CN103614726A - Etching method - Google Patents
Etching method Download PDFInfo
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- CN103614726A CN103614726A CN201310557770.1A CN201310557770A CN103614726A CN 103614726 A CN103614726 A CN 103614726A CN 201310557770 A CN201310557770 A CN 201310557770A CN 103614726 A CN103614726 A CN 103614726A
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- China
- Prior art keywords
- compound
- etching
- ion
- copper
- acid
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- 238000005530 etching Methods 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims description 58
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000007788 liquid Substances 0.000 claims abstract description 58
- 239000000460 chlorine Substances 0.000 claims abstract description 48
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 46
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 31
- 230000002378 acidificating effect Effects 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims description 68
- 239000002253 acid Substances 0.000 claims description 45
- 239000012452 mother liquor Substances 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 34
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 32
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 31
- 229940045803 cuprous chloride Drugs 0.000 claims description 31
- 241000370738 Chlorion Species 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 8
- 229960003280 cupric chloride Drugs 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- -1 wherein Chemical compound 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 230000000536 complexating effect Effects 0.000 claims description 7
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 claims description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 5
- 229940095064 tartrate Drugs 0.000 claims description 5
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000010933 acylation Effects 0.000 claims description 4
- 238000005917 acylation reaction Methods 0.000 claims description 4
- 235000004279 alanine Nutrition 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002228 disulfide group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 claims description 3
- 150000003230 pyrimidines Chemical class 0.000 claims description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 4
- 239000000758 substrate Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 239000012224 working solution Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 76
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 46
- 229910052802 copper Inorganic materials 0.000 description 42
- 239000000243 solution Substances 0.000 description 40
- 238000004519 manufacturing process Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- 239000005750 Copper hydroxide Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- 206010000372 Accident at work Diseases 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009719 regenerative response Effects 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- HLDJIDQLYGRBBP-UHFFFAOYSA-N guanidine;1h-pyrrole Chemical class NC(N)=N.C=1C=CNC=1 HLDJIDQLYGRBBP-UHFFFAOYSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention discloses an acidic etching liquid without generating chlorine. The acidic etching liquid mainly comprises the following components according to working solution concentration: 80-180g/L of copper chloride (by content of copper ion), 0.3-5.0mol/L of hydrochloric acid and the balance of water, and the acidic etching liquid is characterized by also comprising a catalyst the content of which accounts for 0.1%-15% of the mass of the acidic etching liquid, wherein the catalyst has complexation on univalent or bivalent copper ion in the acidic etching liquid or can generate stable complex, and also can regulate reaction A so as to move toward the direction generating bivalent copper ion, the reaction A is shown in the specification.
Description
Related application
The application is to be on March 4th, 2011 application for a patent for invention day, application number is 201110053012.7, and denomination of invention is that mono-kind of < < does not produce the acidic etching liquid of chlorine and dividing an application of catalyzer > > thereof.
Technical field
The present invention is for printed circuit board (PCB) manufacturing, and the acidic copper chloride etching process that high precision and density circuit etching are used, is specifically related to a kind of acidic etching liquid and catalyzer thereof that does not produce chlorine.
Background technology
The development of electronic industry is very fast at present, printed circuit board (PCB) as carrying electronic product, also must be to the future development that can make more accurate circuitous pattern, the present the thinnest level that has reached 25 μ m wire diameters and 25 μ m spacing of accurate circuit, in its manufacturing processed, etching is to manufacture requisite operation in printed circuit board (PCB) process, conventionally adopts etching solution to carry out etching to printed circuit board (PCB), and 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 regeneration, need constantly in etching solution, to add additive.
For alkaline copper chloride etching solution, can utilize airborne oxygen to complete univalent copper ion to the process of bivalent cupric ion conversion, so that the bivalent cupric ion in etching solution is regenerated, also can reach this effect by additive simultaneously, for example, 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 ", promotes the dissolving of copper simple substance in alkaline ammonia cupric chloride etch systems by additive, but different from acid copper chloride etching liquid is, most of alkaline copper chloride etching solutions be take ammonia as main complexing agent, not adding any promotor just can utilize airborne oxygen to complete univalent copper ion to the switching process of bivalent cupric ion, its etching process is isotropic, that is to say in etching process, etching speed to the cunette vertical direction between circuit sidewall horizontal direction and circuit approaches, this has just caused lower etching coefficient and to the excessive etching in circuit side, such as when etching away 35 μ m Copper Foils downwards, it also will etch away the sidewall of 35 μ m, this makes it can only complete at most 100 μ m live widths and figures more than 100 μ m line-spacings, make alkaline copper chloride etching solution cannot complete even 25 μ m wire diameters and the 25 μ m spacing etching process of accurate line pattern like this of 50 μ m wire diameters and 50 μ m spacing.
For acid copper chloride etching liquid, because have than the better etching coefficient of alkaline copper chloride etching solution, can etch meticulousr line pattern (such as the thick 25 μ m wire diameters of 0.5oz copper and 25 μ m spacing or the accurate circuit of the thick 50 μ m wire diameters of 1oz copper and 50 μ m spacing), just more and more be printed the making that circuit-board industry is applied to high precision and highdensity printed-wiring board (PWB), the etched Automatic Control Theory of common acidic copper chloride is as follows:
In etching process, the basic liquid of reaction is printed in circuit-board industry and is commonly called as mother liquor, in industry, be commonly called as sub-liquid with the not supplementary liquid of cupric of comparing with basic liquid for supplementing, acid etching mother liquor is sprayed to the surface of printed circuit board (PCB), and etching mother liquor is removed unwanted copper.Because etching mother liquor reacts with copper, in etching mother liquor, bivalent cupric ion is reduced into univalent copper ion, need univalent copper ion be oxidized to bivalent cupric ion with oxygenant, and 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 the sub-liquid of etching is joined in acid etching mother liquor, unnecessary mother liquor is drained, and in this process, oxygenate content raises rapidly, when oxygenate content reaches certain value, added automatically system stops.In addition, because etching mother liquor reacts with copper, in etching mother liquor, dissolved in copper, the proportion of mother liquor is more and more higher.When proportion reaches certain value, added automatically system starts, and water is joined in acid etching mother liquor, and unnecessary mother liquor is drained, and in this process, proportion raises gradually, and when proportion reaches certain value, added automatically system stops.Due to cupric not in the sub-liquid of etching, thus the proportion of mother liquor also part by the sub-liquid of etching, adjusted.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 airborne oxygen, in existing printed circuit board acidic etching process, all to use strong oxidizer, the promotor that for example hydrogen peroxide, sodium chlorate, superoxide, nitric acid and his salt are changed to bivalent cupric ion as univalent copper ion, this class strong oxidizer singly can not promote univalent copper ion to change to bivalent cupric ion, can be 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) forming is not soluble in water, is having excessive chlorion (Cl
-) in situation about existing, 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, must add additive by univalent copper ion (Cu
1+) again convert bivalent cupric ion (Cu to
2+), guarantee etch capabilities, be called in the industry the regeneration of etching solution, the principle of regeneration is mainly to utilize 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, and this has caused the generation of following side reaction and has emitted chlorine.
Side reaction is: 2Cl
-+ oxygenant → Cl
2emit chlorine pollution environment, this has not singly polluted environment and has brought production safety problem, and make oxygenant by excessive consumption, the effective acting time of oxygenant is very short, to production process, bring very large inconvenience, 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 is directly to reclaim unnecessary copper, makes again Cu simultaneously
1+be oxidized to Cu
2+, etching solution is regenerated, larger but the reclaim equiment of this method drops into, and need to consume more electric energy;
At anode, also occur: 2Cl
-→ Cl
2+ e
-, equally emit chlorine pollution environment.
Therefore, in existing acidic copper chloride etching process, because the contribution of cuprous chloride to etching coefficient eliminated in the use of oxygenant, for more accurate line pattern, use the acidic etching liquid of oxygenant to be still difficult to realize, such as be manufactured with the precision graphic of 50 μ m live widths and 50 μ m line-spacings on 1oz thickness Copper Foil, not enough for improving the etching coefficient using after oxygenant, Japan patentee “Ji Fei electricity Co., Ltd. " application the patent No. be ZL200580001298.7, patent name is " etching solution, engraving method and printed circuit board (PCB) " patent, this patent has disclosed a kind of method that acid copper chloride etching liquid to using oxygenant adds tensio-active agent and azole raising etching coefficient, and patentee " Shantou ultrasonic PCB (two factories) company limited ", the application number of application is 200810026451.7, denomination of invention is " for the manufacture of etching solution and the engraving method of printed circuit board ", and the improvement of making needn't be added tensio-active agent but add the material that gathers guanidine class.These two kinds of methods all must be added etched inhibitor, use the reaction mechanism of inhibitor and oxygenant as follows:
Bivalent cupric ion generates univalent copper ion by copper oxidation in the situation that oxygenant exists,
Cu
2++Cu→Cu
+
Univalent copper ion and inhibitor K(B) generate to suppress film stable,
Cu
1++ K(B) → [Cu+K(B)] inhibition film ↓
The thickness of this inhibition film and the pressure of spray are inversely proportional to and play the provide protection to circuit sidewall, and suppress film simultaneously and coordinated and generate and be transferred in solution by excessive chlorion,
[Cu+K(B)] inhibition film ↓+Cl
-→ [CuCl
2]
-
Meanwhile, [CuCl
2]
-oxidized dose is oxidized to cupric,
[CuCl
2]
-+ oxygenant → Cu
2++ Cl
-
So circulation guarantees that reaction keeps continuously always.
And only use the reaction mechanism of oxygenant as follows:
Bivalent cupric ion generates univalent copper ion by copper oxidation in the situation that oxygenant exists,
Cu
2++Cu→Cu
1+
Univalent copper ion rapidly oxidized dose be oxidized to bivalent cupric ion,
Cu
1++ oxygenant → Cu
2+
So circulation guarantees that reaction keeps continuously always.
Add its object of etched inhibitor and realize high etching coefficient by forming the method for loose insoluble film, this can cause etching speed very slow, being not only the modern industry of pursuit production efficiency can not accept, also more mean that resistance erosion dry film or ink need to tolerate the attack of longer time, to covering that pitting carves, be disadvantageous, two methods of more crucial this do not solve the problem that chlorine overflows yet.
Meanwhile, by adding oxygenant, maintain the method for bivalent cupric ion content, can be because of oxygenant constantly by chlorion (Cl
-) in the mode of release chlorine, consume, and be prone to bivalent cupric ion (Cu under copper concentration
2+) local overrich phenomenon, be difficult to the etching speed that remains fast, and in etched process, need constantly oxygen consumed agent, improved raw materials cost and for controlling the added automatically system cost of oxygenant filling.
Summary of the invention
The first object of the present invention is to overcome 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 monovalence copper in copper chloride acid etching liquid be oxidized to cupric to improve etched speed, and etching speed is stable, etching coefficient is high, avoid producing the catalyzer that chlorine overflows.
In order to realize above-mentioned the first object, a kind of acidic etching liquid that does not produce chlorine, this solution comprises mother liquor and sub-liquid, described mother liquor is comprised 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 comprised 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 comprise to the monovalence in acidic etching liquid and bivalent cupric ion have complexing action maybe can generate stable complex, and adjustable reaction A in redox potential and do not produce the catalyzer of chlorine; Further technical scheme is, described catalyzer choose in following compounds a kind of compound or multiple compounds composite;
A：
Described compound is:
Containing amino or/and acylations 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 the acid of the haloid element except chlorion and salt, or the derivative of heterogeneous ring compound and heterogeneous ring compound.
Further technical scheme is, a kind of compound or multiple compounds that described catalyzer is chosen in ammonia, quadrol, EDTA, trolamine, ethanamide, DMF, guanidine, triethylene tetramine, polyethylene polyamine are composite.
Further technical scheme is, a kind of compound or multiple compounds that described catalyzer is chosen in alanine, Padil, halfcystine, tartrate, nitrilotriacetic acid(NTA), citric acid, methylsulfonic acid, thionamic acid, phenol sulfonic acid are composite.
Further technical scheme is, the pyridine of the derivative compound that belongs to heterogeneous ring compound and heterogeneous ring compound chosen by described catalyzer, a kind of compound or multiple compounds in the derivative of pyridine, quinoline, quinoline, pyrimidine, pyrimidine derivatives are composite.
Further technical scheme is, a kind of compound or multiple compounds that described catalyzer is chosen in BTA, disulfide group benzo thiazole, benzoglyoxaline, dipyridyl, oxine are 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 the second object, a kind of catalyzer that does not produce the acidic etching liquid of chlorine, described acidic etching liquid is acid copper chloride etching liquid, described catalyzer to the monovalence in acidic etching liquid and bivalent cupric ion have complexing action maybe can generate stable complex, and adjustable reaction A in redox potential and do not produce chlorine; Further technical scheme is, described catalyzer choose in following compounds a kind of compound or multiple compounds composite;
A：
Described compound is:
Containing amino or/and acylations 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 the acid of the haloid element except chlorion and salt, or the derivative of heterogeneous ring compound and heterogeneous ring compound.
Further technical scheme is, a kind of compound or multiple compounds that described catalyzer is chosen in ammonia, quadrol, EDTA, trolamine, ethanamide, DMF, guanidine, triethylene tetramine, polyethylene polyamine are composite.
Further technical scheme is, a kind of compound or multiple compounds that described catalyzer is chosen in alanine, Padil, halfcystine, tartrate, nitrilotriacetic acid(NTA), citric acid, methylsulfonic acid, thionamic acid, phenol sulfonic acid are composite.
Further technical scheme is, the pyridine of the derivative compound that belongs to heterogeneous ring compound and heterogeneous ring compound chosen by described catalyzer, a kind of compound or multiple compounds in the derivative of pyridine, quinoline, quinoline, pyrimidine, pyrimidine derivatives are composite.
Further technical scheme is, described catalyzer choose a kind of compound in BTA, disulfide group benzo thiazole, 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, the present invention has realized without the monovalence copper under chlorine generation to cupric smooth conversion, avoided chlorine to overflow, because chlorine is a kind of severe corrosive yellow-green colour gas of severe toxicity, in World War II, Zeng Zuowei chemical weapons are used, particularly the proportion of chlorine is heavier than air, chlorine is not easy to fly away when overflow in Residential areas and city, therefore to overflow be the industrial accident that has hazardness to chlorine, in these several years, the chlorine of industry of printed circuit boards overflows in rising trend, special in the Chinese intensive areas of printed-wiring board (PWB) manufacturing enterprise such as Pearl River Delta, always there are every year several accidents to occur, use of the present invention can be stopped the generation of this class 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 copper concentration high (such as copper concentration 140g/L) in the situation that is used oxygenant more quickly and effectively, the more important thing is that it provides than using the higher etching coefficient of oxidisability additive, for example: more than 5.4 etching coefficients, in the epoch of hyundai electronics industry develop rapidly, wiring board is to the meticulousr future development trend that is inevitable, and can the height of the etching coefficient of circuit etching be realize the key of making accurate circuit, although the substantial risk that the acid copper chloride etching liquid that industry is generally used has chlorine to overflow, but constantly replace safe alkaline copper chloride etching solution, caving-in bash under the operation pressure of making accurate circuit just, and the present invention has obtained higher etching coefficient when solution chlorine overflows, this just each printed-wiring board (PWB) manufacturing concern be badly in need of, can allow user make more accurate line pattern, the demand that can better adapt to electron trade development, the ability of 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 is than using the more effective speed that improves acid etching of oxidisability additive, in etching process, when catalyzer, choose to copper is had complexing action or can generate and stablize the amino that contains of joining with thing with copper, or/and acylations is 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 copper is had complexing action or can generate stable acid and salt of joining with the haloid element except chlorion of thing with copper, or copper is had complexing action or can generate stable joining and the heterogeneous ring compound of thing and the derivative of heterogeneous ring compound with copper, choose in above compound a kind of compound or multiple compounds composite, adopt such catalyzer, itself can not be consumed first catalyzer, it two is that etching speed is faster than using the acid copper chloride etching liquid of oxygenant under high copper content, this has not only improved the efficiency of producing, reduced the consumption of etching solution, reduced the treatment capacity of waste liquid, in etched process, do not need oxygen consumed agent simultaneously, the added automatically system cost that has reduced raw materials cost and annotated for controlling oxygenant, the manufacturing cost of whole reduction printed-wiring board (PWB), the whole economic efficiency of inevitable raising industry.
Embodiment
Below in conjunction with embodiment, further describe in detail.
(1) in acid copper chloride etching liquid, univalent copper ion is difficult to bivalent cupric ion conversion, its former because:
(in neutral environment) in the ordinary course of things, univalent copper ion is as follows to the standard potential of bivalent cupric ion conversion:
Under alkaline condition:
The reduction potential of oxygen in the aqueous solution is:
This that is to say that the easier dissolved oxygen of monovalence copper is oxidized to cupric in neutral and alkali solution; And in acid and high chloride ion environment, univalent copper ion and chlorion formation stable complex [CuCl2]-, molecular balance sharply tilts to generating univalent copper ion direction.According to Nernst equation, calculate actual redox potential following (concrete calculation procedure is known by each chemical industry dealer, omits) herein:
The reduction potential of oxygen in the aqueous solution is:
Under this condition, univalent copper ion is also larger than the reduction potential of oxygen to the redox potential of bivalent cupric ion conversion, 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, with copper powder, reduces acid Cupric Chloride Solution and obtains white cuprous chloride and precipitate to produce cuprous chloride.
(2) the present invention is by adding non-oxidizing catalyzer, and bivalent cupric ion forms stable compound and allow reaction balance 2. carry out left, and its reaction mechanism is as follows:
Cu
2++Cu+Cl
-+e-→CuCl
Cuprous chloride precipitation is coordinated and is transferred in solution by excessive chlorion,
CuCl↓+Cl
-→[CuCl
2]
-
At catalyzer and spray and take out [CuCl2] under wind action-reacted by airborne dioxygen oxidation, its reaction is as follows:
[CuCl
2]
-+ catalyzer+O
2→ [Cu
2++ catalyzer]+Cl
-
Whole reaction process realizes without the conversion under chlorine generation condition.
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, the embodiment that Cupric Chloride Solution content is chosen 80g/L, 140g/L, 175g/L, tri-values of 180g/L with copper (comprising monovalence and bivalent cupric ion) calculating does to verify, the source of chlorion is hydrochloric acid, and chloride ion content is chosen 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 of copper hydroxide precipitation, it is not the scope that mandatory requirement limits, as long as meet, do not cause occurring copper hydroxide precipitation, do not cause corrosion preventing layer corrosion come off can, actually implement according to the difference of the catalyzer adding and change (specifically seeing in embodiment), in sub-liquid, the source of chlorion is hydrochloric acid, chloride ion content is chosen 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 of copper hydroxide precipitation, it is not the scope that mandatory requirement limits, as long as meet, do not cause occurring copper hydroxide precipitation, not causing corrosion preventing layer corrosion to come off can, actual enforcement changes (specifically seeing in embodiment) according to the difference of the catalyzer adding, the preparation of described sub-liquid is except not forming basic identical with mother liquor copper ions, because copper in etching process constantly incorporates in mother liquor, mother liquor content of copper ion is increased, the object of add supplementing sub-liquid is constant in order to maintain in mother liquor the content of cupric ion, 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 base material 1oz thickness Copper Foil conventional in printed-wiring board (PWB) manufacturing and that be made with 50 μ m live widths and 50 μ m line-spacings, do example, use the existing fan nozzle generally adopting, nozzle distance plate face 10cm, spray presses the sprinkling system of 0.3MPa as facilities and equipments, the operating temperature range of controlling mother liquor is 40～50 ℃, it is actual that to choose best working temperature be 45 ℃, 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 comparison of the copper chloride acid etching liquid of embodiment 16A is in Table 1, the component providing according to table 1 and ratio preparation copper chloride acid etching liquid.
Table 1:
" _ _ _ _ _ _ _ _ _ " represent not add any catalyzer.
Concrete operating process is as follows:
First in mother liquor to the continuous etching of base material a few hours, best elects 8 hours as; In etching process, constantly add and compare the sub-liquid that does not contain copper with mother liquor, to maintain copper (comprising monovalence and the bivalent cupric ion) content in solution; The sub-liquid of adding compare with mother liquor except other components cupric not identical with mother liquor; This sub-liquid is removed beyond comparative example, all contains catalyzer listed in table 1.After 4 hours, observe following items:
A, bivalent cupric ion content;
B, etching speed slow down with respect to comparative example or accelerate, with respect to the speed of comparative example is fast, more than 30% be designated as A, with respect to the speed of comparative example is fast, more than 10% be designated as B, with respect to the speed of comparative example suitable be designated as C, with respect to the speed of comparative example is slow, more than 15% be designated as D; With respect to the speed of comparative example with before 8 hours, compared constant being designated as steadily, % is accelerated in being designated as of accelerating with respect to the speed of comparative example, that with respect to the speed of comparative example, slows down 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,
Etching coefficient etching line pattern wire diameter out between 4.0～5.0 diminishes, but is less than 30% be designated as: qualified,
Etching coefficient diminishes in 5.0 above etchings wire diameter out, is less than 20% be designated as: good;
The air ambient at e, scene, has no irritating odor; Divide non-stimulated smell, slight smell, three grades of serious pungent odours.
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, show and add after catalyzer, 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 just can obtain high etching coefficient by adding etched inhibitor.In acidic copper chloride etching process relatively in the past, although added the acidic etching liquid etching speed of oxygenant, become faster, but the oxygenant using has been eliminated the contribution of cuprous chloride to etching coefficient, this is because the interpolation of oxygenant, make the cuprous chloride that generates in etching process destroyed, cannot form at copper face the cause of protochloride copper film, this also makes the acid etching of having added oxygenant be difficult to obtain gratifying etching coefficient.
The present invention does not use oxygenant, and has just promoted reaction balance 2. to carry out left, still maintains certain cuprous ion after molecular balance.The film that forms cuprous chloride at copper face is not damaged, need not adds inhibitor and just obtain high etching coefficient.Its reaction mechanism is as follows:
Bivalent cupric ion is oxidized to copper cuprous chloride and suppresses film in the situation that chlorion exists,
Cu
2++ Cu → CuCl ↓ inhibition film
The thickness of this inhibition film and the pressure of spray are inversely proportional to, and play the provide protection to circuit sidewall;
Cuprous chloride suppresses film and is coordinated and be transferred in solution by 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
-
So circulation guarantees that reaction keeps continuously always.
Retain cleverly in the present invention a small amount of cuprous chloride, to obtain high etching coefficient, certainly, further added inhibitor, as azole guanidine class can strengthen very high etching coefficient; But blocked up and stable inhibition film can bring slower etching speed, and this will be according to specific circumstances, decide the amount of interpolation 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 not promoting univalent copper ion changes to bivalent cupric ion, so etched speed will slow down because bivalent cupric ion constantly consumes minimizing, the existing content that maintains bivalent cupric ion by adding oxygenant, but because oxygenant constantly can be by chlorion (Cl
-) in the mode of release chlorine, consume, so the time maintaining is very short, if continuous, maintain fast speed after each interpolation, must continuous adding oxygenant; 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 is 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 higher speed of oxygenant, its experimental result is as shown in table 3.In the embodiment of table 3 15A, 16A, under higher copper concentration 175g/L and 180g/L, the etching speed that has added the etching solution of catalyzer is used the etching speed of oxygenant to compare with comparative example 3A, obviously faster, and in comparative example 3A, because the impact of the bivalent cupric ion of local overrich, etched speed significantly declines compared with comparative example 2.This main difference because of chemical dynamics process, under the higher situation of content of copper ion, the mantoquita that copper surface is oxidized to divalence can not be dissolved in solution in time because partial concn is too high, and at this moment reaction is subject to concentration difference control and etching speed is declined.Its reaction mechanism is as follows:
Bivalent cupric ion generates univalent copper ion by copper oxidation in the situation that oxygenant exists,
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 is because local overrich can not dissolve into solution timely,
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 in the situation that using catalyzer, and the process that the course of reaction is left copper face at cupric ion is that the mode with cuprous title complex occurs, is not therefore subject to the impact of copper ion concentration height.
In a word, the present invention is not by using under the precondition of 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 or multiple compounds in BTA, disulfide group benzo thiazole, benzoglyoxaline, dipyridyl, oxine are composite as catalyzer, to regulate in reaction A redox potential in suitable scope
A：
The method that keeps cupric concentration in copper chloride acid etching liquid, has avoided the chlorine overflow problem that uses oxygenant to occur; Simultaneously do not use oxygenant, allow cuprous chloride insoluble film be utilized and obtained high etching coefficient; The catalyzer adding 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, does not allow to be subject to the impact of content of copper ion.
It should be noted that, embodiments of the invention are only that the present invention is described targetedly, practice is not only confined to the compound using in lifted embodiment, its preferred embodiment be not also likely in optimum example, above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, according to the prompting of above-described embodiment, do apparent change, and other every changes that do not depart from essence of the present invention, within all should being included in the scope described in claim.
Claims (10)
1. an engraving method, is characterized in that comprising the following steps: a) comprise the acidic etching liquid mother liquor of catalyzer to the continuous etching of base material; B) described catalyzer 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 that generates bivalent cupric ion; C) in oxytropism etching solution mother liquor, add sub-liquid, to maintain the content of cupric ion and catalyzer in acidic etching liquid, described cupric ion is monovalence cuprous ion and bivalent cupric ion;
Reaction A:
2. engraving method according to claim 1, it is characterized in that, described mother liquor is mainly comprised of Cupric Chloride Solution, chlorion and hydrogen ion, cupric chloride is calculated as 80～180g/L with content of copper ion, hydrogen ion content is 0.3～5.0N, chloride ion content is 160～330g/L, and the content of described compound is the 0.1%-15% that accounts for mother liquor quality; Mother liquor is initialization etching solution.
3. engraving method according to claim 1, is characterized in that, described sub-liquid is mainly comprised of chlorion and hydrogen ion, wherein, hydrogen ion content is 0.3～6.0N, and chloride ion content is 160～330g/L, and the content of described compound is the 0.1%-15% that accounts for sub-liquid quality; It is constant to maintain in etching solution content of copper ion that sub-liquid is used for being added into mother liquor.
4. engraving method according to claim 1, is characterized in that, does not produce chlorine in the process of described engraving method.
5. engraving method according to claim 1, is characterized in that, has all the time cuprous chloride in described acidic etching liquid, and described cuprous chloride forms and suppresses film at substrate surface.
6. engraving method according to claim 1; it is characterized in that; described compound choose a kind of compound in following compounds or multiple compounds composite: containing amino and/or acylations is amino and/or the organic or inorganic compound of hydroxyl and/or carbonyl and/or alcohol acid group and/or sulfenyl and/or sulfonate radical; or the acid of the haloid element except chlorion and salt, or the derivative of heterogeneous ring compound and heterogeneous ring compound.
7. engraving method according to claim 6, is characterized in that, a kind of compound or multiple compounds that described compound is chosen in ammonia, quadrol, EDTA, trolamine, ethanamide, DMF, guanidine, triethylene tetramine, polyethylene polyamine are composite.
8. engraving method according to claim 6, it is characterized in that, a kind of compound or multiple compounds that described compound is chosen in alanine, Padil, halfcystine, tartrate, nitrilotriacetic acid(NTA), citric acid, methylsulfonic acid, thionamic acid, phenol sulfonic acid are composite.
9. engraving method according to claim 6, it is characterized in that, described compound chooses the pyridine of the derivative compound that belongs to heterogeneous ring compound and heterogeneous ring compound, a kind of compound or multiple compounds in the derivative of pyridine, quinoline, quinoline, pyrimidine, pyrimidine derivatives are composite.
10. engraving method according to claim 9, is characterized in that, a kind of compound or multiple compounds that described compound is chosen in BTA, disulfide group benzo thiazole, benzoglyoxaline, dipyridyl, oxine are composite.
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| CN105479965A (en) * | 2015-12-16 | 2016-04-13 | 东莞运城制版有限公司 | Copper chloride corrosion device and method for printing roller |
| CN116103655A (en) * | 2022-12-25 | 2023-05-12 | 江苏中德电子材料科技有限公司 | Metal alkaline etching solution for integrated circuit and preparation method thereof |
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| 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 |
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| 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 |