CN104177879A - Surface treating agent for no-outline electrolytic copper foils - Google Patents
Surface treating agent for no-outline electrolytic copper foils Download PDFInfo
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- CN104177879A CN104177879A CN201410347996.3A CN201410347996A CN104177879A CN 104177879 A CN104177879 A CN 104177879A CN 201410347996 A CN201410347996 A CN 201410347996A CN 104177879 A CN104177879 A CN 104177879A
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Abstract
The invention belongs to the technical field of electrolytic copper foil processing, and particularly relates to a surface treating agent for no-outline electrolytic copper foils. Every liter of surface treating agent water solution contains 0.5-2.0g of N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, 0.5-2.0g of N- vinylbenzyl-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and 0.1-0.4g of ethyl silicate. The surface treating agent has the advantages of simple components and accessible raw materials, and is convenient to use. When being sprayed on the surface of the no-outline copper foil, the surface treating agent can obviously enhance the peel strength of the no-outline copper foil on a high-frequency microwave circuit board, so that the peel strength of the no-outline copper foil on a polyamide resin or polytetrafluoroethylene substrate is greater than or equal to 0.6 N/mm.
Description
Technical field
The invention belongs to electrolytic copper foil processing technique field, relate in particular to a kind of without profile electrolytic copper foil surface treatment agent.
Background technology
Along with the social level of informatization improves constantly, people's daily information processing capacity, day by day increasing, has proposed more and more higher requirement to the information processing capability of electronic product.Now, shorter and shorter, little, light, the thinning of electronic product.The quick progress of communication industry, makes original commercial communication frequency range seem very crowded, the high-frequency communication of some former military use, and since 21 century, band segment is given civilian gradually, makes civilian high-frequency communication obtain unconventional speed development.The high security of communication product, high-transmission specification of quality, also force mobile telephone, automobile telephone, cableless communication to be drawn close to high frequency direction.The increase of computer process ability in addition, information storage increases, the high speed of an urgent demand signal transmission.
Conventionally, we are called microwave by range of frequency at the hertzian wave of 300MHZ-3000GHZ (wavelength 1m-0.1mm), for transmitting the wiring board of this class electromagnetic signal, are called high-frequency microwave printed circuit plate.In recent years, the demand of high-density multi-layered plate for high frequency microwave (PWBs) was increasing year by year, and PWBs requires higher circuit to print density and thinner insulation layer.The electronic product demand of miniaturisation high-performance is increasing, requires accordingly wiring board high-density and high-frequency signal transmission.Printed circuit board high-speed signal transmission lines can be divided into two large classes: a class is high-frequency signal transmission class, it is relevant with wireless hertzian wave, with sine wave transmissions signal, as radar, broadcast television and communication (mobile telephone, microwave communication, optical-fibre communications etc.); Another kind of is high-speed logic signal transmission class, with digital data transmission, relevant with electromagnetic square wave transmission, mainly in computer, computer, applies, and has been applied to now in household electrical appliances and communication class electronic product.Use the printed circuit board (PCB) of high density interconnect and high-frequency transmission characteristic, become the trend of development.In the society of advanced IT application, quantity of information can be increasing, and transmission speed is more and more faster, signal frequency from the ultra-high frequency below 3GHz (UHF), develop into 10GHz, to ultra-high frequency (SHF).High-frequency signal is limited by surface action, can only transmit on the top layer of copper wire (l-2 μ m), and coarse surface will increase the linear impairments of high-frequency signal.Research discovery, the electromagnetic signal that frequency is 10GHz, is conductor transmission loss-15.8dB/m of 0 μ m in surface roughness, surface roughness is 0.5 μ m, 1.0 μ m, be followed successively by-20dB/m of conductor the transmission loss ,-24dB/m of 3 μ m ,-26dB/m.Aspect containment transmission loss, what have smooth surface has clear superiority without profile Copper Foil.Therefore, for the high-frequency microwave printed circuit plate of PWBs, will realize less line-spacing, application is the trend of development without profile (Rz<1.5 μ m, iso standard) electrolytic copper foil.Current PCB makes and takes subtractive process operation more, can reach the level of 10-20 μ m line-spacing.Use general Copper Foil (as standard STD, high temperature extension HTE Copper Foil, belong to MP Copper Foil), when making fine circuitry, more coarse to be difficult to etching clean for copper foil surface, easily occur that short circuit is abnormal, even if adopt ultralow profile (VLP, Rz2-3 μ m) Copper Foil, the processing procedure of printed wiring is also limited in 50 μ m line-spacings, and without profile Copper Foil for the PWBs of high-frequency transmission, L/S is 25 μ m/25 μ m.
High-density and high-frequency microwave printed circuit plate are used without profile electrolytic copper foil, belong to high-end special Copper Foil product.At present, only have the Japanese part Copper Foil producer can volume production.Domestic high frequency microwave plate producer and high-caliber PWBs manufacturing enterprise, Copper Foil used mainly relies on import.At home, seldom there is producer can produce high frequency board-use copper-clad.My company has developed VLP type high frequency microwave board-use copper-clad in 2012, be devoted to afterwards the research without profile high frequency microwave board-use copper-clad always, the second half year in 2013, succeeds.
High-density and high-frequency microwave printed circuit plate adopt without profile Copper Foil, and to compare its Production Flow Chart basic identical with general Copper Foil, and its technological difficulties have two: the one, electrolytic copper foil without contoured, wherein additive formulations is crucial; The 2nd, without the Copper Foil of profile, under the surface treatment condition of coarsening-free, how to improve its peel strength.
General electrolytic copper foil, need to pass through roughening treatment and silane coating coupling agent, improves the peel strength of Copper Foil on resin base material.Hair side (crystal aufwuchsplate) Rz without profile Copper Foil requires <1.5 μ m, and glossiness (60 °) is more than 700, and the way of obviously using alligatoring is worthless.Feasible technical scheme is the effect of research interfacial force, with special coupling agent, increases bond strength.Electrolytic copper foil is produced, common silane coupling agent is as the γ of epoxy group(ing)-(2,3-epoxy the third oxygen) γ-aminopropyl triethoxysilane (KH550) of propyl trimethoxy silicane (KH560), amino etc., the Copper Foil of these coupling agent treatment on high-frequency microwave printed circuit sheet material, the raising DeGrain to peel strength.This is the subject matter that the present invention will solve.
Summary of the invention
The present invention is directed to the deficiency that above-mentioned prior art exists, a kind of surface treatment agent is provided, its surface being sprayed on without profile Copper Foil can significantly improve the peel strength of Copper Foil on high frequency microwave circuit card.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of without profile electrolytic copper foil surface treatment agent, in the aqueous solution of every liter of surface treatment agent, contain: N-Yi Xi Ji Benzyl base-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride KH559 of the N-of 0.5-2.0g (β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792,0.5-2.0g and the tetraethyl silicate TEOS of 0.1-0.4g.
At K
4p
2o
7150g/L, Zn
2+under the condition of 5g/L, PH9.4,36 ℃ of temperature, additive (additive be in the vitriol of Mo, Co, Ni, Fe or chlorate a kind of) 60mg/L, carry out zinc-plated; Then Passivation Treatment under potassiumchromate 8g/L, PH11.5,35 ℃ of conditions of temperature; After Copper Foil is carried out to zinc-plated and Passivation Treatment, then apply the above-mentioned surface treatment agent of one deck, spraying temperature is 20-30 ℃, and the time is 2-6s.
The invention has the beneficial effects as follows: surface treatment agent composition of the present invention is simple, and raw material is easy to get, easy to use.Surface treatment agent of the present invention is sprayed on to the surface without profile Copper Foil, can significantly improves its peel strength on high frequency microwave circuit card, the peel strength >=0.6N/mm without profile Copper Foil on polyimide resin or tetrafluoroethylene base material.
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
Without a profile electrolytic copper foil surface treatment agent, in the aqueous solution of every liter of surface treatment agent, contain: N-Yi Xi Ji Benzyl base-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride KH559 of the N-of 0.5g (β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792,0.5g and the tetraethyl silicate TEOS of 0.1g.
At K
4p
2o
7150g/L, Zn
2+under the condition of 5g/L, PH9.4,36 ℃ of temperature, additive (additive be in the vitriol of Mo, Co, Ni, Fe or chlorate a kind of) 60mg/L, carry out zinc-plated; Then Passivation Treatment under potassiumchromate 8g/L, PH11.5,35 ℃ of conditions of temperature; After Copper Foil is carried out to zinc-plated and Passivation Treatment, then apply the above-mentioned surface treatment agent of one deck, spraying temperature is 28 ℃, and the time is 3s.
12 μ m after processing are without profile Copper Foil, the peel strength 0.65N/mm on tetrafluoroethylene base material.
Embodiment 2
The present embodiment difference from Example 1 is:
In the aqueous solution of every liter of surface treatment agent, contain: N-Yi Xi Ji Benzyl base-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride KH559 of the N-of 1.0g (β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792,1.0g and the tetraethyl silicate TEOS of 0.2g.Spraying temperature is 25 ℃, and the time is 4s.
12 μ m after processing are without profile Copper Foil, the peel strength 0.66N/mm on tetrafluoroethylene base material.
Embodiment 3
The present embodiment difference from Example 1 is:
In the aqueous solution of every liter of surface treatment agent, contain: N-Yi Xi Ji Benzyl base-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride KH559 of the N-of 2.0g (β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792,1.5g and the tetraethyl silicate TEOS of 0.3g.Spraying temperature is 30 ℃, and the time is 2s.
12 μ m after processing are without profile Copper Foil, the peel strength 0.70N/mm on tetrafluoroethylene base material.
Embodiment 4
The present embodiment difference from Example 1 is:
In the aqueous solution of every liter of surface treatment agent, contain: N-Yi Xi Ji Benzyl base-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride KH559 of the N-of 1.5g (β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792,2.0g and the tetraethyl silicate TEOS of 0.4g.Spraying temperature is 23 ℃, and the time is 5s.
12 μ m after processing are without profile Copper Foil, the peel strength 0.62N/mm on tetrafluoroethylene base material.
Embodiment 5
The present embodiment difference from Example 1 is:
In the aqueous solution of every liter of surface treatment agent, contain: N-Yi Xi Ji Benzyl base-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride KH559 of the N-of 0.8g (β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792,1.2g and the tetraethyl silicate TEOS of 0.25g.Spraying temperature is 26 ℃, and the time is 3s.
12 μ m after processing are without profile Copper Foil, the peel strength 0.64N/mm on tetrafluoroethylene base material.
For better illustrating, effect of the present invention below provide three comparative examples:
Comparative example 1
This comparative example difference from Example 1 is:
After Copper Foil is carried out to zinc-plated and Passivation Treatment, apply the above-mentioned surface treatment agent of one deck, this surface treatment agent is: γ-(2,3-epoxy the third oxygen) the propyl trimethoxy silicane KH560 that contains 4g in the aqueous solution of every liter of surface treatment agent.Spraying temperature is 26 ℃, and the time is 3s.
12 μ m after processing are without profile Copper Foil, the peel strength 0.25N/mm on tetrafluoroethylene base material.
Comparative example 2
This comparative example is with comparative example 1 difference:
After Copper Foil is carried out to zinc-plated and Passivation Treatment, apply the above-mentioned surface treatment agent of one deck, this surface treatment agent is: the γ-aminopropyl triethoxysilane KH550 that contains 3.5g in the aqueous solution of every liter of surface treatment agent.
12 μ m after processing are without profile Copper Foil, the peel strength 0.22N/mm on tetrafluoroethylene base material.
Comparative example 3
This comparative example is with comparative example 1 difference:
After Copper Foil is carried out to zinc-plated and Passivation Treatment, apply the above-mentioned surface treatment agent of one deck, this surface treatment agent is: γ-(2,3-epoxy the third oxygen) the propyl trimethoxy silicane KH560 that contains 3.0g in the aqueous solution of every liter of surface treatment agent.
12 μ m after processing are without profile Copper Foil, the peel strength 0.20N/mm on tetrafluoroethylene base material.
For clearer description the present invention, table 1 has been listed the performance data contrast of the Copper Foil that each embodiment, comparative example obtain.
Table 1
As can be seen from Table 1, the embodiment of the present invention is compared to comparative example, adopt that surface treatment agent of the present invention makes without profile Copper Foil, its peel strength on tetrafluoroethylene base material significantly improves.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (1)
1. without a profile electrolytic copper foil surface treatment agent, it is characterized in that containing in the aqueous solution of every liter of surface treatment agent: N-second alkene base Benzyl base-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride KH559 of the N-of 0.5-2.0g (β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792,0.5-2.0g and the tetraethyl silicate TEOS of 0.1-0.4g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410347996.3A CN104177879B (en) | 2014-07-22 | 2014-07-22 | Without profile electrolytic copper foil surface conditioning agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410347996.3A CN104177879B (en) | 2014-07-22 | 2014-07-22 | Without profile electrolytic copper foil surface conditioning agent |
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| CN104177879A true CN104177879A (en) | 2014-12-03 |
| CN104177879B CN104177879B (en) | 2016-08-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111364032A (en) * | 2020-04-22 | 2020-07-03 | 山东金宝电子股份有限公司 | Surface treating agent for copper foil for high-frequency high-speed copper-clad plate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418129A (en) * | 2011-11-18 | 2012-04-18 | 山东金宝电子股份有限公司 | Surface treatment process of copper foil for high-Tg halogen-free plate |
| WO2014088099A1 (en) * | 2012-12-06 | 2014-06-12 | 三菱瓦斯化学株式会社 | Method for producing metal-foil-clad laminate |
-
2014
- 2014-07-22 CN CN201410347996.3A patent/CN104177879B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418129A (en) * | 2011-11-18 | 2012-04-18 | 山东金宝电子股份有限公司 | Surface treatment process of copper foil for high-Tg halogen-free plate |
| WO2014088099A1 (en) * | 2012-12-06 | 2014-06-12 | 三菱瓦斯化学株式会社 | Method for producing metal-foil-clad laminate |
Non-Patent Citations (1)
| Title |
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| 徐树民等: ""挠性印刷电路板用超低轮廓铜箔的表面处理工艺"", 《电镀与涂饰》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111364032A (en) * | 2020-04-22 | 2020-07-03 | 山东金宝电子股份有限公司 | Surface treating agent for copper foil for high-frequency high-speed copper-clad plate |
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| CN104177879B (en) | 2016-08-24 |
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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: No. 128, Wenquan Road, Zhaoyuan, Yantai, Shandong 265700 Patentee before: SHANDONG JINBAO ELECTRONICS Co.,Ltd. |
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