CN102002737A - Composite additive for producing electrolytic copper foil with high bending resistance and low outline - Google Patents
Composite additive for producing electrolytic copper foil with high bending resistance and low outline Download PDFInfo
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- CN102002737A CN102002737A CN 201010572965 CN201010572965A CN102002737A CN 102002737 A CN102002737 A CN 102002737A CN 201010572965 CN201010572965 CN 201010572965 CN 201010572965 A CN201010572965 A CN 201010572965A CN 102002737 A CN102002737 A CN 102002737A
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Abstract
The invention relates to a composite additive for producing an electrolytic copper foil with high bending resistance and a low outline, which belongs to the technical field of the production process of highly precise electrolytic copper foils. The composite additive for producing the electrolytic copper foil with the high bending resistance and the low outline is characterized by consisting of cellulose, glutin, thiazoline based sodium dithiopropanesulphonate and succinic acid ester sulfonate. The additive and the formula adopted by the invention have the advantages that: the tensile strength and elongation of a product at normal temperature and high temperature is improved, and the defect of low bending resistance of the electrolytic copper foil is effectively overcome; and the surface roughness of the electrolytic copper foil for high peak valve is more than or equal to 3 mu m, the transmission distance of a signal in a flexible printed circuit (FPC) is extended, attenuation and delay can be generated, so a high-frequency signal cannot be transmitted at a high speed, but the additive and the formula adopted by the invention ensure that the product has low outline property, has the rough surface roughness of less than or equal to 1.5mu m, can meet the using requirement of the FPC on a precise circuit and high-frequency high-speed transmission, and has a simple production process and lower cost.
Description
Technical field
The present invention relates to a kind of composite additive, belong to the high-precision electrolytic copper foil technical field of producing.
Background technology
Electrolytic copper foil is the important starting material that copper-clad plate (CCL) and printed circuit board (pcb) are made.High speed development along with informationized society, industries such as electronics, information and 3G communication all trend towards " miniaturization, precise treatment, ultra-thinization, portability " development, in recent years, China numerous electrolytic copper foils downstream client is in order to realize compactization of electronic product, in succession from the rigidity wiring board flex circuit application of changing the line of production.
Flex circuit application (Flexible Printed Circuit), english abbreviation FPC, be commonly called as soft board, have light, thin, but free bend, coiling, can arbitrarily move at three-dimensional space and reach advantages such as flexible, now be widely used in MP3, MP4 player, portable CD player, family expenses DVD, digital camera, mobile phone and battery of mobile phone, medical treatment, automobile, space flight and military field.
Copper Foil is one of main raw material(s) of producing FPC, can divide calendering and two kinds of manufacture crafts of electrolysis by production method.Rolled copper foil belongs to the plate crystal weave construction, density is higher, so have excellent unit elongation, anti-bending, the performances such as smoothness of high temperature recrystallization and uniform surface, this also is the reason that former FPC manufacturer only uses rolled copper foil, but rolled copper foil complete processing complexity, cost is higher, make and have same property, competitively priced FPC more and more substitutes rolled copper foil with electrolytic copper foil and is used in FPC, because FPC has gently, thin, but free bend, advantages such as coiling, this requires employed electrolytic copper foil must have stable physics, chemical property, the low profile and the resistance to bend(ing) of special electrolytic copper foil.
Summary of the invention
The object of the present invention is to provide a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil, the electrolytic copper foil that uses this composite additive to produce, thickness≤12um, when having good normal, high temperature tensile strength and unit elongation, have more excellent high resistance to bend(ing) and low profile, hair side roughness≤1.5um, and production technique is simple, and cost is lower.
The technical solution used in the present invention is as follows:
A kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil is made up of Mierocrystalline cellulose, gelatin, thiazolinyl dithio propane sulfonic acid sodium, four kinds of raw materials of sulphosuccinates;
The consumption of above-mentioned four kinds of raw materials is: contain Mierocrystalline cellulose 40-90mg in the aqueous solution of every liter of composite additive, gelatin 10-50mg, thiazolinyl dithio propane sulfonic acid sodium 5-25mg, sulphosuccinates 50-50mg;
The optimum amount of above-mentioned four kinds of raw materials is: contain Mierocrystalline cellulose 50-80mg in the aqueous solution of every liter of composite additive, gelatin 20-40mg, thiazolinyl dithio propane sulfonic acid sodium 10-20mg, sulphosuccinates 60-300mg;
Described Mierocrystalline cellulose is the plain ethers of non-ionic type soluble fiber.
Described Mierocrystalline cellulose is any in hydroxyethylmethyl-cellulose ether, hydroxypropylcelluloether ether, the hydroxyethyl ether cellulose.
Described gelatin is the gelatin of the small molecular weight of molecular weight between 2000～4000.
Described sulphosuccinates is the tensio-active agent that has in a kind of sulphosuccinates series than long ester chain.
Described sulphosuccinates is any in dibutyl Succinic Acid sodium sulfonate, the diamyl Succinic Acid sodium sulfonate.
A kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil of the present invention by using composite additive, is produced high resistance to bend(ing) and low profile electrolytic copper foil, can substitute rolled copper foil fully and be applied to FPC; Hair side roughness≤1.5um low profile, in the FPC of high-frequency high-speed transmission, fine-line, " the epidermis effect " that is produced in the time of can overcoming electric current under the above condition of frequency 1GHz by conductive layer reduces the impedance that produces, and helps the quick transmission of signal.
Additive of the present invention and proportioning advantage: improve tensile strength and the unit elongation of product under normal, high temperature, effectively solve the deficiency of electrolytic copper foil resistance to bend(ing); Electrolytic copper foil surface roughness 〉=the 3um that is used for peak value, signal is elongated in the FPC propagation distance, will produce decay and delay, being not suitable for high-frequency signal transmits at a high speed, additive of the present invention and proportioning make product have low profile, and hair side roughness≤1.5um satisfies the FPC service requirements of fine-line, high-frequency high-speed transmission, and production technique is simple, and cost is lower.
Description of drawings
Fig. 1: adopt the SEM photo under 2000 times of the high resistance to bend(ing) of 12 μ m, the low profile electrolytic copper foils that the composite additive among the present invention produces.
Fig. 2: adopt the SEM photo under 2000 times of the high resistance to bend(ing) of 9 μ m, the low profile electrolytic copper foils that the composite additive among the present invention produces.
Embodiment
Below in conjunction with specific embodiments of the present invention, further specify technical scheme of the present invention, but embodiments of the present invention are not limited to following specific embodiments.
Composite additive of the present invention is when making high resistance to bend(ing) and low profile electrolytic copper foil, copper content 70-110g/L, sulfuric acid 120-140g/L in the electrolytic solution, chlorion 10-20ppm, temperature 46-56 ℃, in process of production following composite additive lysate is added continuously in the electrolytic solution, addition is 20-200L/h, adopts the production of known electrolytic copper foil electro-deposition process parameter.
Embodiment 1: a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil, contain hydroxyethyl ether cellulose 40mg in the aqueous solution of every liter of composite additive, gelatin 10mg, thiazolinyl dithio propane sulfonic acid sodium 5mg, dibutyl Succinic Acid sodium sulfonate 50mg.
Embodiment 2: a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil, contain hydroxyethylmethyl-cellulose ether 90mg in the aqueous solution of every liter of composite additive, gelatin 50mg, thiazolinyl dithio propane sulfonic acid sodium 25mg, diamyl Succinic Acid sodium sulfonate 500mg.
Embodiment 3: a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil, contain hydroxypropylcelluloether ether 50mg in the aqueous solution of every liter of composite additive, gelatin 20mg, thiazolinyl dithio propane sulfonic acid sodium 10mg, diamyl Succinic Acid sodium sulfonate 60mg.
Embodiment 4: a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil, contain hydroxypropylcelluloether ether 80mg in the aqueous solution of every liter of composite additive, gelatin 40mg, thiazolinyl dithio propane sulfonic acid sodium 20mg, dibutyl Succinic Acid sodium sulfonate 300mg.
Embodiment 5: a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil, contain hydroxyethylmethyl-cellulose ether 65mg in the aqueous solution of every liter of composite additive, gelatin 30mg, thiazolinyl dithio propane sulfonic acid sodium 15mg, dibutyl Succinic Acid sodium sulfonate 180mg.
High resistance to bend(ing) that the present invention makes and low profile electrolytic copper foil be after testing: thickness≤12um, hair side roughness≤1.5um, unit elongation 〉=3.5%, room temperature tensile strength 〉=380MPa, high temperature tensile strength 〉=205MPa, the flexibility coat copper plate resistance to bend(ing) of making reaches more than 100,000 times, as table 1.
High resistance to bend(ing) of table 1 and low profile electrolytic copper foil performance
Claims (8)
1. a composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil is characterised in that by Mierocrystalline cellulose, gelatin, thiazolinyl dithio propane sulfonic acid sodium, four kinds of raw materials of sulphosuccinates and forms.
2. according to the described a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil of claim 1, the consumption that it is characterized in that above-mentioned four kinds of raw materials is: contain Mierocrystalline cellulose 40-90mg in the aqueous solution of every liter of composite additive, gelatin 10-50mg, thiazolinyl dithio propane sulfonic acid sodium 5-25mg, sulphosuccinates 50-500mg.
3. according to the described a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil of claim 2, the optimum amount that it is characterized in that above-mentioned four kinds of raw materials is: contain Mierocrystalline cellulose 50-80mg in the aqueous solution of every liter of composite additive, gelatin 20-40mg, thiazolinyl dithio propane sulfonic acid sodium 10-20mg, sulphosuccinates 60-300mg.
4. according to the described a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil of claim 1, it is characterized in that described Mierocrystalline cellulose is the plain ethers of non-ionic type soluble fiber.
5. according to the described a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil of claim 4, it is characterized in that described Mierocrystalline cellulose is any in hydroxyethylmethyl-cellulose ether, hydroxypropylcelluloether ether, the hydroxyethyl ether cellulose.
6. according to the described a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil of claim 1, it is characterized in that described gelatin is the gelatin of the small molecular weight of molecular weight between 2000～4000.
7. according to the described a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil of claim 1, it is characterized in that described sulphosuccinates is the tensio-active agent that has in a kind of sulphosuccinates series than long ester chain.
8. according to the described a kind of composite additive that can be used for producing high resistance to bend(ing) and low profile electrolytic copper foil of claim 7, it is characterized in that described sulphosuccinates is any in dibutyl Succinic Acid sodium sulfonate, the diamyl Succinic Acid sodium sulfonate.
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| CN102002737B CN102002737B (en) | 2012-10-31 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603501A (en) * | 2016-01-17 | 2016-05-25 | 莫镇威 | Electrolytic copper foil surface treatment additive, preparation method, treatment method and device |
| CN106521564A (en) * | 2016-10-27 | 2017-03-22 | 建滔（连州）铜箔有限公司 | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive |
| EP2771303B1 (en) * | 2011-12-09 | 2018-10-31 | Dow Global Technologies LLC | A method for reducing agglomeration in gypsum plaster or filling compositions comprising cellulose ether |
| 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 |
| CN111394754A (en) * | 2020-04-30 | 2020-07-10 | 东强（连州）铜箔有限公司 | Copper foil additive for fifth-generation mobile communication board, copper foil and production process of copper foil |
| CN111962109A (en) * | 2020-08-20 | 2020-11-20 | 苏州大学 | Acid copper additive and preparation method thereof |
| CN112469194A (en) * | 2020-11-27 | 2021-03-09 | 广东嘉元科技股份有限公司 | Low-profile electrolytic copper foil for high-density interconnected circuit board |
| 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 |
| CN113638016A (en) * | 2021-08-06 | 2021-11-12 | 佛冈建滔实业有限公司 | Additive for improving stripping resistance of electrolytic copper foil and preparation method thereof |
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| CN1551710A (en) * | 2003-02-12 | 2004-12-01 | �źӵ�·ͭ����ʽ���� | Copper foil for fine pattern printed circuits and method of production of same |
| CN1854347A (en) * | 2005-04-20 | 2006-11-01 | Lg电线有限公司 | Low roughness copper foil with high strength and manufacture thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2771303B1 (en) * | 2011-12-09 | 2018-10-31 | Dow Global Technologies LLC | A method for reducing agglomeration in gypsum plaster or filling compositions comprising cellulose ether |
| US10457600B2 (en) | 2011-12-09 | 2019-10-29 | Dow Global Technologies Llc | Method for reducing agglomeration in gypsum plaster or filling compositions comprising cellulose ether |
| CN105603501A (en) * | 2016-01-17 | 2016-05-25 | 莫镇威 | Electrolytic copper foil surface treatment additive, preparation method, treatment method and device |
| CN106521564A (en) * | 2016-10-27 | 2017-03-22 | 建滔（连州）铜箔有限公司 | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive |
| CN110042438B (en) * | 2019-04-24 | 2021-02-05 | 福建清景铜箔有限公司 | Method for preparing electrolytic copper foil |
| 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 |
| CN111394754A (en) * | 2020-04-30 | 2020-07-10 | 东强（连州）铜箔有限公司 | Copper foil additive for fifth-generation mobile communication board, copper foil and production process of copper foil |
| CN111962109A (en) * | 2020-08-20 | 2020-11-20 | 苏州大学 | Acid copper additive and preparation method thereof |
| CN112469194A (en) * | 2020-11-27 | 2021-03-09 | 广东嘉元科技股份有限公司 | Low-profile electrolytic copper foil for high-density interconnected circuit board |
| WO2022110536A1 (en) * | 2020-11-27 | 2022-06-02 | 广东嘉元科技股份有限公司 | Low-profile electrolytic copper foil for high-density interconnection circuit board |
| 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 |
| CN112839436B (en) * | 2020-12-30 | 2022-08-05 | 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 |
| CN113638016A (en) * | 2021-08-06 | 2021-11-12 | 佛冈建滔实业有限公司 | Additive for improving stripping resistance of electrolytic copper foil and preparation method thereof |
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| CN102002737B (en) | 2012-10-31 |
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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. |