CN105648426B - 沉铜组合液 - Google Patents
沉铜组合液 Download PDFInfo
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- CN105648426B CN105648426B CN201610167882.XA CN201610167882A CN105648426B CN 105648426 B CN105648426 B CN 105648426B CN 201610167882 A CN201610167882 A CN 201610167882A CN 105648426 B CN105648426 B CN 105648426B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 239000010949 copper Substances 0.000 title claims abstract description 191
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 190
- 239000007788 liquid Substances 0.000 title claims abstract description 174
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- -1 hydroxypropyl Chemical group 0.000 claims description 3
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 claims description 2
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical class C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 2
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 abstract 1
- 230000003138 coordinated effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910002668 Pd-Cu Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 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 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 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 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 210000003038 endothelium Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/422—Plated through-holes or plated via connections characterised by electroless plating method; pretreatment therefor
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemically Coating (AREA)
Abstract
本发明公开了一种沉铜组合液，该沉铜组合液含有多种有效成分，如无机盐、氢氧化钠、络合剂、稳定剂、还原剂、工业酒精等，各种组分相互协调作用，性质稳定，沉铜效果好，改善了以往沉铜液对小孔径的PCB板材沉着不上铜及背光不良，影响板材品质的问题。此外，该沉铜组合液配制时先分别配制化铜A液，化铜B液、化铜C液和化铜M液，使用时用去离子水将上述四种溶液按一定的比例稀释，可以避免沉铜操作时药液不断补充的情况，减少废液的排放量，对环境的影响程度降低。
Description
技术领域
本发明涉及印制电路板孔内金属化技术，尤其涉及在印制线路板化学沉铜技术领域。
背景技术
随着电子产品朝向精密细化发展方向趋势日益明朗，对电子元器件相互连接的紧密程度的要求也越来越高。组装电子厂家往往需把电子元器件通过元器件孔内薄铜镀层与锡焊接进行电路导电，电路板材孔内沉铜层通常会受到导电元器件发热引起板材热胀冷缩现象引起断路问题，因此PCB线路板的化学沉铜品质是影响导电元器件质量的重要因素。
通信技术的高速发展，电子产品的不断升级，PCB设计线路精密细化，因此PCB板的孔径也逐渐变小。由于孔内表面张力等因素，纵横比高的PCB板在沉铜工艺上会产生沉不上铜或背光不良等异常结果，板材也会最终因开路报废。
以往化学镀铜是指在没有外加电流的条件下，利用溶液中的金属铜盐及还原剂，在具有催化活性的基体表面(钯表面)上进行自催化氧化还原反应，在基体表面形成具有一定厚度和功能的金属铜的一种表面处理技术。化学沉铜原理反应式：
CuSO4+2HCHO+4NaOH→Cu+NaSO4+2HCOONa+2H2O+H2↑
1.电子的形成：HCHO+OH-→H3COO-
H3COO-+OH-→HCOO-+H2O+H-
H-→H0+e-(在Pd的导电作用下)
2.钯表面起始反应：Pd+2e-+Cu2+→Pd-Cu
Pd-Cu+2e-+Cu2+→Pd-Cu+Cu
3.自我催化反应：Cu0+2e-+Cu2+→CuO+CuO
沉铜的目的是使双层或多层印制电路板的非金属孔，通过氧化还原反应达到在孔壁沉积上一层均匀的铜箔然后通过加镀铜厚形成导电回路。目前化学沉铜液主要成分为甲醛、氢氧化钠、硫酸铜及相应的络合剂，对小孔径的PCB板材普遍存在沉着不上铜及背光不良等品质缺陷，并且沉铜药水废液排放量大，对环境造成较大污染。
发明内容
本发明的目的在于提供一种沉铜组合液，以解决现有技术中的沉铜液对小孔径的PCB板材沉着不上铜及背光不良、板材品质差和沉铜操作时需要不断补充药液，废液排放量大的问题。
为了解决上述技术问题，本发明所采用的技术方案为：
本发明提供一种沉铜组合液，由单独储存的化铜A液、化铜B液、化铜C液、化铜M液与去离子水按比例混合而成，其中：所述化铜A液包含在该化铜A液中占以下浓度的各组分：510-540g/L无机盐、20-60g/L络合剂，所述浓度为各组分在该化铜A液中所占的浓度；所述化铜B液包含在该化铜B液中占以下浓度的各组分：430-580g/L氢氧化钠、30-60ml/L工业酒精、20-60g/L络合剂、0.01-0.02g/L稳定剂，所述浓度为各组分在该化铜B液中所占的浓度；所述化铜C液包含在该化铜C液中占以下浓度的各组分：200-400g/L还原剂，所述浓度为各组分在该化铜C液中所占的浓度；所述化铜M液包含在该化铜M液中占以下浓度的各组分：40-50ml/L工业酒精、2-6g/L加速剂、0.008-0.15g/L稳定剂、190-400g/L络合剂，所述浓度为各组分在该化铜M液中所占的浓度。
优选地，所述化铜A液中无机盐的浓度为530-535g/L，所述化铜A液中无机盐为氯化铜。
优选地，所述化铜B液中氢氧化钠的浓度为440-455g/L。
优选地，所述化铜B液中的络合剂的浓度为35-45g/L。
优选地，所述化铜A液和化铜B液中的络合剂均选自于：酒石酸钾钠、EDTA-4Na、羟乙基乙二胺三乙酸、四羟乙基乙二胺乙酸、四羟丙基乙二胺、乙二胺四乙酸、乙二胺四丙酸、1，2-环己二胺四乙酸、二羟甲基乙二胺四乙酸中的至少一种。
优选地，所述化铜M液中的加速剂选自于：聚乙二醇、聚丙二醇、环氧乙烷类表面活性剂中的至少一种。
优选地，所述化铜B液和化铜M液中的稳定剂均选自于：2，2-联吡啶、1，1-菲咯林、亚铁氰化钾中的至少一种。
优选地，所述化铜C液中的还原剂选自于：甲醛、非甲醛还原剂中的至少一种。
优选地，所述非甲醛还原剂选自于：次磷酸钠、乙醛酸、二甲氨基硼烷中的至少一种。
优选地，所述沉铜组合液中化铜A液、化铜B液、化铜C液、化铜M液与去离子水的体积比为0.6-1.2∶2.6∶10∶10∶76.2-76.8。
本发明的有益效果是：
1、本发明沉铜组合液采用氯化铜作为无机盐，氯化铜溶解度大，可以做成几十倍浓缩液，从而减少药水用量达到减少废液量排出的目的，相对比硫酸铜体系更加符合环保趋势；
2、络合剂可以与铜离子形成配位，阻止化学镀铜液中氢氧化铜沉淀形成，避免沉淀对沉铜速率和沉铜效果的影响；
3、沉铜组合液是通过配制化铜A液、化铜B液、化铜C液、化铜M四种化铜液后，再用去离子水按一定比例稀释混合而成的，达到了减少沉铜操作过程不断补充的药液用量以及达到减少废液排放量的目的；
4、本发明沉铜组合液对小孔径的PCB板材同样适用，保证了沉铜高级别的背光品质，不会因为小孔径PCB板材孔内表面张力而沉不上铜，影响电子元件的质量。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
【实施例1】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例1沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例1沉铜组合液中各组分的体积为：
【实施例2】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例2沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例2沉铜组合液中各组分的体积为：
【实施例3】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例3沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例3沉铜组合液中各组分的体积为：
【实施例4】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例4沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例4沉铜组合液中各组分的体积为：
【实施例5】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例5沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例5沉铜组合液中各组分的体积为：
【实施例6】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例6沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例6沉铜组合液中各组分的体积为：
【实施例7】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例7沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例7沉铜组合液中各组分的体积为：
【实施例8】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例8沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例2沉铜组合液中各组分的体积为：
【实施例9】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例9沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例9沉铜组合液中各组分的体积为：
【实施例10】
以配制化铜A液、化铜B液、化铜C液、化铜M液各1L为例，本实施例10沉铜组合液中各组分及含量如下：
以配制1L沉铜组合液为例，本实施例10沉铜组合液中各组分的体积为：
除以上列举的实施例外，本发明还包含在权利要求范围内各组分和含量组合而成的其他实施例。
对比例
【对比例1】
以配制1L化铜液为例，本对比例1化铜液中各组分及含量如下：
【对比例2】
以配制1L化铜液为例，本对比例2化铜液中各组分及含量如下：
实验例
【实验例1】
配制等量的实施例1-9的沉铜组合液和对比例1-2的化铜液，运用上述配制好的溶液对同样品质同样大小的PCB板沉铜，沉铜槽液PH值控制为12.5-13，温度为25-35℃，镀覆时间为15-30分钟，选取小孔径高纵横比的PCB多层板材做为实验测试基板。
沉铜结束后取出PCB板进行背光测试，实验步骤如下：1、剪下板子上预留的切片孔，用研磨机把所取切片磨到一排孔的中心线；2、用研磨机研磨，使切片厚度小于1/8英寸；3、将切片放在放大镜的光源上面，在10-50x放大镜下去观测孔内沉积层的覆盖情形，实验结果如表1。
表1实施例1-9的沉铜组合液和对比例1-2的化铜液背光测试结果
| 外观 | 背光等级 | 镀通孔不良率 | 废液排出量 | |
| 实施例1 | 粉红色 | 10级 | 0 | 少 |
| 实施例2 | 粉红色 | 10级 | 0 | 少 |
| 实施例3 | 粉红色 | 10级 | 0 | 少 |
| 实施例4 | 粉红色 | 10级 | 0 | 少 |
| 实施例5 | 粉红色 | 10级 | 0 | 少 |
| 实施例6 | 粉红色 | 10级 | 0 | 少 |
| 实施例7 | 粉红色 | 10级 | 0 | 少 |
| 实施例8 | 粉红色 | 10级 | 0 | 少 |
| 实施例9 | 粉红色 | 10级 | 0 | 少 |
| 比较例1 | 粉红色 | 8级 | 10％ | 多 |
| 比较例2 | 粉红色 | 7级 | 30％ | 多 |
从上述实验结果可知，运用本发明的沉铜组合液沉铜后，小孔径PCB板可以得到较高的背光等级，色泽度好，也没有镀通孔不良的现象，废液排出量少，对环境污染程度低。
以上所述仅为本发明的具体实施例和实验例，本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。
Claims (9)
1.一种沉铜组合液，其特征在于，由单独储存的化铜A液、化铜B液、化铜C液、化铜M液与去离子水按体积比为0.6-1.2:2.6:10:10:76.2-76.8的比例混合而成，其中：
所述化铜A液包含以下浓度的各组分：510-540g/L无机盐、20-60g/L络合剂，所述浓度为各组分在该化铜A液中所占的浓度；所述化铜A液中无机盐为氯化铜；
所述化铜B液包含占以下浓度的各组分：430-580g/L氢氧化钠、30-60ml/L工业酒精、20-60g/L络合剂、0.01-0.02g/L稳定剂，所述浓度为各组分在该化铜B液中所占的浓度；
所述化铜C液包含在占以下浓度的各组分：200-400g/L还原剂，所述浓度为各组分在该化铜C液中所占的浓度；
所述化铜M液包含占以下浓度的各组分：40-50ml/L工业酒精、2-6g/L加速剂、0.008-0.15g/L稳定剂、190-400g/L络合剂，所述浓度为各组分在该化铜M液中所占的浓度。
2.如权利要求1所述的沉铜组合液，其特征在于，所述化铜A液中无机盐的浓度为530-535g/L。
3.如权利要求1所述的沉铜组合液，其特征在于，所述化铜B液中氢氧化钠的浓度为440-455g/L。
4.如权利要求1所述的沉铜组合液，其特征在于，所述化铜B液中的络合剂的浓度为35-45g/L。
5.如权利要求1所述的沉铜组合液，其特征在于，所述化铜A液和化铜B液中的络合剂均选自于：酒石酸钾钠、EDTA-4Na、羟乙基乙二胺三乙酸、四羟乙基乙二胺乙酸、四羟丙基乙二胺、乙二胺四乙酸、乙二胺四丙酸、1,2-环己二胺四乙酸、二羟甲基乙二胺四乙酸中的至少一种。
6.如权利要求1所述的沉铜组合液，其特征在于，所述化铜M液中的加速剂选自于：聚乙二醇、聚丙二醇、环氧乙烷类表面活性剂中的至少一种。
7.如权利要求1所述的沉铜组合液，其特征在于，所述化铜B液和化铜M液中的稳定剂均选自于：2,2-联吡啶、1,1-菲咯林、亚铁氰化钾中的至少一种。
8.如权利要求1所述的沉铜组合液，其特征在于，所述化铜C液中的还原剂选自于：甲醛、非甲醛还原剂中的至少一种。
9.如权利要求8所述的沉铜组合液，其特征在于，所述非甲醛还原剂选自于：次磷酸钠、乙醛酸、二甲氨基硼烷中的至少一种。
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