CN101457375A - Electroplate copper liquor for printed circuit board - Google Patents

Electroplate copper liquor for printed circuit board Download PDF

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Publication number
CN101457375A
CN101457375A CNA2007101250131A CN200710125013A CN101457375A CN 101457375 A CN101457375 A CN 101457375A CN A2007101250131 A CNA2007101250131 A CN A2007101250131A CN 200710125013 A CN200710125013 A CN 200710125013A CN 101457375 A CN101457375 A CN 101457375A
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Prior art keywords
copper
circuit board
printed circuit
electroplating
solution
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CNA2007101250131A
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Chinese (zh)
Inventor
王海粟
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SHENZHEN TIANZE SCIENCE INDUSTRY Co Ltd
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SHENZHEN TIANZE SCIENCE INDUSTRY Co Ltd
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Priority to CNA2007101250131A priority Critical patent/CN101457375A/en
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Abstract

The invention belongs to the electroplating field, in particular relates to a novel electroplating solution with excellent plating property used in the process of plating copper in the production and manufacturing of a circuit board. The electroplating copper solution of a printed circuit board comprises a copper sulphate solution and a dispersant; the dispersant is mainly sodium salt solution containing sulfosuccinate group and ethylene oxide group, and the dispersant comprises alkyl ester sodium sulfonate salt of succinic acid, succinate sodium salt containing amine and the succinate sodium salt containing ethoxy. An anion surfactant containing the sodium salt of the sulfosuccinate group and the ethylene oxide group is taken as the dispersant for a used additive, which significantly improves the comprehensive electroplating property of the electroplating copper solution, and ensures that the electroplating solution has high dispersing property, excellent ductibility and better plating homogeneity. The invention can provide the novel electroplating copper solution with the high dispersing property, the excellent ductibility and the better plating homogeneity. The copper solution can meet requirements for high density and high accuracy of plating copper on the printed circuit board.

Description

A kind of electroplate copper liquor for printed circuit board
[technical field]
The invention belongs to field of electroplating, especially use a kind of in the copper facing process in the board production manufacturing has the good novel electroplate liquid that is coated with performance.
[background technology]
Just found that as far back as the beginning of this century gelatin, glycine, materials such as Gelucystine and thiocarbamide can make copper sulfate bath obtain the coating of light.Once had behind the fifties with thiocarbamide or the same respectively dextrin of thiocarbamide, multiple material such as mercaptobenzothiazole cooperates the patent as the hydrosulphate copper brightener, though these additives can make the coating light, grain refining, but the mechanical property of coating can not meet the demands, as: additives such as gelatin cause coating to be mingled with, and coating fragility and porosity increase; And the additive that thiocarbamide is formed can reduce the flexibility of coating greatly, and layering and the coating mechanical property is reduced easily.To the seventies, relevant polymkeric substance, organic dye or complicated sulfur-bearing, the additive of nitrogenate combination emerges, can obtain highly leveling, light, soft good China starts from the seventies to the development of bright acidic copper plating additive, early seventies, the Computer Department of the Chinese Academy of Science and department of chemistry of Beijing University cooperate, and take the lead in developing high dispersive ability acidic copper-plating of bright liquid at home, adopt the low copper prescription of peracid, make solution dispersibility good, outward appearance and mechanical property are all good.Simultaneously, external a large amount of document and patent are collected and put in order in four cyanideless electro-plating working groups of machine portion, and organized research of technique, on the basis of a large amount of scientific experimentations and production practice, the seventies latter stage, released and be used for the copper-plated electroplating additive SH-110 of printed board, use this additive, match with other material, can obtain light, the copper coating of leveling, plating bath has good dispersive ability and covering power, even under 40 ℃, also can normally carry out work and can not decompose, be particularly useful for printed board copper facing, it is the high dispersive ability acid copper plating bath of brightening agent that 15 priorities of the ministry of electronics industry have been released with LC151 and LC153, equally can be 10-40 ℃ of following works better.Yet the layer bright film of surging arranged on the copper coating that obtains with these additives, must this tunic be destroyed through peracid or alkali lye, just the unlikely bonding force that influences copper layer and other coating.Released the copper coating of two kinds of LC154 and FDT-1 again for this reason.Additive has been eliminated the film of surging of copper laminar surface, and quality of coating has had large increase.
Copper sulfate is electroplated in PCB electroplates and is being accounted for very consequence, and the galvanized quality of sour copper directly influences the quality and the related mechanical properties of copper electroplating layer, and following process is produced certain influence.Have only plate face and through-hole plating thickness even, could guarantee that coating has enough intensity and conduction to give birth to.This just needs plating bath that good dispersive ability and covering power are arranged.Along with printed board to high-density, the development of high precision direction, thickness of slab (〉=7.2mm), aperture (have higher requirement to the copper facing technology in the Φ≤0.35mm), 2.54mm grid by five lines of cloth or five above printed boards of line.The performance that is coated with of the electroplate liquid in the existing industry has been difficult to satisfied copper facing requirement to high-density, high-precision circuit plate.
[summary of the invention]
The purpose of this invention is to provide a kind of high dispersive performance that has, good ductility, the novel electrolytic copper plating solution of good covering power, this copper liquid can satisfy copper-plated requirement on high-density, the high precision printed circuit board (PCB).
In order to reach above-mentioned technical purpose, the technical solution that the present invention adopts comprises technology contents: a kind of electroplate copper liquor for printed circuit board, comprise copper-bath and dispersion agent, the main dispersion agent that adopts is the sodium salt solution that contains sulfo-succinic acid fat base and oxyethylene group.Dispersion agent comprises the alkyl lipid sulfonate sodium of succsinic acid, contains the amber acid ester sodium salt of amine, contains the amber acid ester sodium salt of oxyethyl group.The interpolation scope is 0.05-5g/L in plating bath, and the best is 0.1-2g/L.For example alcohol ether sulfo-succinic acid monoester disodium (DAPS), Succinic Acid diamyl fat sodium sulfonate (AY-65), 1-sulphonyl amber acid ester-2-oxyethylene group-3-hydroxyl-4-sodium succinate (TPSO3), Succinic Acid dihexyl sodium sulfonate (MA-80), Succinic Acid alkyl polyoxyethylene ether monoesters disodium sulfonate salt (A-102) etc. can effectively improve the quality of coating.
Main ingredient in above-mentioned electrolytic copper plating solution is a copper-bath, and the component of copper-bath is copper sulfate 50-90g/L, sulfuric acid 160-200g/L, chlorion 35-80ppm.The best configuration ratio of the component of copper-bath is copper sulfate 75g/L, sulfuric acid 180g/L, chlorion 60ppm.State in the use and add dispersion agent in the copper-bath of concentration the performance that is coated with of electrolytic copper plating solution is promoted significantly.
Better be coated with performance for electrolytic copper plating solution is had, in electrolytic copper plating solution, also be added with crystallization fining agent and brightening agent.
The crystallization fining agent that adds in the copper electroplating solution, its composition are benzene a pair of horses going side by side thiazole or benzimidazolyl, and consumption is 0.05-10ppm, and the best is 0.2-5ppm.For example 2-mercaptobenzoimidazole (M) can plate out leveling and the good all bright cladding of toughness in wide temperature range, can enlarge the bright range of coating.
In electrolytic copper plating solution brightening agent can also be arranged in addition, its composition is a sulfo-propyl sodium sulfonate, and consumption is 1-20ppm, and the best is 2-10ppm.For example SP, SH110, itself and M, N, MBT are used that effect is remarkable, and use range is wide, is suitable for the wiring board electro-coppering.
Above-mentioned electrolytic copper plating solution need carry out after the multiple times of filtration after each component interpolation is finished, and moves processing at the pneumatic blending and the mechanical type negative electrode that carry out fierceness, and degree is 0.6-1.5 meters/minutes, and continues to keep solution circulated in galvanized process.
By adopting above-mentioned technical solution, the present invention has obtained following technological merit and effect: adopt in the present invention to be dispersion agent by the additive that uses with the anion surfactant of the sodium salt that contains sulfo-succinic acid fat base and oxyethylene group, improved the comprehensive plating performance of electrolytic copper plating solution significantly, make it have the high dispersive performance, good ductility, good covering power has more characteristic when wiring board is made the perforation plating; By adding the crystallization fining agent, can in wide temperature range, plate out leveling and the good all bright cladding of toughness, can enlarge the bright range of coating, further improved the quality of coating.Be the experimental data of electrolytic copper plating solution of the present invention performance under different proportionings below:
Survey dispersive ability with the far and near cathode method in the Haring cell, be formulated as sour copper additives with other components, be electroplated to the specified time under certain condition after, with analytical balance weigh up closely, the weightening finish m1 and the m2 of negative electrode far away, according to following calculating formula calculating covering power T:
T = K - ( m 1 / m 2 ) K + ( m 1 / m 2 ) - 2 × 100 %
In the formula: T-dispersive ability
K-far and near negative electrode and anode spacing from ratio
M1-nearly negative electrode weightening finish, g
M2-negative electrode weightening finish far away, the g cathode current density is 0.5A/dm 2The time, the dispersive ability of additive different content
Additive level (mM) Dispersive ability
0 12.3%
0.5 51.7%
1 74.6%
1.5 73.9%
Below for aperture ratio be the data determination of the homogeneity of 2:1-10:1:
Homogeneity in the hole:
Figure A200710125013D00071
Below electroplate the data determination of homogeneity for whole plate:
Whole plate homogeneity: (ft 2-square feet)
The plate area Homogeneity
0.5ft 2 >90%
0.5ft 2-1ft 2 >85%
1ft 2-1.5ft 2 >80%
1.5ft 2-2ft 2 >75%
>2ft 2 >70%
[embodiment]
Be the specific embodiment of the present invention below.
In concrete the use, the specific requirement that can be used in combination is set size of current and the electroplating time that is fit to oneself according to the requirement that its electro-coppering is thick, under the situation that required electroplating thickness is determined:
A: negative film way
1: electric current is big more, and the time is short more, and the galvanized copper layer of institute is thick more, and the metal level space is big more, and ductility is poor more, and the effect of heat shock resistance is very bad, but highly efficient in productivity.
2: electric current is more little, and the time is long more, and the galvanized copper layer of institute is thin more, the densification of metal level space, and ductility is good, and the effect of heat shock resistance is fine, but production efficiency is lower.
B: positive way
The needed thickness of positive way is disposablely to reach needed thickness, so require client's electroplating time long and current density is bigger.
In printed circuit board was produced, along with the raising of present product structure, various electronic products were walked under the situation of " little ", require each vigour part of electronic product and accessory complicated and simple little, the variation that wiring board is also so thereupon is mainly reflected in diminishing of live width line-spacing, the diminishing of aperture.Also there are those to have the wiring board of a large amount of separate wells, its requirement is higher, harsher, a maximum difficult problem is that the homogeneous performance of its plate face separate wells and circuit differs greatly, if galvanized equipment own is limited, so just cause hole, high electric current position little easily, the insufficient serious phenomenon of low current position thickness, under these circumstances, it requires the performance of electroplating additive can adapt to such wiring board and electroplates requirement.
In printed circuit board is produced, along with the increase of aperture ratio, the homogeneity of hole coating particularly is particular about on the basis of efficient also worse and worse now, galvanized current density is substantially all bigger, guarantee that the homogeneity of hole coating just necessarily requires all platings of copper plating additive very good.This cover product in lay special stress on the effect of this performance,
Core content in the present invention is to have on the basis of technology, adding novel dispersant, and concrete material comprises the alkyl lipid sulfonate sodium of succsinic acid, contains the amber acid ester sodium salt of amine, contains the amber acid ester sodium salt of oxyethyl group.The interpolation scope is 0.05-5g/L in plating bath, and the best is 0.1-2g/L.For example alcohol ether sulfo-succinic acid monoester disodium (DAPS), Succinic Acid diamyl fat sodium sulfonate (AY-65), 1-sulphonyl amber acid ester-2-oxyethylene group-3-hydroxyl-4-sodium succinate (TPSO3), Succinic Acid dihexyl sodium sulfonate (MA-80), Succinic Acid alkyl polyoxyethylene ether monoesters disodium sulfonate salt (A-102) etc. can effectively improve the quality of coating.For on the basis of above-mentioned electrolytic copper plating solution, further improve the effect and the quality of coating, can add some crystallization fining agent and brightening agents again.
Embodiment 1:
Each set of dispense of electrolytic copper plating solution is such as following:
Copper sulfate: 50g/L
Sulfuric acid: 160g/L
Chlorine ion concentration: 35ppm
Dispersion agent uses: ether sulfosuccinic acid monoester disodium (DAPS) adding proportion is: 0.05g/L
The crystallization fining agent: 2-mercaptobenzoimidazole (M) adding proportion is: 0.5ppm
Brightening agent: sulfo-propyl sodium sulfonate adding proportion is: 1ppm
Temperature: 20-30 ℃
Current density: 2A/dm 2
Anodic current density: 1A/dm 2
According to the electrolytic copper plating solution of above-mentioned component configuration, through multiple times of filtration, fierce pneumatic blending, the mechanical type negative electrode moves, and it is 0.6 meter/minute that its translational speed is controlled at, and continues to keep the electrolytic copper plating solution circulation in electroplating process.
Embodiment 2:
Each set of dispense of electrolytic copper plating solution is such as following:
Copper sulfate: 90g/L
Sulfuric acid: 200g/L
Chlorine ion concentration: 80ppm
Dispersion agent uses: Succinic Acid diamyl fat sodium sulfonate (AY-65) adding proportion is: 10g/L
The crystallization fining agent: the mercaptobenzothiazole adding proportion is: 0.2ppm
Brightening agent: thiazoline propane sulfonic acid sodium adding proportion is: 5ppm
Temperature: 20-30 ℃
Current density: 3/dm 2
Anodic current density: 1A/dm 2
According to the electrolytic copper plating solution of above-mentioned component configuration, through multiple times of filtration, fierce pneumatic blending, the mechanical type negative electrode moves, and it is 1 meter/minute that its translational speed is controlled at, and continues to keep the electrolytic copper plating solution circulation in electroplating process.
Embodiment 3:(most preferred embodiment)
Each set of dispense of electrolytic copper plating solution is such as following:
Copper sulfate: 75g/L
Sulfuric acid: 180g/L
Chlorine ion concentration: 60ppm
Dispersion agent uses: 1-sulphonyl amber acid ester-2-oxyethylene group-3-hydroxyl-4-sodium succinate (TPSO3) adding proportion is: 2.5g/L
The crystallization fining agent: 2-mercaptobenzoimidazole (M) adding proportion is: 0.4ppm
Brightening agent: the sodium polydithio-dipropyl sulfonate adding proportion is: 3ppm
Temperature: 20-30 ℃
Current density: 2.2A/dm 2
Anodic current density: 1A/dm 2
According to the electrolytic copper plating solution of above-mentioned component configuration, through multiple times of filtration, fierce pneumatic blending, the mechanical type negative electrode moves, and it is 1.2 meters/minute that its translational speed is controlled at, and continues to keep the electrolytic copper plating solution circulation in electroplating process.
Embodiment 4:
Each set of dispense of electrolytic copper plating solution is such as following:
Copper sulfate: 75g/L
Sulfuric acid: 180g/L
Chlorine ion concentration: 60ppm
Dispersion agent uses: Succinic Acid dihexyl sodium sulfonate (MA-80) adding proportion is: 2.5g/L
The crystallization fining agent: 2-mercaptobenzoimidazole (M) adding proportion is: 0.4ppm
Brightening agent: the sodium polydithio-dipropyl sulfonate adding proportion is: 4ppm
Temperature: 20-30 ℃
Current density: 2.5A/dm 2
Anodic current density: 1A/dm 2
According to the electrolytic copper plating solution of above-mentioned component configuration, through multiple times of filtration, fierce pneumatic blending, the mechanical type negative electrode moves, and it is 1 meter/minute that its translational speed is controlled at, and continues to keep the electrolytic copper plating solution circulation in electroplating process.
Embodiment 5:
Each set of dispense of electrolytic copper plating solution is such as following:
Copper sulfate: 60g/L
Sulfuric acid: 170g/L
Chlorine ion concentration: 65ppm
Dispersion agent uses: Succinic Acid alkyl polyoxyethylene ether monoesters disodium sulfonate salt (A-102) adding proportion is: 4.5g/L
The crystallization fining agent: the mercaptobenzothiazole adding proportion is: 0.2ppm
Brightening agent: thiazoline propane sulfonic acid sodium adding proportion is: 5ppm
Temperature: 20-30 ℃
Current density: 2.5A/dm 2
Anodic current density: 1.8A/dm 2
According to the electrolytic copper plating solution of above-mentioned component configuration, through multiple times of filtration, fierce pneumatic blending, the mechanical type negative electrode moves, and it is 1.5 meters/minute that its translational speed is controlled at, and continues to keep the electrolytic copper plating solution circulation in electroplating process.
Embodiment 6:
Each set of dispense of electrolytic copper plating solution is such as following:
Copper sulfate: 40g/L
Sulfuric acid: 190g/L
Chlorine ion concentration: 45ppm
Dispersion agent uses: Succinic Acid alkyl polyoxyethylene ether monoesters disodium sulfonate salt (A-102) adding proportion is: 1g/L
Temperature: 20-30 ℃
Current density: 1.8A/dm 2
Anodic current density: 1.4A/dm 2
According to the electrolytic copper plating solution of above-mentioned component configuration, through multiple times of filtration, fierce pneumatic blending, the mechanical type negative electrode moves, and it is 1.5 meters/minute that its translational speed is controlled at, and continues to keep the electrolytic copper plating solution circulation in electroplating process.
Foregoing description can only be counted as preferred embodiment.Those those of skill in the art in the art and those manufacturings or use people of the present invention should recognize other multiple variation pattern of the present invention.Therefore, it being understood that the foregoing description usefulness that only presents a demonstration, it can't be construed as limiting scope of the present invention, scope of the present invention by according to the principle of patent law, comprise that the following claim that the principle of equivalent is explained limits.

Claims (7)

1, a kind of electroplate copper liquor for printed circuit board comprises copper-bath and dispersion agent, it is characterized in that: described dispersion agent contains the sodium salt solution of sulfo-succinic acid fat base and oxyethylene group for this.
2, a kind of electroplate copper liquor for printed circuit board according to claim 1 is characterized in that: dispersion agent comprises the alkyl lipid sulfonate sodium of succsinic acid, contains the amber acid ester sodium salt of amine, contains the amber acid ester sodium salt of oxyethyl group.
3, according to claim 1 or 2 any one described a kind of electroplate copper liquor for printed circuit board, it is characterized in that: described dispersion agent interpolation scope in copper sulfate bath is 0.05-5g/L.
4, according to claim 1 or 2 any one described a kind of electroplate copper liquor for printed circuit board, it is characterized in that: described dispersion agent interpolation scope the best in sulfuric acid ` copper electrolyte is 0.1-2g/L.
5, a kind of electroplate copper liquor for printed circuit board according to claim 1 is characterized in that: the component of described copper-bath is copper sulfate 50-90g/L, sulfuric acid 160-200g/L, chlorion 35-80ppm.
6, according to claim 1 or 5 any one described a kind of electroplate copper liquor for printed circuit board, it is characterized in that: the best configuration ratio of the component of copper-bath is copper sulfate 75g/L, sulfuric acid 180g/L, chlorion 60ppm.
7, a kind of electroplate copper liquor for printed circuit board according to claim 1 is characterized in that: also include crystallization fining agent and brightening agent in the described electrolytic copper plating solution.
CNA2007101250131A 2007-12-14 2007-12-14 Electroplate copper liquor for printed circuit board Pending CN101457375A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534702A (en) * 2010-12-15 2012-07-04 罗门哈斯电子材料有限公司 Method of electroplating uniform copper layer
CN102534715A (en) * 2012-02-18 2012-07-04 沈阳飞机工业(集团)有限公司 Process method for electroplating copper on surface of micro aluminum wire
CN103046089A (en) * 2012-12-28 2013-04-17 广东达志环保科技股份有限公司 Functional copper electroplating solution of and method thereof
CN104213170A (en) * 2014-09-16 2014-12-17 四川海英电子科技有限公司 Copper plating method for high-order high-density circuit board
CN106939432A (en) * 2017-04-25 2017-07-11 东强(连州)铜箔有限公司 A kind of compound additive and its process for producing of think gauge Copper Foil
CN107858717A (en) * 2017-12-25 2018-03-30 深圳市新日东升电子材料有限公司 flexible high speed copper plating additive and preparation method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102534702A (en) * 2010-12-15 2012-07-04 罗门哈斯电子材料有限公司 Method of electroplating uniform copper layer
CN102534702B (en) * 2010-12-15 2015-06-03 罗门哈斯电子材料有限公司 Method of electroplating uniform copper layer
CN102534715A (en) * 2012-02-18 2012-07-04 沈阳飞机工业(集团)有限公司 Process method for electroplating copper on surface of micro aluminum wire
CN103046089A (en) * 2012-12-28 2013-04-17 广东达志环保科技股份有限公司 Functional copper electroplating solution of and method thereof
CN103046089B (en) * 2012-12-28 2015-06-24 广东达志环保科技股份有限公司 Functional copper electroplating solution of and method thereof
CN104213170A (en) * 2014-09-16 2014-12-17 四川海英电子科技有限公司 Copper plating method for high-order high-density circuit board
CN106939432A (en) * 2017-04-25 2017-07-11 东强(连州)铜箔有限公司 A kind of compound additive and its process for producing of think gauge Copper Foil
CN106939432B (en) * 2017-04-25 2018-05-08 东强(连州)铜箔有限公司 A kind of compound additive and its process for producing of think gauge copper foil
CN107858717A (en) * 2017-12-25 2018-03-30 深圳市新日东升电子材料有限公司 flexible high speed copper plating additive and preparation method thereof

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