polydithio-dipropyl sulfonate be configured to close in advance in Agitation Tank
The aqueous solution of suitable concentration, then pressing KH-5 respectively is 50-100mL/min, and low molecule glue is 50-100mL/min, poly- two sulphur dipropyl
Alkyl sulfonic acid sodium is that the flow of 150-200mL/min is delivered in copper sulfate electrolyte, prepares upper liquid；Wherein low molecule glue used is
The collagen that molecular weight is 2000 ~ 2500.
Embodiment 1
A kind of 6 μm of double low warpage electrolytic copper foils of light the preparation method is as follows:
Additive composition: KH-5 is the aqueous solution of 2g/L, and low molecule glue is the aqueous solution of 5g/L, and sodium polydithio-dipropyl sulfonate is
The aqueous solution of 4g/L.
(1) by raw material copper wire in copper-bath, through ventilation and heating, dissolution generates copper sulfate electrolyte.
(2) after filtering, adjust content of copper ion therein is 75g/L, H to copper sulfate electrolyte2SO4Concentration is 90g/L,
Chloride ion content is 25ppm, and temperature is 47 DEG C.
(3) additive is then added according to liquor capacity, in 60mL/min, low molecule glue is for the flow control of KH-5
The upper flow quantity of 70mL/min, sodium polydithio-dipropyl sulfonate 165mL/min, copper sulfate electrolyte are 45m3/h, and electric current is close
Degree is 40000A/ ㎡, carries out electro-deposition using foil machine.
Diameter 10cm sample is chosen, chooses highest point, survey warpage is 5mm, and has done sem test to the sample, such as
Shown in Fig. 1, it can be seen that the crystal grain in copper foil is comparatively fine.
Embodiment 2
The low warpage electrolytic copper foils of the double light of 6 μm of the present embodiment the preparation method is as follows:
Additive composition: KH-5 is the aqueous solution of 4g/L, and low molecule glue is the aqueous solution of 4g/L, and sodium polydithio-dipropyl sulfonate is
The aqueous solution of 6g/L.
(1) by raw material copper wire in copper-bath, through ventilation and heating, dissolution generates copper sulfate electrolyte.
(2) after filtering, adjust content of copper ion therein is 100g/L, H to copper sulfate electrolyte2SO4Concentration is 130g/
L, chloride ion content 30ppm, temperature are 54 DEG C.
(3) additive is then added according to liquor capacity, in 90mL/min, low molecule glue is for the flow control of KH-5
The upper flow quantity of 90mL/min, sodium polydithio-dipropyl sulfonate 200mL/min, copper sulfate electrolyte are 50m3/h, and electric current is close
Degree is 6000A/m2, electro-deposition is carried out using foil machine.
Diameter 10cm sample to be chosen, highest point is chosen, survey warp value is 3mm, and has done sem test to the sample,
As shown in fig. 2, it can be seen that the crystal grain in copper foil is more tiny, this may be the reason for increasing KH-5 dosage.
Embodiment 3
The low warpage electrolytic copper foils of the double light of 6 μm of the present embodiment the preparation method is as follows:
Additive composition: KH-5 is the aqueous solution of 6g/L, and low molecule glue is the aqueous solution of 4g/L, and sodium polydithio-dipropyl sulfonate is
The aqueous solution of 5g/L.
(1) by raw material copper wire in copper-bath, through ventilation and heating, dissolution generates copper sulfate electrolyte.
(2) after filtering, adjust content of copper ion therein is 90g/L to copper sulfate electrolyte, and H2SO4 concentration is
110g/L, chloride ion content 25ppm, temperature are 50 DEG C.
(3) additive is then added according to liquor capacity, in 80mL/min, low molecule glue is for the flow control of KH-5
The upper flow quantity of 80mL/min, sodium polydithio-dipropyl sulfonate 180mL/min, copper sulfate electrolyte are 55m3/h, and electric current is close
Degree is 5000A/ ㎡, carries out electro-deposition using foil machine.
Diameter 10cm sample to be chosen, highest point is chosen, survey warp value is 2mm, and has done sem test to the sample,
Fig. 3, it is shown that the crystal grain in the present embodiment in copper foil is the most tiny in three embodiments, therefore can push away
Disconnected, additive of the present invention can reduce copper foil crystal grain gap, promote copper foil hardness, and then reach the technology effect for reducing warpage
Fruit, it is contemplated that the various comprehensive performances of copper foil, the dosage of each component is also appropriate in additive.
To sum up, the warpage of the copper foil of the low warpage electrolytic copper foil preparation method production of of the invention 6 μm double light in 5mm hereinafter,
Meet requirement of the downstream client to warpage, be able to ascend the competitiveness of enterprise, and production process is easy to control, is suitable for batch
Metaplasia produces.
It should be noted last that: technical solution of the present invention that the above embodiments are only illustrative and not limiting is any right
The equivalent replacement and do not depart from the modification of spirit and scope of the invention or locally replace that the present invention carries out, should all cover in this hair
Within bright protective scope of the claims.
Claims (5)
1. a kind of low warpage additive for electrolytic copper foil of 6 μm of double light, which is characterized in that the additive is 2-6g/L by concentration
KH-5 aqueous solution, concentration be 4-8g/L low molecule glue solution and concentration be 4-8g/L sodium polydithio-dipropyl sulfonate water
Solution composition, and when electro-deposition generates copper foil, it is 50-100mL/ that the aqueous solution of three kinds of components of additive presses KH-5 respectively
Min, low molecule glue are 50-100mL/min, and sodium polydithio-dipropyl sulfonate is that the flow of 100-150mL/min is added to sulfuric acid
In copper electrolyte, and the upper flow quantity of copper sulfate electrolyte is 40-60m3/h。
2. the 6 μm according to claim 1 low warpage additive for electrolytic copper foil of double light, which is characterized in that the low molecule
Glue is collagen of the molecular weight less than 3000.
3. the 6 μm according to claim 1 low warpage additive for electrolytic copper foil of double light, which is characterized in that the KH-5 purchase
It buys from Shenzhen An Difa Science and Technology Ltd..
4. utilizing the work of the low warpage additive for electrolytic copper foil production electrolytic copper foil of any one of the claims 1 to 336 μm pairs of light
Skill, which is characterized in that the copper ion concentration first in adjusting copper sulfate electrolyte is 70-100g/L, H2SO4Concentration is 80-
130g/L, chlorine ion concentration 25-45ppm, copper sulfate electrolyte temperature are 45-55 DEG C, and are added by described in flow addition
Add agent, then under conditions of the upper flow quantity, carry out electro-deposition using foil machine, double light is low sticks up to generate described 6 μm
Bent electrolytic copper foil.
5. the technique of the low warpage additive for electrolytic copper foil production electrolytic copper foil of 6 μm pairs of light according to claim 4, feature
It is, when electro-deposition, current density 4000-6000A/m2。
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| CN201910247097.9A CN109763152A (en) | 2019-03-29 | 2019-03-29 | A kind of production technology of 6 μm of double low warpage additive for electrolytic copper foil of light and the electrolytic copper foil |
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| CN201910247097.9A CN109763152A (en) | 2019-03-29 | 2019-03-29 | A kind of production technology of 6 μm of double low warpage additive for electrolytic copper foil of light and the electrolytic copper foil |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894616A (en) * | 2019-12-30 | 2020-03-20 | 中国科学院青海盐湖研究所 | High-density copper foil and preparation method thereof |
| CN111455414A (en) * | 2020-03-09 | 2020-07-28 | 深圳市惟华电子科技有限公司 | Additive for producing gradual change type electrolytic copper foil |
| CN114351190A (en) * | 2021-12-27 | 2022-04-15 | 安徽华威铜箔科技有限公司 | Preparation method of additive for flexible copper clad laminate electrolytic copper foil, product and application thereof |
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| CN102965698A (en) * | 2012-11-28 | 2013-03-13 | 山东金宝电子股份有限公司 | Production process of low-warpage electrolytic copper foil |
| CN103276416A (en) * | 2013-06-27 | 2013-09-04 | 灵宝华鑫铜箔有限责任公司 | Additive for electrolytic copper foil, and production technique of electrolytic copper foil |
| CN105002524A (en) * | 2015-07-28 | 2015-10-28 | 灵宝华鑫铜箔有限责任公司 | Addition agent and process for producing 6-micron low-warping-degree electrolytic copper foil through addition agent |
-
2019
- 2019-03-29 CN CN201910247097.9A patent/CN109763152A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965698A (en) * | 2012-11-28 | 2013-03-13 | 山东金宝电子股份有限公司 | Production process of low-warpage electrolytic copper foil |
| CN103276416A (en) * | 2013-06-27 | 2013-09-04 | 灵宝华鑫铜箔有限责任公司 | Additive for electrolytic copper foil, and production technique of electrolytic copper foil |
| CN105002524A (en) * | 2015-07-28 | 2015-10-28 | 灵宝华鑫铜箔有限责任公司 | Addition agent and process for producing 6-micron low-warping-degree electrolytic copper foil through addition agent |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894616A (en) * | 2019-12-30 | 2020-03-20 | 中国科学院青海盐湖研究所 | High-density copper foil and preparation method thereof |
| CN110894616B (en) * | 2019-12-30 | 2021-04-20 | 中国科学院青海盐湖研究所 | High-density copper foil and preparation method thereof |
| CN111455414A (en) * | 2020-03-09 | 2020-07-28 | 深圳市惟华电子科技有限公司 | Additive for producing gradual change type electrolytic copper foil |
| CN114351190A (en) * | 2021-12-27 | 2022-04-15 | 安徽华威铜箔科技有限公司 | Preparation method of additive for flexible copper clad laminate electrolytic copper foil, product and application thereof |
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