CN1245060C - A method for manufacturing plated-through-hole non-formaldehyde electrolytic thick copper - Google Patents
A method for manufacturing plated-through-hole non-formaldehyde electrolytic thick copper Download PDFInfo
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- CN1245060C CN1245060C CN 02153642 CN02153642A CN1245060C CN 1245060 C CN1245060 C CN 1245060C CN 02153642 CN02153642 CN 02153642 CN 02153642 A CN02153642 A CN 02153642A CN 1245060 C CN1245060 C CN 1245060C
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Abstract
The present invention relates to a method for manufacturing non-formaldehyde electrolytic thick copper plated with through holes, particularly to a method for plating through holes without using formaldehyde. The present invention is mainly characterized in that irregular charges on the hole wall are adjusted to uniformly arranged charges after a circuit board is drilled, and meanwhile, copper foil on the surface of the circuit board generates a uniform slight rough phenomenon; a colloid catalyst activating agent is added on the hole wall of the through holes and is attached to the hole wall; atoms on the hole wall are removed, and one kind of platinum atoms or copper atoms are left; atomic compounds containing sulfur are attached on the platinum atoms or copper atoms on the hole wall so as to increase the electric conductivity of the hole wall; copper plating liquid having good coating properties is plated on the hole wall so as to achieve the effect on switching on current.
Description
Technical field
The invention relates to a kind of thick copper production method of formaldehydeless electrolysis of plated-through-hole, it refers to a kind of formaldehydeless plated-through-hole manufacture method especially, its be with printed circuit board (PCB) after boring, and need not use any chemical mixing soup that contains formaldehyde, go to plate a method of metal copper.
Background technology
Printed circuit board (PCB) provides the main support body of electronics spare part when installing with interconnection, is the indispensable main fundamental parts of all electronic products.Because the quality of design quality of printed circuit board (PCB) not only directly influences outside the reliability of electronic product, but the also competitiveness of left and right sides system product integral body, so can the say so mother of electronic system product of circuit board.Printed circuit board (PCB) is because the cost and the yield rate height of its product, become the emphasis of various countries' development in the past during the decade with surging forward, in Taiwan, because the circuit board industry is to be only second to integrated circuit, the output value ranks the industry (annual value of production of nineteen ninety-five has promptly reached 45,900,000,000 yuan of New Taiwan Currencies) in full court gulf second, and is distinguished to the contribution of Taiwan macroeconomy.Yet more than the material and chemical raw material that uses in the board, printed circuit board manufacturing method, its manufacture method complicated is if not effectively management will cause the greatest influence of environment.Therefore, how reducing its impact to environment, can take into account the development that industry continues again, is the task of top priority of this industry.
The purpose of plated-through-hole is to make the non-conductor through hole after boring, and the closely knit firm also metal copper layer of tool conductivity of deposition one deck on its hole wall is as the base material (substrate) of follow-up electro-coppering.The most frequently used plated-through-hole manufacture method is electroless copper (electroless copper) at present, is called the method for electroless copper again.See also Fig. 1, it is the flow chart for known plated-through-hole manufacture method; As shown in the figure, its step is to include:
Step 10 is removed the particulate on substrate through-hole and surface, whole hole/adjustment (conditioner) unit of fingerprint with alkaline cleaning solution (cleaner);
Step 20 is used solution such as sulfuric acid/hydrogen peroxide, sodium peroxydisulfate or ammonium persulfate, and slight corrosion copper clad laminate surface to be to increase roughness, makes follow-uply when carrying out activation process, with catalyst microetch (microetch) unit of preferable adherence is arranged;
Step 30 is soaked circuit board and is placed the acid tank liquor that contains stannous chloride and palladium bichloride, makes catalyst (palladium) be reduced and be deposited on substrate through-hole and lip-deep catalysis/activation (catalyst) unit;
Step 40, excessive colloidal tin is removed in dissolving, makes palladium fully expose out, as accelerationization (accelerator) unit of the ground of chemical copper deposition; And
Step 50 is soaked the circuit board after the above-mentioned conductor processing and is placed the chemical copper tank liquor, and the bivalent cupric ion in the tank liquor promptly is reduced into metallic copper, and is deposited on substrate through-hole and lip-deep electroless copper (electroless copper) unit.
The advantage of the method is easy and with low cost for control, and also can obtain good quality, its shortcoming is then tediously long for taking, and in manufacture method, can use formaldehyde (a kind of carcinogen), if the miscarriage meeting causes the severe contamination of environment to reach for the operator of factory and the harm of common people's health, in addition, this manufacture method is used very a large amount of water, and the use of multiple chelating agent then is to have increased the difficulty of waste water treatment and cost.
Content of the present invention
Therefore, how a kind of thick copper wet type of formaldehydeless electrolysis manufacture method of plated-through-hole is proposed at the problems referred to above, not only can improve tradition and use the shortcoming of formaldehyde, be not to use for a long time the person earnestly to look forward to and the inventor bears in mind always always, and the inventor is based on the research of the plated-through-hole Related product of engaging in printed circuit board (PCB) for many years, exploitation, and sale practical experience, it is the idea of thinking and improveing, poor its people's professional knowledge, through research and design in many ways, special topic is inquired into, finally work out a kind of formaldehydeless wet type manufacture method improvement of plated-through-hole, can solve the above problems.So
Main purpose of the present invention, be to provide a kind of thick copper production method of formaldehydeless electrolysis of plated-through-hole, printed circuit board (PCB) is finished boring back via inwall, plate a metallic copper, wet type copper facing manufacture method by plated-through-hole of the present invention, the reagent of its adding does not contain formaldehyde, can reduce environmental hazard and lifting operating personnel's safety.
Traditional printed circuit board (PCB) needs thereon cloth to build metal copper layer after the interlayer conduction duct is shaped, with the conducting of circuit between complete layer; Earlier with burr on the mode cleaning eye of severe brushing and high pressure washing and the break flour in the hole, again with the glue slag on the liquor potassic permanganate removal hole wall copper face; On the hole wall of cleaning out, soak again and adhere to tin palladium gelatinous layer, again it is reduced into Metal Palladium; Circuit board is dipped in the chemical copper solution, the copper ion reduce deposition in the solution is attached on the hole wall, form the through hole circuit through the catalytic action of palladium metal; Bathe the mode of electroplating with copper sulphate again and the copper layer in the via is thickeied the thickness of enough opposing following process and environment for use impact.
The present invention is the electrolytic metal copper by a kind of wet type thereafter, the manufacture method that need not use formaldehyde of bringing into plated-through-hole, it mainly is with behind the circuit boring, add a reagent, arrange to adjust electric charge disorderly on the hole wall to the electric charge of uniformity, use solution such as one sulfuric acid/hydrogen peroxide, a sodium peroxydisulfate or an ammonium persulfate, slight corrosion plate face Copper Foil produces little coarse phenomenon uniformly; This printed circuit board (PCB) is soaked in the acid solution that contains monochlor(in)ate sodium and the inferior tin of monochlor(in)ate in advance; Add colloid catalyst activator again on the hole wall of via, it is attached on the hole wall; Subsequently the atom on the hole wall is removed, only stayed one of them of palladium atom or copper atom; Then the sulfur atom-containing compound is bonded on the palladium atom or copper atom on the hole wall, to increase the conductivity of hole wall; And the good copper plating bath of lining property is plated on the hole wall, to reach the effect of conducting electric current.
The reagent that the present invention adds is to be a levelling agent; The concentration of this levelling agent is 0.01～10%V/V; During the step of the reagent of this adding, its operating temperature is to be 15～60 ℃, 1～5 minute operating time.Its concentration of this sulfuric acid is 1～10%V/V; Its concentration of this hydrogen peroxide is 5～10%V/V; It is the hybrid metal atom colloid that is selected from tin palladium or tin copper for the colloid catalyst activator of this adding; The colloid catalyst activator of this adding is to be a palladium salt or a mantoquita; This palladium salt or its total concentration of mantoquita are to be 10～600ppm/l.The colloid catalyst activator of this adding is to be a pink salt.This pink salt is to be 0.6～30g/l.The step of the colloid catalyst activator of this adding, its operating temperature is 20～50 ℃, the time is 1～9 minute.In the step with the removing of the atom on the hole wall, it is to use a fluoboric acid and sulfuric acid mixed solution to remove other atoms; The total concentration of this fluoboric acid and sulfuric acid mixed solution is 0.1～20%V/V; In the step with the removing of the atom on the hole wall, its operating condition is under room temperature, 1～5 minute; This sulfur atom-containing compound concentrations is 0.1～20%V/V; The sulfur atom-containing compound is bonded in the palladium atom or the step on the copper atom on the hole wall, and its operating condition is under room temperature, 1～5 minute; The good copper plating bath of lining property is plated in the step on the hole wall, is with an electrolysis mode its metallic copper to be plated under the hole wall; This copper plating bath is to include sulfuric acid, copper sulphate and chloride ion.The concentration of sulfuric acid is 8～15%V/V.The concentration of copper sulphate is 60～100g/l; The concentration of chloride ion is 30～120ppm/l.The good copper plating bath of lining property is plated in the step on the hole wall, and its operating condition is under room temperature, electric current 0.5～4ASD, and the time is 2～30 minutes; The concentration of this sodium chloride is that the concentration of 10～300g/l and stannous chloride is 1～100g/l.
Further understand and understanding for your juror is had architectural feature of the present invention and the effect that realized, with preferred embodiment and cooperate detailed explanation, illustrate as after:
Description of drawings:
Fig. 1 is the flow chart of known plated-through-hole manufacture method.
Fig. 2 is the manufacture method flow chart of a preferred embodiment of the present invention.
Specific implementation
In making pcb board, its inside comprises buried via hole or the region between the heart and the diaphragm hole, and each laminate must hole earlier and electroplate before bonding.If without this step, so just can not be connected to each other.
After holing by machinery equipment according to the boring demand, and the necessary process plating in hole wall the inside (plated through hole technology, Plated-Through-Hole technology, PTH).After metal treatment is made in hole wall inside, can allow each inner layer line road be connected to each other.Before beginning plating, must fall earlier the foreign material in the hole clearly.This is because can produce some physics and chemical change after the heating of the high-speed drilling of epoxy resin, as: glue slag, plethora etc., and it can cover inner PCB layer, so want to fall clearly earlier.Remove with the plating action and all can in chemical manufacturing method, finish.
The clearer production technology of most important manufacture method one plated-through-hole in the printed circuit board assembly line; The purpose of plated-through-hole is to make the closely knit firm also metal copper layer of tool conductivity of deposition one deck on the non-conductor through-hole wall after the boring, as the base material of follow-up electro-coppering.Plated-through-hole manufacture method the most commonly used at present is an electroless copper, is called the method for electroless copper again.
See also shown in Figure 2, its be for the manufacture method flow process of a preferred embodiment of the present invention as; As shown in the figure, it provides the manufacture method of a formaldehydeless plated-through-hole the present invention, and it is to include for its main step:
In step 100, the reagent that is added is to be a levelling agent, and full name of this agent is PVI, and its concentration is 0.01～10%V/V, and its operating temperature is to be 15～60 ℃, and 1～5 minute operating time, this reagent can be made into acidity or aqueous alkali, and both are all applicable.
In step 110, its concentration of sulfuric acid is 1～10%V/V, and its concentration of hydrogen peroxide is 5～10%V/V.
In step 120, it is by the acid solution of sodium chloride and stannous chloride so that this printed circuit board (PCB) purifies, and with the useful life and the life-span of extension colloid catalyst activator, and the concentration of this sodium chloride be the concentration of 10～300g/l and stannous chloride is 1～100g/l.
In step 130, wherein the colloid catalyst activator of this adding its be the hybrid metal atom colloid that is selected from tin palladium or tin copper, it is to include a palladium salt or a mantoquita, its operation concentration be to be 10～600ppm/l; And a pink salt, its operation concentration is to be 0.6～30g/l, and its operating temperature is 20～50 ℃, and the time is 1～9 minute.
In step 140, in its step with the removing of the atom on the hole wall, it is to use a fluoboric acid and sulfuric acid mixed solution to remove other atoms, and total concentration is 0.1～20%V/V, and its operating condition is under room temperature, 1～5 minute.
In step 150, this sulfur atom-containing compound concentrations is 0.1～20%V/V, and its operating condition is under room temperature, 1～5 minute.
In step 160, it is with a special copper plating bath it to be plated on the hole wall, wherein this copper plating bath is to include sulfuric acid, copper sulphate and chloride ion, wherein the concentration of this sulfuric acid is that the concentration of 8～15%V/V, copper sulphate is that the concentration of 60～100g/l and this chloride ion is 30～120ppm/l, its operating condition is under room temperature, electric current 0.5～4ASD, the time is 2～30 minutes.
Traditional electroless copper mainly is as reducing agent with formaldehyde, because the carcinogenic character of formaldehyde, therefore the present invention its provide the plated through hole technology of a formaldehydeless manufacture method, be provided in to use levelling agent, sulfuric acid and hydrogen peroxide are so that disorderly electric charge on the hole wall, its electric charge that is adjusted into uniformity is arranged, make plate face Copper Foil produce little coarse phenomenon uniformly simultaneously, and after adding colloid activation catalyst, add the sulfur atom-containing compound and be bonded on the palladium atom or copper atom on the hole wall, to strengthen its hole wall conductivity, just need not use the plated-through-hole manufacture method that contains formaldehyde by such step.
So the present invention one has novelty, progressive and can supply the industry utilization, the patent application important document that should meet China's Patent Law defined proposes application for a patent for invention undoubtedly in accordance with the law.
Only the above, it only is a preferred embodiment of the present invention, be not to be used for limiting scope of the invention process, in every case change and modify, all should be included in the claim of the present invention according to the described shape of the present patent application claim, structure, feature and the equalization of doing.
Claims (21)
1, the thick copper production method of a kind of formaldehydeless electrolysis of plated-through-hole, it is that printed circuit board (PCB) via inwall is plated layer of metal copper, it is characterized in that key step is to comprise at least:
Behind printed circuit board drilling, add a levelling agent, arrange to adjust electric charge disorderly on the hole wall to the electric charge of uniformity;
Use sulfuric acid or hydrogen peroxide, a sodium peroxydisulfate or an ammonium persulfate solution, slight this printed circuit board surface of corrosion is to increase roughness;
This printed circuit board (PCB) is soaked in the acid solution that contains monochlor(in)ate sodium and the inferior tin of monochlor(in)ate in advance;
Add colloid catalyst activator on the hole wall of via, this colloid catalyst activator is selected from the hybrid metal atom colloid of tin palladium or tin copper;
Use a fluoboric acid and sulfuric acid mixed solution that the atom on the hole wall is removed, only stay one of them of palladium atom or copper atom;
The sulfur atom-containing compound is bonded on the palladium atom or copper atom on the hole wall, to increase the conductivity of hole wall; And
Copper plating bath is plated on the hole wall.
2, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1, it is characterized in that: the concentration of this levelling agent is 0.01～10%V/V.
3, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: during the step of the reagent of this adding, its operating temperature is to be 15～60 ℃, 1～5 minute operating time.
4, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1, it is characterized in that: its concentration of this sulfuric acid is 1～10%V/V.
5, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1, it is characterized in that: its concentration of this hydrogen peroxide is 5～10%V/V.
6, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: the colloid catalyst activator of this adding is to be a palladium salt or a mantoquita.
7, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: this palladium salt or its total concentration of mantoquita are to be 10～600ppm/l.
8, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: the colloid catalyst activator of this adding is to be a pink salt.
9, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1, it is characterized in that: this pink salt is to be 0.6～30g/l.
10, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: the step of the colloid catalyst activator of this adding, and its operating temperature is 20～50 ℃, the time is 1～9 minute.
11, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1, it is characterized in that: the total concentration of this fluoboric acid and sulfuric acid mixed solution is 0.1～20%V/V.
12, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: in the step with the removing of the atom on the hole wall, its operating condition is under room temperature, 1～5 minute.
13, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1, it is characterized in that: this sulfur atom-containing compound concentrations is 0.1～20%V/V.
14, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: the sulfur atom-containing compound is bonded in the palladium atom or the step on the copper atom on the hole wall, and its operating condition is under room temperature, 1～5 minute.
15, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: copper plating bath is plated in the step on the hole wall, is with an electrolysis mode its metallic copper to be plated on the hole wall.
16, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1, it is characterized in that: this copper plating bath is to include sulfuric acid, copper sulphate and chloride ion.
17, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 16, it is characterized in that: the concentration of sulfuric acid is 8～15%V/V.
18, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 16, it is characterized in that: the concentration of copper sulphate is 60～100g/l.
19, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 16, it is characterized in that: the concentration of chloride ion is 30～120ppm/l.
20, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: copper plating bath is plated in the step on the hole wall, and its operating condition is under room temperature, electric current 0.5～4ASD, and the time is 2～30 minutes.
21, the thick copper production method of the formaldehydeless electrolysis of plated-through-hole as claimed in claim 1 is characterized in that: the concentration of this sodium chloride is that the concentration of 10～300g/l and stannous chloride is 1～100g/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02153642 CN1245060C (en) | 2002-12-03 | 2002-12-03 | A method for manufacturing plated-through-hole non-formaldehyde electrolytic thick copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02153642 CN1245060C (en) | 2002-12-03 | 2002-12-03 | A method for manufacturing plated-through-hole non-formaldehyde electrolytic thick copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1505461A CN1505461A (en) | 2004-06-16 |
| CN1245060C true CN1245060C (en) | 2006-03-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02153642 Expired - Fee Related CN1245060C (en) | 2002-12-03 | 2002-12-03 | A method for manufacturing plated-through-hole non-formaldehyde electrolytic thick copper |
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| CN (1) | CN1245060C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029409B (en) * | 2006-11-24 | 2011-03-16 | 江苏工业学院 | Pretreatment and pretreatment solution for direct porous metallizing printing IC board |
| CN101951726A (en) * | 2010-09-17 | 2011-01-19 | 昆山华扬电子有限公司 | Resistor built-in printing circuit board and manufacturing process thereof |
| US20140262801A1 (en) * | 2013-03-14 | 2014-09-18 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes |
| CN107587174A (en) * | 2017-08-30 | 2018-01-16 | 深圳市博敏兴电子有限公司 | High thickness to diameter ratio wiring board Deep hole electroplating method |
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2002
- 2002-12-03 CN CN 02153642 patent/CN1245060C/en not_active Expired - Fee Related
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| CN1505461A (en) | 2004-06-16 |
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