CN103614726B - A kind of engraving method - Google Patents
A kind of engraving method Download PDFInfo
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- CN103614726B CN103614726B CN201310557770.1A CN201310557770A CN103614726B CN 103614726 B CN103614726 B CN 103614726B CN 201310557770 A CN201310557770 A CN 201310557770A CN 103614726 B CN103614726 B CN 103614726B
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Abstract
The invention discloses a kind of acidic etching liquid not producing chlorine, wherein mainly comprise cupric chloride, hydrochloric acid and water, it is characterized in that also comprising catalyzer in described acidic etching liquid, calculate by working fluid concentration, the content of each component is: cupric chloride is calculated as 80-180g/L with content of copper ion; Content of hydrochloric acid is 0.3-5.0mol/L; Surplus is water; Wherein, the content of described catalyzer is the 0.1%-15% accounting for acidic etching liquid quality; Described catalyzer has complexing action maybe can generate stable complex to the monovalence in acidic etching liquid and bivalent cupric ion, and reaction A can be regulated to move to the direction generating bivalent cupric ion; A:
Description
Related application
The application is application for a patent for invention day is on March 4th, 2011, and application number is 201110053012.7, and denomination of invention is the divisional application of " a kind of acidic etching liquid and catalyzer thereof not producing chlorine ".
Technical field
The present invention is used in printed circuit board (PCB) manufacturing, the acidic copper chloride etching process that high precision and density lines etching use, and is specifically related to a kind of acidic etching liquid and the catalyzer thereof that do not produce chlorine.
Background technology
The development of current electronic industry is very fast, as the printed circuit board (PCB) of carrying electronic product, also must to the future development that can make more accurate circuitous pattern, the level of what present precise circuit was the thinnest reach 25 μm of wire diameters and 25 μm of spacing, in its manufacturing processed, etching manufactures requisite operation in printed circuit board (PCB) process, and usually adopt etching solution to etch printed circuit board (PCB), conventional etching solution is divided into alkaline copper chloride etching solution and acid copper chloride etching liquid; And in etching process, etching solution needs reprocessing cycle to use, therefore, in order to make etching solution regenerate, need constantly in etching solution, to add additive.
For alkaline copper chloride etching solution, the process that the oxygen in air is changed to complete univalent copper ion to bivalent cupric ion can be utilized, regenerated to make the bivalent cupric ion in etching solution, also can reach this effect by additive simultaneously, such as, patent applicant Phibro Tech. Inc., the patent No. of application is ZL94193307.5, denomination of invention is the patent of invention of " copper etchant solution additives ", is promoted the dissolving of copper simple substance in alkaline ammonia cupric chloride etch systems by additive, but with acid copper chloride etching liquid unlike, most of alkaline copper chloride etching solution take ammonia as primary complexing agent, not adding any promotor just can utilize the oxygen in air to complete the switching process of univalent copper ion to bivalent cupric ion, its etching process is isotropic, that is in etching process, close to the etching speed of the cunette vertical direction between circuit sidewall horizontal direction and circuit, which results in lower etching coefficient and to the excessive etching in circuit side, the sidewall that such as etch away 35 μm of Copper Foils downwards while, it also will etch away 35 μm, this makes it can only complete at most the figure of more than 100 μm of live widths and 100 μm of line-spacings, make alkaline copper chloride etching solution cannot complete 50 μm of wire diameters and 50 μm of spacing even etching processes of 25 μm of wire diameters and 25 μm of so accurate line patterns of spacing.
For acid copper chloride etching liquid, because have etching coefficient more better than alkaline copper chloride etching solution, meticulousr line pattern (the thick 25 μm of wire diameters of such as 0.5oz copper and 25 μm of spacing or the precise circuit of the thick 50 μm of wire diameters of 1oz copper and 50 μm of spacing) can be etched, just more and more printed circuit-board industry is applied to the making of high precision and highdensity printed-wiring board (PWB), and the Automatic Control Theory of common acidic copper chloride etching is as follows:
In etching process, the basic liquid of reaction is printed in circuit-board industry and is commonly called as mother liquor, with for supplement compared with basic liquid not the replenisher of cupric be commonly called as in industry as sub-liquid, acid etching mother liquor is sprayed to the surface of printed circuit board (PCB), etching mother liquor unwanted copper is removed.Because etching mother liquor and copper react, in etching mother liquor, bivalent cupric ion is reduced into univalent copper ion, and with oxygenant, univalent copper ion need be oxidized to bivalent cupric ion, in mother liquor, the content of oxygenant is more and more lower.When oxygenate content is low to moderate certain value, added automatically system starts, and joins in acid etching mother liquor by sub-for etching liquid, unnecessary mother liquor is drained, and in the process, oxygenate content raises rapidly, when oxygenate content reaches certain value, added automatically system stops.In addition, because etching mother liquor and copper react, dissolved in copper in etching mother liquor, the proportion of mother liquor is more and more higher.When proportion reaches certain value, added automatically system starts, and joined by water in acid etching mother liquor, unnecessary mother liquor is drained, and in the process, proportion raises gradually, and when proportion reaches certain value, added automatically system stops.Owing to etch in sub-liquid not cupric, therefore the proportion of mother liquor also part adjusted by the sub-liquid of etching.In etching, said process circulation occurs.
In detailed process, at acid and high chloride ion (Cl
-) under environment, univalent copper ion in printed circuit board acidic cupric chloride etching solution is difficult to be oxidized to bivalent cupric ion by the oxygen in air, in existing printed circuit board acidic etching process, all use strong oxidizer, the promotor that such as hydrogen peroxide, sodium chlorate, superoxide, nitric acid and his salt are changed to bivalent cupric ion as univalent copper ion, this kind of strong oxidizer singly can not promote that univalent copper ion is changed to bivalent cupric ion, can by the chlorion (Cl in etching solution yet
-) be oxidized to chlorine (Cl
2), this side reaction is sometimes very fierce, produces a large amount of chlorine and causes security incident.
The reaction mechanism of acid etching is as follows:
Bivalent cupric ion (Cu in etching solution
2+) there is oxidisability, copper simple substance can be oxidized to univalent copper ion (Cu
1+), its reaction is as follows:
Etching reaction: Cu+CuCl
2→ 2CuCl,
The cuprous chloride (CuCl) formed is not soluble in water, is having excessive chlorion (Cl
-) deposit in case, can form the complexing ion of solubility, its reaction is as follows:
Complex reaction: CuCl+4Cl
-→ 2 [CuCl
2]
-,
Along with the etching of copper, the univalent copper ion (Cu in solution
1+) more and more, etch capabilities will soon decline, and to the last loses usefulness; For keeping etch capabilities, additive must be added by univalent copper ion (Cu
1+) again convert bivalent cupric ion (Cu to
2+), ensure etch capabilities, be called in the industry the regeneration of etching solution, the principle of regeneration mainly utilizes oxygenant by the univalent copper ion (Cu in solution
1+) being oxidized to bivalent cupric ion (Cu2+), renovation process generally has following several:
A) oxygenant regeneration, main regenerative response is:
[CuCl
2]
-+ oxygenant → 2CuCl
2,
Oxygenant generally adopts the strong oxidizers such as chlorine, sodium chlorate, hydrogen peroxide, nitrate radical, which results in the generation of following side reaction and releases chlorine.
Side reaction is: 2Cl
-+ oxygenant → Cl
2release chlorine pollution environment, this does not singly pollute environment and brings production safety problem, and make oxygenant by excessive consumption, the effective acting time of oxygenant is very short, bring very large inconvenience to production process, such as etching speed fluctuation is large, must adopt the addition of accurately complicated automatic controlling system oxygenant.
B) electrolytic regeneration, main regenerative response is:
Under galvanic effect,
At anode: Cu
1+> Cu
2++ e
-;
At negative electrode: Cu
1++ e
-> Cu
0, the advantage of this method can directly reclaim unnecessary copper, makes Cu again simultaneously
1+be oxidized to Cu
2+, etching solution is regenerated, but the reclaim equiment of this method drops into comparatively large, and needs to consume more electric energy;
Also occur at anode: 2Cl
-→ Cl
2+ e
-, equally release chlorine pollution environment.
Therefore, in existing acidic copper chloride etching process, use due to oxygenant eliminates the contribution of cuprous chloride to etching coefficient, for more accurate line pattern, the acidic etching liquid of oxygenant is used still to be difficult to realize, on 1oz thickness Copper Foil, be such as manufactured with the precision graphic of 50 μm of live widths and 50 μm of line-spacings, not enough for improving the etching coefficient after using oxygenant, the patent No. that the patentee " Ji Fei electricity Co., Ltd. " of Japan applies for is ZL200580001298.7, patent name is " etching solution, engraving method and printed circuit board (PCB) " patent, this patent diselosesll is a kind of to use the acid copper chloride etching liquid of oxygenant to add method that tensio-active agent and azole improve etching coefficient, and patentee " Shantou ultrasonic PCB (two factories) company limited ", the application number of application is 200810026451.7, denomination of invention is " etching solution and engraving method for the manufacture of printed circuit board ", and the improvement made need not be added tensio-active agent but add the material of poly-guanidine class.These two kinds of methods all must add the inhibitor of etching, use the reaction mechanism of inhibitor and oxygenant as follows:
Bivalent cupric ion is deposited at oxygenant and in case copper oxidation is generated univalent copper ion,
Cu
2++Cu→Cu
+
Univalent copper ion and inhibitor K(B) generate and suppress film to be stablized,
Cu
1++ K(B) → [Cu+K(B)] suppression film ↓
The thickness of this suppression film and the pressure of spray are inversely proportional to the provide protection played circuit sidewall, suppress film to be coordinated by excessive chlorion simultaneously and generate and be transferred in solution,
[Cu+K(B)] suppress film ↓+Cl
-→ [CuCl
2]
-
Meanwhile, [CuCl
2]
-oxidized dose is oxidized to cupric,
[CuCl
2]
-+ oxygenant → Cu
2++ Cl
-
Circulation like this ensures that reaction keeps continuously always.
And only use the reaction mechanism of oxygenant as follows:
Bivalent cupric ion is deposited at oxygenant and in case copper oxidation is generated univalent copper ion,
Cu
2++Cu→Cu
1+
Univalent copper ion rapidly oxidized dose be oxidized to bivalent cupric ion,
Cu
1++ oxygenant → Cu
2+
Circulation like this ensures that reaction keeps continuously always.
Its object of inhibitor of adding etching realizes high etching coefficient by the method forming loose insoluble film, this can cause etching speed very slow, be not only the modern industry pursuing production efficiency can not accept, also the attack of resistance erosion dry film or ink needs tolerance longer time is more meaned, to cover pitting carve be disadvantageous, these more crucial two methods do not solve yet chlorine overflow problem.
Meanwhile, maintain the method for bivalent cupric ion content by adding oxygenant, can because oxygenant be constantly by chlorion (Cl
-) consume in the mode of release chlorine, and bivalent cupric ion (Cu is easily there is under copper concentration
2+) local over-concentration phenomenon, be difficult to maintain fast etching speed, and need constantly oxygen consumed agent in the process of etching, improve raw materials cost and the added automatically system cost for controlled oxidization agent filling.
Summary of the invention
The first object of the present invention overcomes deficiency of the prior art, provides in a kind of etching process by not producing chlorine, etching coefficient is high, etching speed is fast and stable copper chloride acid etching liquid after disposable filling catalyzer.
The second object of the present invention is to provide and a kind ofly makes the monovalence copper in copper chloride acid etching liquid be oxidized to cupric to improve the speed of etching, and etching speed is stablized, etching coefficient is high, avoid producing the catalyzer that chlorine overflows.
In order to realize above-mentioned first object, a kind of acidic etching liquid not producing chlorine, this solution comprises mother liquor and sub-liquid, described mother liquor is made up of Cupric Chloride Solution, chlorion and acid group, wherein, Cupric Chloride Solution content is calculated as 80 ~ 180g/L with cupric ion, and the content of acid group is 0.3 ~ 5.0N, the source of chlorion is the salt of hydrochloric acid or various hydrochloric acid, and chloride ion content is 160 ~ 330g/L; Described sub-liquid is made up of chlorion and acid group, and wherein, the content of acid group is 0.3 ~ 6.0N, and the source of chlorion is the salt of hydrochloric acid or various hydrochloric acid, and chloride ion content is 160 ~ 330g/L; This solution also comprises has complexing action maybe can generate stable complex to the monovalence in acidic etching liquid and bivalent cupric ion and redox potential and do not produce the catalyzer of chlorine in adjustable reaction A; Further technical scheme is, described catalyzer to choose in following compounds a kind of compound or multiple compounds composite;
A：
Described compound is:
Containing amino or/and acylated amino is or/and hydroxyl is or/and carbonyl is or/and alcohol acid group is or/and sulfenyl is or/and the organic or inorganic compound of sulfonate radical; or the acid of haloid element outside removing chloride and salt, or the derivative of heterogeneous ring compound and heterogeneous ring compound.
Further technical scheme is, described catalyzer choose a kind of compound in ammonia, quadrol, EDTA, trolamine, ethanamide, DMF, guanidine, triethylene tetramine, polyethylene polyamine or multiple compounds composite.
Further technical scheme is, described catalyzer choose a kind of compound in alanine, Padil, halfcystine, tartrate, nitrilotriacetic acid(NTA), citric acid, methylsulfonic acid, thionamic acid, phenol sulfonic acid or multiple compounds composite.
Further technical scheme is, described catalyzer choose a kind of compound in the pyridine of the derivative compound belonging to heterogeneous ring compound and heterogeneous ring compound, the derivative of pyridine, quinoline, quinoline, pyrimidine, pyrimidine derivatives or multiple compounds composite.
Further technical scheme is, described catalyzer choose a kind of compound in BTA, disulfide group benzothiazole, benzoglyoxaline, dipyridyl, oxine or multiple compounds composite.
Further technical scheme is, the mass percent that described catalyzer accounts for whole acidic etching liquid is 0.1% ~ 15%.
In order to realize above-mentioned second object, a kind of catalyzer not producing the acidic etching liquid of chlorine, described acidic etching liquid is acid copper chloride etching liquid, described catalyzer have complexing action maybe can generate stable complex to the monovalence in acidic etching liquid and bivalent cupric ion and adjustable reaction A in redox potential and do not produce chlorine; Further technical scheme is, described catalyzer to choose in following compounds a kind of compound or multiple compounds composite;
A：
Described compound is:
Containing amino or/and acylated amino is or/and hydroxyl is or/and carbonyl is or/and alcohol acid group is or/and sulfenyl is or/and the organic or inorganic compound of sulfonate radical; or the acid of haloid element outside removing chloride and salt, or the derivative of heterogeneous ring compound and heterogeneous ring compound.
Further technical scheme is, described catalyzer choose a kind of compound in ammonia, quadrol, EDTA, trolamine, ethanamide, DMF, guanidine, triethylene tetramine, polyethylene polyamine or multiple compounds composite.
Further technical scheme is, described catalyzer choose a kind of compound in alanine, Padil, halfcystine, tartrate, nitrilotriacetic acid(NTA), citric acid, methylsulfonic acid, thionamic acid, phenol sulfonic acid or multiple compounds composite.
Further technical scheme is, described catalyzer choose a kind of compound in the pyridine of the derivative compound belonging to heterogeneous ring compound and heterogeneous ring compound, the derivative of pyridine, quinoline, quinoline, pyrimidine, pyrimidine derivatives or multiple compounds composite.
Further technical scheme is, described catalyzer choose a kind of compound in BTA, disulfide group benzothiazole, benzoglyoxaline, dipyridyl, oxine or multiple compound composite.
Further technical scheme is, the mass percent that described catalyzer accounts for whole acidic etching liquid is 0.1% ~ 15%.Advantage of the present invention:
1, present invention achieves without the monovalence copper under chlorine generation to cupric smooth conversion, avoid chlorine to overflow, due to the severe corrosive yellow-green colour gas that chlorine is a kind of severe toxicity, in World War II, Zeng Zuowei chemical weapons use, particularly the proportion of chlorine is heavier than air, chlorine is not easy to fly away when Residential areas and city are overflowed, therefore chlorine overflows is the industrial accident having hazardness, in these several years, the chlorine of industry of printed circuit boards overflows in rising trend, especially in the area that the printed-wiring board (PWB) manufacturing enterprises such as the Pearl River Delta of China are intensive, annual always have several accidents to occur, use of the present invention can stop the generation of this kind of accident thoroughly, and this is avoided industrial injury and industrial accident to have revolutionary meaning to safety in production and cleaner production, has high social benefit,
2, etching speed of the present invention ratio when copper concentration high (such as copper concentration 140g/L) uses oxygenant more quickly and effectively, priorly be that it provides than using the etching coefficient that oxidisability additive is higher, such as: the etching coefficient of more than 5.4, in the epoch of hyundai electronics industry develop rapidly, wiring board to be inevitable trend to meticulousr future development, and can the height of the etching coefficient of circuit etching be the key that realize making precise circuit, although the substantial risk that the acid copper chloride etching liquid that industry generally uses has chlorine to overflow, but safe alkaline copper chloride etching solution is constantly replaced, caving-in bash just under the operation pressure making precise circuit, and the present invention obtains higher etching coefficient while solution chlorine overflows, this just each printed-wiring board (PWB) manufacturing concern be badly in need of, user can be allowed to make more accurate line pattern, the demand of electron trade development can better be adapted to, the ability better making fine-line is provided, manufacture better printed-wiring board (PWB), be very beneficial for the development of electron trade,
3, the present invention's speed of improve acid etching more more effective than use oxidisability additive, in etching process, when catalyzer choose to copper have complexing action or can and copper generates stable join and thing containing amino, or/and acylated amino, or/and hydroxyl, or/and carbonyl, or/and alcohol acid group, or/and sulfenyl, or/and the organic or inorganic compound of sulfonate radical, or to copper have complexing action or can and copper generates stablize join and thing removing chloride outside the acid of haloid element and salt, or to copper have complexing action or can and copper generates to stablize and joins and the heterogeneous ring compound of thing and the derivative of heterogeneous ring compound, to choose in above compound a kind of compound or multiple compounds composite, adopt such catalyzer, first catalyzer can not be consumed itself, it two is that etching speed is faster than using the acid copper chloride etching liquid of oxygenant under high copper content, which not only improves the efficiency of production, decrease the consumption of etching solution, decrease the treatment capacity of waste liquid, in the process of etching, do not need oxygen consumed agent simultaneously, decrease raw materials cost and the added automatically system cost for controlled oxidization agent filling, the manufacturing cost of overall reduction printed-wiring board (PWB), the whole economic efficiency of inevitable raising industry.
Embodiment
Further describe in detail below in conjunction with embodiment.
(1) in acid copper chloride etching liquid, univalent copper ion is difficult to bivalent cupric ion conversion, and its reason is:
In the ordinary course of things (in neutral environment), the standard potential that univalent copper ion is changed to bivalent cupric ion is as follows:
In the basic conditions:
Oxygen reduction potential is in aqueous:
This is that is in neutrality and alkali solution, and monovalence copper is more easily oxidized to cupric by dissolved oxygen; And in acid and high chloride ion environment, univalent copper ion and chlorion formed stable complex [CuCl2]-, molecular balance is sharply to generating the inclination of univalent copper ion direction.Calculate according to Nernst equation, actual redox potential following (concrete calculation procedure, known by each chemical industry dealer, is omitted herein):
Oxygen reduction potential is in aqueous:
The redox potential changed to bivalent cupric ion of univalent copper ion is also larger than the reduction potential of oxygen under these conditions, univalent copper ion cannot be changed to bivalent cupric ion by the mode of inflating or spray exhausting, this etching process is similar to the production process of industrial cuprous chloride very much, and the cuprous chloride precipitation namely using copper powder reduction acidic cupric chloride solutions to obtain white produces cuprous chloride.
(2) the present invention is by adding non-oxidizing catalyzer, and bivalent cupric ion formation stable compound allows reaction balance 2. carry out left, and its reaction mechanism is as follows:
Cu
2++Cu+Cl
-+e-→CuCl
Cuprous chloride precipitation is transferred in solution by the cooperation of excessive chlorion,
CuCl↓+Cl
-→[CuCl
2]
-
At catalyzer and spray and [CuCl2] under taking out wind action-reacted by the dioxygen oxidation in air, its reaction is as follows:
[CuCl
2]
-+ catalyzer+O
2→ [Cu
2++ catalyzer]+Cl
-
Whole reaction process realizes without the conversion under chlorine Production conditions.
In order to prove the present invention, a kind of compound in quadrol, thionamic acid, benzotriazole, benzoglyoxaline, multi-hydroxy carboxy acid's (citric acid, tartrate), brometo de amonio and ammonia selected by catalyzer or multiple compounds is composite tests, for consisting of of the copper chloride acid etching liquid tested:
In mother liquor, Cupric Chloride Solution content calculates with copper (comprising monovalence and bivalent cupric ion) embodiment choosing 80g/L, 140g/L, 175g/L, 180g/L tri-values and does with checking, the source of chlorion is hydrochloric acid, and chloride ion content chooses 220g/L, the content of acid group (H+) is 0.3 ~ 5.0N, this selection range be in etching process corrosion preventing layer can restrain oneself with high content of copper ion under there is not the optimal choice scope that copper hydroxide precipitates, it is not the scope that mandatory requirement limits, do not cause occurring that copper hydroxide precipitates as long as meet, do not cause corrosion preventing layer to corrode coming off can, actual enforcement according to the difference of the catalyzer added and change (specifically seeing in embodiment), in sub-liquid, the source of chlorion is hydrochloric acid, chloride ion content chooses 220g/L, the content of acid group (H+) is 0.3 ~ 6.0N, this selection range be in etching process corrosion preventing layer can restrain oneself with high content of copper ion under there is not the optimal choice scope that copper hydroxide precipitates, it is not the scope that mandatory requirement limits, do not cause occurring that copper hydroxide precipitates as long as meet, not causing corrosion preventing layer corrosion to come off can, actual enforcement changes (specifically seeing in embodiment) according to the difference of the catalyzer added, the preparation of described sub-liquid forms substantially identical with mother liquor except not copper ions, because copper in etching process constantly incorporates in mother liquor, mother liquor content of copper ion is increased, add the object of supplementing sub-liquid constant in order to maintain the content of cupric ion in mother liquor, catalyzer is chosen and is accounted for 0.1% ~ 15% of whole mother liquor and sub-liquid (being whole solution) mass percent, and concrete content is shown in embodiment.
In experimentation, with 1oz thickness Copper Foil conventional in printed-wiring board (PWB) manufacturing and be made with the base material of 50 μm of live widths and 50 μm of line-spacings to do example, use the existing fan nozzle generally adopted, nozzle distance plate face 10cm, spray the sprinkling system of 0.3MPa as facilities and equipments, the operating temperature range controlling mother liquor is 40 ~ 50 DEG C, the actual working temperature choosing the best is 45 DEG C, select the copper chloride acid etching liquid comparative example 1-2 of regular convention formula, comparative example 3A and embodiment 1-14, embodiment 15A, the copper chloride acid etching liquid of embodiment 16A relatively in table 1, the component provided according to table 1 and proportions copper chloride acid etching liquid.
Table 1:
" _ _ _ _ _ _ _ _ _ " represent and do not add any catalyzer.
Concrete operating process is as follows:
First in mother liquor, etch a few hours continuously to base material, best elects 8 hours as; The sub-liquid not containing copper compared with mother liquor is constantly added, to maintain copper (comprising monovalence and the bivalent cupric ion) content in solution in etching process; The sub-liquid added compared with mother liquor except not cupric other components identical with mother liquor; Beyond this sub-liquid removing comparative example, all contain catalyzer listed in table 1.Following items is observed after 4 hours:
A, bivalent cupric ion content;
B, etching speed slow down relative to comparative example or accelerate, fast relative to the speed of comparative example more than 30% be designated as A, fast relative to the speed of comparative example more than 10% be designated as B, suitable relative to the speed of comparative example is designated as C, slow relative to the speed of comparative example more than 15% be designated as D; Constantly compared with before 8 hours relative to the speed of comparative example be designated as steadily, that accelerates relative to the speed of comparative example is designated as quickening %, and that slows down relative to the speed of comparative example is designated as the % that slows down;
Whether c, etching process have chlorine to overflow;
D, detection etching coefficient:
Etching coefficient can not etch line pattern and be designated as between 1.0 ~ 2.0: extreme difference,
Etching coefficient can not etch being designated as of line pattern between 2.0 ~ 3.0: poor,
Etching coefficient can make line pattern between 3.0 ~ 4.0 but wire diameter obviously diminishes, and is less than 40% be designated as: scrape through,
The line pattern wire diameter that etching coefficient etches out between 4.0 ~ 5.0 diminishes, but is less than 30% be designated as: qualified,
The wire diameter that etching coefficient etches out more than 5.0 diminishes, and is less than 20% be designated as: excellent;
E, on-the-spot air ambient, have no irritating odor; Divide non-stimulated smell, faint odor, serious pungent odour three grades.
Result of implementation is as table 2 below and table 3.
Table 2:
Table 3:
In above embodiment, as shown in table 2 and table 3, after catalyzer is added in display, its bivalent cupric ion relatively example 1 is all significantly improved, the combination that more preferably in embodiment 8,9,10,11,12, multiple catalysts coordinates.
Meanwhile, the present invention can maintain high etching coefficient in etching process, and acid copper chloride etching liquid disclosed by the invention no longer needs the inhibitor by adding etching just can obtain high etching coefficient.In acidic copper chloride etching process relatively in the past, although the acidic etching liquid etching speed that with the addition of oxygenant becomes faster, but the oxygenant used eliminates the contribution of cuprous chloride to etching coefficient, this is because the interpolation of oxygenant, the cuprous chloride generated in etching process is destroyed, cannot form the cause of protochloride copper film at copper face, this also makes the acid etching that with the addition of oxygenant be difficult to obtain gratifying etching coefficient.
The present invention does not use oxygenant, and just facilitates reaction balance 2. and carry out left, after molecular balance, still maintain certain cuprous ion.The film forming cuprous chloride at copper face is not damaged, inhibitor need not be added and just obtain high etching coefficient.Its reaction mechanism is as follows:
Bivalent cupric ion is deposited at chlorion and in case copper is oxidized to cuprous chloride suppression film,
Cu
2++ Cu → CuCl ↓ suppression film
The thickness of this suppression film and the pressure of spray are inversely proportional to, and play the provide protection to circuit sidewall;
Cuprous chloride suppresses film to be transferred in solution by the cooperation of excessive chlorion,
CuCl↓+Cl
-→[CuCl
2]
-
Under catalyzer provided by the invention exists, this title complex is converted into bivalent cupric ion,
[CuCl
2]
-+O
2→Cu
2++Cl
-
Circulation like this ensures that reaction keeps continuously always.
Remain a small amount of cuprous chloride cleverly in the present invention, to obtain high etching coefficient, certainly, add inhibitor further, as azole guanidine class can strengthen very high etching coefficient; But blocked up and stable suppression film can bring slower etching speed, and this will according to specific circumstances, the amount deciding to add is to change enhancing degree.
In addition, the present invention can be stable in etching process raising etching speed, in copper chloride acid etching liquid, if do not promote that univalent copper ion is changed to bivalent cupric ion, the speed so etched will slow down because bivalent cupric ion constantly consumes minimizing, the existing content maintaining bivalent cupric ion by adding oxygenant, but because oxygenant constantly can by chlorion (Cl
-) consume in the mode of release chlorine, so the time maintained after each addition is very short, if want continuous print to maintain fast speed, oxygenant must be added continuously; The non-oxidizable catalyzer that the present invention is used, in fact just plays katalysis and itself does not consume to univalent copper ion to the conversion of bivalent cupric ion.This makes it be stable to the raising of etching speed, and in fact in some occasion, as under high content of copper ion, it can obtain than using the speed that oxygenant is higher, its experimental result is as shown in table 3.In the embodiment 15A, 16A of table 3, under higher copper concentration 175g/L and 180g/L, compared with the etching speed that the etching speed that with the addition of the etching solution of catalyzer and comparative example 3A use oxygenant, obviously faster, and in comparative example 3A, because the impact of the bivalent cupric ion of local over-concentration, the speed of etching comparatively comparative example 2 significantly declines.This is main because the difference of chemical dynamics process, and when content of copper ion is higher, the mantoquita that copper surface is oxidized to divalence can not be dissolved in solution because partial concn is too high in time, and at this moment reaction makes etching speed decline by concentration difference controls.Its reaction mechanism is as follows:
Bivalent cupric ion is deposited at oxygenant and in case copper oxidation is generated univalent copper ion,
Cu
2++Cu→Cu
1+
Univalent copper ion rapidly oxidized dose be oxidized to bivalent cupric ion,
Cu
1++ oxygenant → Cu
2++ Cl
-
Cupric salt can not dissolve into solution timely due to local over-concentration,
Cu
2++ Cl
-(high density) → CuCl
2↓
Therefore the speed-raising of oxygenant not obvious in the solution of high copper content.
The present invention is when using catalyzer, and the process that the course of reaction leaves copper face at cupric ion occurs in the mode of cuprous title complex, therefore not by the impact of copper ion concentration height.
In a word, the present invention is by under the precondition that do not use oxygenant, by choosing ammonia, quadrol, EDTA, trolamine, ethanamide, DMF, guanidine, triethylene tetramine, polyethylene polyamine, alanine, Padil, halfcystine, tartrate, nitrilotriacetic acid(NTA), citric acid, methylsulfonic acid, tosic acid, phenol sulfonic acid, a kind of compound in BTA, disulfide group benzothiazole, benzoglyoxaline, dipyridyl, oxine or multiple compounds composite as catalyzer, with regulate reaction A in redox potential in suitable scope
A：
Keep the method for cupric concentration in copper chloride acid etching liquid, avoid the chlorine overflow problem using oxygenant to occur; Do not use oxygenant simultaneously, allow cuprous chloride insoluble film be utilized and to obtain high etching coefficient; The catalyzer added in fact just catalysis monovalence copper itself does not consume to cupric conversion, and copper leaves copper face with cupprous form, and this makes the raising of etching speed more stable, is not easy the impact by content of copper ion.
It should be noted that, embodiments of the invention are only targetedly the present invention is described, practice is not only confined to the compound used in lifted embodiment, its preferred embodiment be also not likely in optimum example, above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, apparent variation is done according to the prompting of above-described embodiment, and other every changes not departing from essence of the present invention, all should be included within the scope described in claim.
Claims (4)
1. an engraving method, is characterized in that comprising the following steps: a) the acidic etching liquid mother liquor of inclusion compound etches continuously to base material; B) add sub-liquid in oxytropism etching solution mother liquor, to maintain the content of cupric ion and compound in acidic etching liquid, described cupric ion is monovalence cuprous ion and bivalent cupric ion; Wherein, described compound has complexing action maybe can generate stable complex to the monovalence in acidic etching liquid mother liquor and bivalent cupric ion, and regulates reaction A to move to the direction generating bivalent cupric ion; Wherein,
Reaction A:
Wherein, described mother liquor forms primarily of described compound, Cupric Chloride Solution, chlorion and hydrogen ion; Described sub-liquid forms primarily of described compound, chlorion and hydrogen ion; Wherein, described compound chooses one or more in ammonia, quadrol, brometo de amonio, thionamic acid, tartrate, citric acid, benzoglyoxaline, benzotriazole.
2. engraving method according to claim 1, is characterized in that, the cupric chloride in described mother liquor is calculated as 80 ~ 180g/L with content of copper ion, and hydrogen ion content is 0.3 ~ 5.0N, and chloride ion content is 160 ~ 330g/L, and mother liquor is initialization etching solution; Hydrogen ion content in described sub-liquid is 0.3 ~ 6.0N, and chloride ion content is 160 ~ 330g/L, and sub-liquid is used for being added in mother liquor constant to maintain content of copper ion in etching solution; The content of described compound is the 0.1%-15% accounting for whole acidic etching liquid quality.
3. engraving method according to claim 1, is characterized in that, does not produce chlorine in the process of described engraving method.
4. engraving method according to claim 1, is characterized in that, bivalent cupric ion is deposited in case at chlorion, and copper is oxidized to cuprous chloride, and it is formed at substrate surface and suppresses film, and this suppression film is coordinated by excessive chlorion subsequently to be transferred in solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100530127A CN102154646A (en) | 2011-03-04 | 2011-03-04 | Acidic etching solution not generating chlorine and catalyst of acidic etching solution |
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| CN2011100530127A Division CN102154646A (en) | 2011-03-04 | 2011-03-04 | Acidic etching solution not generating chlorine and catalyst of acidic etching solution |
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| CN103614726B true CN103614726B (en) | 2015-07-29 |
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| CN201310557770.1A Active CN103614726B (en) | 2011-03-04 | 2011-03-04 | A kind of engraving method |
| CN2011100530127A Pending CN102154646A (en) | 2011-03-04 | 2011-03-04 | Acidic etching solution not generating chlorine and catalyst of acidic etching solution |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321908A (en) * | 2011-09-02 | 2012-01-18 | 广州市天承化工有限公司 | Recycling and regenerating process method and metal copper recovery system of acid chloride etching solution |
| CN102464392A (en) * | 2011-10-20 | 2012-05-23 | 常州亚环环保科技有限公司 | Composite dechlorination agent for removing high-concentration chlorine-containing wastewater and application method thereof |
| CN106480473B (en) * | 2015-08-31 | 2019-08-13 | 广东德同环保科技有限公司 | A kind of method of electrolytic acid copper chloride |
| CN105369251A (en) * | 2015-12-16 | 2016-03-02 | 无锡吉进环保科技有限公司 | Etching liquid for circuit board based on nano sulfur dioxide |
| CN105479965B (en) * | 2015-12-16 | 2018-12-25 | 东莞运城制版有限公司 | A kind of the copper chloride corrosion device and caustic solution of roller |
| CN107740107A (en) * | 2017-10-30 | 2018-02-27 | 珠海市智宝化工有限公司 | A kind of etching solution recycling accelerator |
| CN107740106A (en) * | 2017-10-30 | 2018-02-27 | 珠海市智宝化工有限公司 | A kind of acidic etching liquid method for reclaiming that will not produce expansion |
| CN108774747A (en) * | 2018-06-12 | 2018-11-09 | 江苏博敏电子有限公司 | A kind of electrolytic etching prepares the electrolytic etching liquid of PCB fine-lines |
| CN109234736B (en) * | 2018-08-31 | 2020-08-11 | 深圳市华星光电技术有限公司 | Long-life copper-molybdenum etching solution and etching method |
| CN110904456B (en) * | 2019-12-28 | 2022-01-14 | 上海天承化学有限公司 | Copper etching solution and preparation method and application thereof |
| CN112626523A (en) * | 2020-11-24 | 2021-04-09 | 苏州美源达环保科技股份有限公司 | Regeneration and recycling method of acidic etching solution |
| CN112831784A (en) * | 2020-12-31 | 2021-05-25 | 惠州市鸿宇泰科技有限公司 | Acidic etching solution and control method for improving etching precision thereof |
| CN113637971A (en) * | 2021-07-29 | 2021-11-12 | 深圳市立春谷雨环保科技有限公司 | Acidic etching solution based on copper extraction waste liquid of PCB (printed Circuit Board) factory and production process thereof |
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|---|---|---|---|---|
| US6129858A (en) * | 1990-07-05 | 2000-10-10 | Elo-Chem Atztechnik Gmbh | Etching solution |
| CN1989274A (en) * | 2004-06-25 | 2007-06-27 | 吉布尔.施密德有限责任公司 | Electrolytically recoverable etching solution |
| CN101443480A (en) * | 2005-11-10 | 2009-05-27 | 伊夫再循环私人有限公司 | Recyclable etching solution |
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- 2011-03-04 CN CN201310557796.6A patent/CN103602986B/en active Active
- 2011-03-04 CN CN201310557770.1A patent/CN103614726B/en active Active
- 2011-03-04 CN CN2011100530127A patent/CN102154646A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6129858A (en) * | 1990-07-05 | 2000-10-10 | Elo-Chem Atztechnik Gmbh | Etching solution |
| CN1989274A (en) * | 2004-06-25 | 2007-06-27 | 吉布尔.施密德有限责任公司 | Electrolytically recoverable etching solution |
| CN101443480A (en) * | 2005-11-10 | 2009-05-27 | 伊夫再循环私人有限公司 | Recyclable etching solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103614726A (en) | 2014-03-05 |
| CN102154646A (en) | 2011-08-17 |
| CN103602986B (en) | 2015-07-29 |
| CN103602986A (en) | 2014-02-26 |
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Effective date of registration: 20151104 Address after: Xiangzhou District 519070 Guangdong city in Zhuhai Province before Pearl Hill Road No. 63 (Kaiweidong Science & Technology Park) 3 Building 3 floor A01 Patentee after: Zhuhai wisdom Chemical Co., Ltd. Address before: 20 5A room, Lily Garden, No. 449 Chang Lu, Gongbei port, Xiangzhou District, Zhuhai, Guangdong, 519020 Patentee before: Hou Yanhui Patentee before: Wang Weiliang |