CN104177879B - Without profile electrolytic copper foil surface conditioning agent - Google Patents
Without profile electrolytic copper foil surface conditioning agent Download PDFInfo
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- CN104177879B CN104177879B CN201410347996.3A CN201410347996A CN104177879B CN 104177879 B CN104177879 B CN 104177879B CN 201410347996 A CN201410347996 A CN 201410347996A CN 104177879 B CN104177879 B CN 104177879B
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- copper foil
- conditioning agent
- surface conditioning
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- electrolytic copper
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Abstract
The invention belongs to electrolytic copper foil processing technique field, particularly relate to a kind of without profile electrolytic copper foil surface conditioning agent, the aqueous solution of every liter of surface conditioning agent contains: N (β aminoethyl) the γ aminopropyl trimethoxysilane of 0.5 2.0g, the N vinyl base 2 aminoethyl 3 aminopropyl trimethoxysilane hydrochlorate of 0.5 2.0g and the silester of 0.1 0.4g.The surface conditioning agent composition of the present invention is simple, and raw material is easy to get, easy to use.The surface conditioning agent of the present invention is sprayed on the surface without profile Copper Foil, is remarkably improved its peel strength on high-frequency microwave circuit board, without profile Copper Foil peel strength >=0.6N/mm on polyimide resin or politef base material.
Description
Technical field
The invention belongs to electrolytic copper foil processing technique field, particularly relate to a kind of without profile electrolytic copper foil table
Face inorganic agent.
Background technology
Along with the level of informatization of society improves constantly, the daily information processing capacity of people is increasing day by day,
The information processing capability of electronic product is proposed the highest requirement.Now, electronic product is increasingly
Short, little, light, thinning.The rapid advances of communication industry, makes original commercial communication frequency range seem and gathers around very much
Squeezing, the high-frequency communication of some former military use, from 21 century, band segment is gradually given civilian,
Civilian high-frequency communication is made to obtain unconventional speed development.The high security of communication product, high-transmission
Prescription, also forces mobile phone, automobile telephone, wireless telecommunications to be drawn close to high frequency direction.Additionally count
The increase of calculation machine disposal ability, information storage increases, the high speed of an urgent demand signal transmission.
Generally, we by frequency range at the electromagnetic wave of 300MHZ-3000GHZ (wavelength 1m-0.1mm)
It is referred to as microwave, is referred to as high-frequency microwave printed circuit plate for transmitting the wiring board of this kind of electromagnetic signal.The most several
Year, the high-frequency microwave demand of high-density multi-layered plate (PWBs) is increasing year by year, and PWBs requires higher
Circuit prints density and thinner insulating barrier.The electronic product demand of miniaturisation high-performance is increasing,
Require wiring board high density and high frequency signal transmission accordingly.Printed circuit board high-speed signal transmission lines can be divided
It is two big classes: a class is high frequency signal transmission class, and it is relevant with wireless electromagnetic wave, passes with sine wave
Defeated signal, such as radar, radio and television and communication (mobile phone, microwave communication, optical-fibre communications etc.)；Separately
One class is that high-speed logic signal transmits class, and with digital data transmission, the square wave transmission with electromagnetic wave is relevant,
Main application in computer, computer, has application in household electrical appliances and communication class electronic product now.Use
High density interconnection and the printed circuit board (PCB) of frequency transfer characteristic, become the trend of development.At height
Spending informationalized society, quantity of information can be increasing, and transmission speed is increasingly faster, and signal frequency is from 3GHz
Following superfrequency (UHF), develop into 10GHz, to hyperfrequency (SHF).High-frequency signal is limited by collection
Skin effect, can only transmit on the top layer (l-2 μm) of copper wire, and coarse surface will increase high-frequency signal
Linear impairments.Research finds, frequency is the electromagnetic signal of 10GHz, is leading of 0 μm in surface roughness
Body loss-15.8dB/m, surface roughness is 0.5 μm, 1.0 μm, the conductor propagation of 3 μm
Loss is followed successively by-20dB/m ,-24dB/m ,-26dB/m.In terms of containment loss, there is light
The Copper Foil without profile on sliding surface has clear superiority.Therefore, for the high-frequency microwave printed circuit of PWBs
Plate to realize less line-spacing, and applying without profile (Rz < 1.5 μm, iso standard) electrolytic copper foil is to send out
The trend of exhibition.Current PCB makes and takes subtractive process operation more, can reach the water of 10-20 μm line-spacing
Flat.Use general Copper Foil (such as standard STD, high temperature extension HTE Copper Foil, belong to MP Copper Foil),
When making fine circuitry, copper foil surface is rougher is difficult to etching totally, easily occurs that short circuit is abnormal, even if adopting
With ultra-low profile (VLP, Rz2-3 μm) Copper Foil, the processing procedure of printed wiring is also limited to 50 μm lines
Away from, and be 25 μm/25 μm without profile Copper Foil for the PWBs, L/S of high-frequency transmission.
High density and high-frequency microwave printed circuit plate, with without profile electrolytic copper foil, belong to high-end special Copper Foil
Product.At present, the part Copper Foil producer of only Japan can volume production.Domestic high-frequency microwave plate producer and
High-caliber PWBs manufacturing enterprise, Copper Foil used relies primarily on import.At home, seldom there is producer
High frequency board-use copper-clad can be produced.My company developed VLP type high-frequency microwave board-use copper-clad in 2012,
It is devoted to the research without profile high-frequency microwave board-use copper-clad the most always, obtains into the second half year in 2013
Merit.
High density and high-frequency microwave printed circuit plate use without profile Copper Foil, and it is raw compared with general Copper Foil
Runoff yield journey is essentially identical, its technological difficulties have two: one be electrolytic copper foil without contoured, wherein add
Agent prescription is crucial；Two is the Copper Foil without profile under the conditions of the surface of coarsening-free processes, and how to improve it
Peel strength.
General electrolytic copper foil, needs, through roughening treatment and silane coating coupling agent, to improve Copper Foil and exist
Peel strength on resin base material.Hair side (crystal growth plane) Rz of Copper Foil without profile requires < 1.5 μ
M, glossiness (60 °) more than 700, it is clear that the way using roughening is worthless.Feasible technology
Scheme is the effect of research interfacial force, uses special coupling agent to increase bonding strength.Electrolytic copper foil is raw
Produce, the γ of common silane coupler such as epoxy radicals-(2,3-epoxy the third oxygen) propyl trimethoxy silicane
(KH560), the γ-aminopropyl triethoxysilane (KH550) etc. of amino, at these coupling agents
The Copper Foil of reason raising DeGrain on high-frequency microwave printed circuit sheet material, to peel strength.This
It is the subject matter that the invention solves the problems that.
Summary of the invention
The present invention is directed to the deficiency that above-mentioned prior art exists, it is provided that a kind of surface conditioning agent, it is sprayed on
The surface of Copper Foil without profile is remarkably improved Copper Foil peel strength on high-frequency microwave circuit board.
The technical scheme is that a kind of without profile electrolytic copper foil surface
Inorganic agent, contains in the aqueous solution of every liter of surface conditioning agent: N-(β-aminoethyl)-γ of 0.5-2.0g-
Aminopropyl trimethoxysilane KH792, the N-vinyl base-2-aminoethyl-3-aminopropyl of 0.5-2.0g
The silester TEOS of trimethoxy silane hydrochlorate KH559 and 0.1-0.4g.
At K4P2O7150g/L、Zn2+5g/L, PH9.4, temperature 36 DEG C, additive (additive be Mo,
One in the sulfate of Co, Ni, Fe or chlorate) under conditions of 60mg/L, carry out zinc-plated；So
After under the conditions of Neutral potassium chromate 8g/L, PH11.5, temperature 35 DEG C Passivation Treatment；Copper Foil is carried out zinc-plated and
After Passivation Treatment, being coated with one layer of above-mentioned surface conditioning agent, spraying temperature is 20-30 DEG C, and the time is
2-6s。
The invention has the beneficial effects as follows: the surface conditioning agent composition of the present invention is simple, and raw material is easy to get, use
Convenient.The surface conditioning agent of the present invention is sprayed on the surface without profile Copper Foil, is remarkably improved it at height
Frequently the peel strength on microwave circuit boards, without profile Copper Foil at polyimide resin or PTFE base
Peel strength >=0.6N/mm on material.
Detailed description of the invention
Principle and feature to the present invention are described below, and example is served only for explaining the present invention, and
Non-for limiting the scope of the present invention.
Embodiment 1
A kind of without profile electrolytic copper foil surface conditioning agent, the aqueous solution of every liter of surface conditioning agent contains:
The N-vinyl of the N-(β-aminoethyl) of 0.5g-γ-aminopropyltrimethoxysilane KH792,0.5g
The silester TEOS of base-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochlorate KH559 and 0.1g.
At K4P2O7150g/L、Zn2+5g/L, PH9.4, temperature 36 DEG C, additive (additive be Mo,
One in the sulfate of Co, Ni, Fe or chlorate) under conditions of 60mg/L, carry out zinc-plated；So
After under the conditions of Neutral potassium chromate 8g/L, PH11.5, temperature 35 DEG C Passivation Treatment；Copper Foil is carried out zinc-plated and
After Passivation Treatment, being coated with one layer of above-mentioned surface conditioning agent, spraying temperature is 28 DEG C, and the time is 3s.
12 μm after process are without profile Copper Foil, the peel strength on politef base material
0.65N/mm。
Embodiment 2
The present embodiment difference from Example 1 is:
The aqueous solution of every liter of surface conditioning agent contains: N-(β-aminoethyl)-γ-aminopropyl three of 1.0g
Methoxy silane KH792, the N-vinyl base-2-aminoethyl-3-aminopropyl trimethoxysilane of 1.0g
The silester TEOS of hydrochlorate KH559 and 0.2g.Spraying temperature is 25 DEG C, and the time is 4s.
12 μm after process are without profile Copper Foil, the peel strength 0.66 on politef base material
N/mm。
Embodiment 3
The present embodiment difference from Example 1 is:
The aqueous solution of every liter of surface conditioning agent contains: N-(β-aminoethyl)-γ-aminopropyl three of 2.0g
Methoxy silane KH792, the N-vinyl base-2-aminoethyl-3-aminopropyl trimethoxysilane of 1.5g
The silester TEOS of hydrochlorate KH559 and 0.3g.Spraying temperature is 30 DEG C, and the time is 2s.
12 μm after process are without profile Copper Foil, the peel strength 0.70 on politef base material
N/mm。
Embodiment 4
The present embodiment difference from Example 1 is:
The aqueous solution of every liter of surface conditioning agent contains: N-(β-aminoethyl)-γ-aminopropyl three of 1.5g
Methoxy silane KH792, the N-vinyl base-2-aminoethyl-3-aminopropyl trimethoxysilane of 2.0g
The silester TEOS of hydrochlorate KH559 and 0.4g.Spraying temperature is 23 DEG C, and the time is 5s.
12 μm after process are without profile Copper Foil, the peel strength 0.62 on politef base material
N/mm。
Embodiment 5
The present embodiment difference from Example 1 is:
The aqueous solution of every liter of surface conditioning agent contains: N-(β-aminoethyl)-γ-aminopropyl three of 0.8g
Methoxy silane KH792, the N-vinyl base-2-aminoethyl-3-aminopropyl trimethoxysilane of 1.2g
The silester TEOS of hydrochlorate KH559 and 0.25g.Spraying temperature is 26 DEG C, and the time is 3s.
12 μm after process are without profile Copper Foil, the peel strength 0.64 on politef base material
N/mm。
For better illustrating the effect of the present invention, three comparative examples given below:
Comparative example 1
This comparative example difference from Example 1 is:
After Copper Foil is carried out zinc-plated and Passivation Treatment, coat one layer of above-mentioned surface conditioning agent, this surface
Reason agent is: contain γ-(2,3-epoxy the third oxygen) propyl group three of 4g in the aqueous solution of every liter of surface conditioning agent
Methoxy silane KH560.Spraying temperature is 26 DEG C, and the time is 3s.
12 μm after process are without profile Copper Foil, the peel strength 0.25 on politef base material
N/mm。
Comparative example 2
This comparative example is with comparative example 1 difference:
After Copper Foil is carried out zinc-plated and Passivation Treatment, coat one layer of above-mentioned surface conditioning agent, this surface
Reason agent is: contain the γ-aminopropyl triethoxysilane of 3.5g in the aqueous solution of every liter of surface conditioning agent
KH550。
12 μm after process are without profile Copper Foil, the peel strength 0.22 on politef base material
N/mm。
Comparative example 3
This comparative example is with comparative example 1 difference:
After Copper Foil is carried out zinc-plated and Passivation Treatment, coat one layer of above-mentioned surface conditioning agent, this surface
Reason agent is: contain γ-(2,3-epoxy the third oxygen) propyl group of 3.0g in the aqueous solution of every liter of surface conditioning agent
Trimethoxy silane KH560.
12 μm after process are without profile Copper Foil, the peel strength 0.20 on politef base material
N/mm。
For the clearer description present invention, the Copper Foil that table 1 lists each embodiment, comparative example obtains
Performance data compares.
Table 1
As can be seen from Table 1, the embodiment of the present invention, compared to comparative example, uses the surface of the present invention to process
The Copper Foil without profile that agent prepares, its peel strength on politef base material significantly improves.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all in the present invention
Spirit and principle within, any modification, equivalent substitution and improvement etc. made, should be included in this
Within bright protection domain.
Claims (1)
1. one kind without profile electrolytic copper foil surface conditioning agent, it is characterised in that every liter of surface conditioning agent
Aqueous solution contains: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792 of 0.5-2.0g,
The N-vinyl base-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochlorate KH559 of 0.5-2.0g
Silester TEOS with 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104177879A CN104177879A (en) | 2014-12-03 |
| CN104177879B true CN104177879B (en) | 2016-08-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410347996.3A Active CN104177879B (en) | 2014-07-22 | 2014-07-22 | Without profile electrolytic copper foil surface conditioning agent |
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Families Citing this family (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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| 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 |
| KR20150092113A (en) * | 2012-12-06 | 2015-08-12 | 미츠비시 가스 가가쿠 가부시키가이샤 | Method for producing metal-foil-clad laminate |
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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. |