RU2729265C1 - Solution for chemical etching of copper - Google Patents
Solution for chemical etching of copper Download PDFInfo
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- RU2729265C1 RU2729265C1 RU2020101878A RU2020101878A RU2729265C1 RU 2729265 C1 RU2729265 C1 RU 2729265C1 RU 2020101878 A RU2020101878 A RU 2020101878A RU 2020101878 A RU2020101878 A RU 2020101878A RU 2729265 C1 RU2729265 C1 RU 2729265C1
- Authority
- RU
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- Prior art keywords
- solution
- copper
- polyvinyl alcohol
- hydroquinone
- etching
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 title claims abstract description 19
- 238000003486 chemical etching Methods 0.000 title claims abstract 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 23
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000005530 etching Methods 0.000 abstract description 19
- 238000004140 cleaning Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004870 electrical engineering Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 102200110702 rs60261494 Human genes 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical class [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
Изобретение относится к области химической обработки меди и может быть использовано при изготовлении микросхем в радиоэлектронной, электротехнической промышленности и гальваническом производстве.The invention relates to the field of chemical processing of copper and can be used in the manufacture of microcircuits in the radio-electronic, electrical industry and galvanic production.
Цель изобретения - повышение качества очистки поверхности меди, скорости травления, обеспечение стабильности раствора.The purpose of the invention is to improve the quality of cleaning the copper surface, the etching rate, to ensure the stability of the solution.
Известен аналог Авторское свидетельство (19) SU ОО 1505983 А1 (51) 4 C23G 1/06 от 07.09.89, раствор для химической обработки поверхности изделий из меди. Известный раствор используют для удаления окалины с поверхности меди. Раствор для удаления окалины с поверхности меди содержит:Known analogue Copyright certificate (19) SU OO 1505983 A1 (51) 4 C23G 1/06 dated 09/07/89, solution for chemical surface treatment of copper products. A known solution is used to remove scale from the copper surface. A solution for descaling copper surfaces contains:
- фосфорная кислота (1,834 г/см3), 19.2-20.8 мл;- phosphoric acid (1.834 g / cm 3 ), 19.2-20.8 ml;
- натрий или калий пирофосфорнокислый 50-150 г.;- sodium or potassium pyrophosphate 50-150 g;
- синтокс-20 м (10%-ный раствор), 0.8-1.2 мл;- Syntox-20 m (10% solution), 0.8-1.2 ml;
- вода до 1 л.- water up to 1 liter.
Однако, известный раствор недостаточно эффективно очищает поверхность меди, на поверхности меди имеются следы окислов и пригара. Из-за малого содержания в растворе синтокса-20М, 0.8-1.2 мл, при обработке поверхности металла трудно соблюдать указанное количество.However, the known solution does not effectively clean the copper surface; there are traces of oxides and burnt on the copper surface. Due to the low content of Syntox-20M, 0.8-1.2 ml, in the solution, it is difficult to observe the specified amount when processing the metal surface.
В качестве прототипа выбран патент (19) RU(11) 2061101 (13) С1Patent (19) RU (11) 2061101 (13) C1 was chosen as a prototype
(51) МПК6 C23G 1/02 от 27.05.1996, раствор для одновременного травления и обезжиривания металлов.(51) IPC 6 C23G 1/02 dated 05/27/1996, solution for simultaneous etching and degreasing of metals.
Известен раствор для травления и обезжиривания черных металлов, меди, алюминия и их сплавов, содержащий ортофосфорную кислоту, поверхностно-активное вещество, комплексообразующую добавку, сульфосалициловую кислоту, ацетон, гидроокись аммония, азотнокислый цинк и воду.Known solution for etching and degreasing ferrous metals, copper, aluminum and their alloys, containing phosphoric acid, surfactant, complexing additive, sulfosalicylic acid, acetone, ammonium hydroxide, zinc nitrate and water.
Однако, известный раствор недостаточно эффективно очищает поверхность металлов при травлении и обезжиривании, скорость травления недостаточно высокая. Из-за сложного многокомпонентного химического состава раствора, при проведении травления и обезжиривания трудно контролировать и обеспечивать соотношение компонентов травильного раствора.However, the known solution does not effectively clean the surface of metals during etching and degreasing, the etching rate is not high enough. Due to the complex multicomponent chemical composition of the solution, during etching and degreasing, it is difficult to control and ensure the ratio of the components of the etching solution.
Предлагаемое изобретение - это раствор для травления меди, содержащий также ортофосфорную кислоту, но в отличие от прототипа, введены гидрохинон и поливиниловый спирт при следующем соотношении компонентов, мас. %:The proposed invention is a solution for etching copper, also containing orthophosphoric acid, but unlike the prototype, hydroquinone and polyvinyl alcohol are introduced with the following ratio of components, wt. %:
- ортофосфорная кислота - 35-45:- orthophosphoric acid - 35-45:
- гидрохинон - 0.5-2.0;- hydroquinone - 0.5-2.0;
- поливиниловый спирт - 0.5-2.0;- polyvinyl alcohol - 0.5-2.0;
- вода, остальное.- water, the rest.
Раствор для травления готовят следующим образом. Производят растворение в воде при комнатной температуре компонентов, мас. %:The pickling solution is prepared as follows. The components are dissolved in water at room temperature, wt. %:
- ортофосфорная кислота (1.69-1.71 г/см3) - 35-45;- orthophosphoric acid (1.69-1.71 g / cm 3 ) - 35-45;
- гидрохинон - 0.5-2.0;- hydroquinone - 0.5-2.0;
- поливиниловый спирт - 0.5-2.0, растворяют в воде при температуре 80-90°С при перемешивании.- polyvinyl alcohol - 0.5-2.0, dissolved in water at a temperature of 80-90 ° C with stirring.
Для приготовления водного раствора поливинилового спирта используют марки поливинилового спирта по ГОСТ 10779-78.To prepare an aqueous solution of polyvinyl alcohol, polyvinyl alcohol grades are used according to GOST 10779-78.
Травящее действие раствора обеспечивается действием ортофосфорной кислоты.The etching action of the solution is provided by the action of phosphoric acid.
Повышение качества очистки поверхности изделий из меди достигается при введении в раствор гидрохинона и поливинилового спирта. Гидрохинон восстанавливает окислы меди на поверхности изделия. Поливиниловый спирт, как поверхностно-активное вещество, образует комплексы с солями фосфорнокислой меди, что способствует повышению качества очистки поверхности изделий из меди.Improving the quality of cleaning the surface of copper products is achieved by introducing hydroquinone and polyvinyl alcohol into the solution. Hydroquinone reduces copper oxides on the surface of the product. Polyvinyl alcohol, as a surfactant, forms complexes with copper phosphate salts, which improves the quality of cleaning the surface of copper products.
В приготовленный раствор для травления погружают изделие из меди на 15 секунд при комнатной температуре. Обработанную поверхность изделия не надо промывать водой.A copper article is immersed in the prepared etching solution for 15 seconds at room temperature. The treated surface of the product does not need to be rinsed with water.
Раствор стабилен в течение 30 суток.The solution is stable for 30 days.
Качество очистки поверхности оценивают внешним осмотром. Поверхность должна быть чистой, без следов смазки, цветов побежалости, потемнений. Поверхность должна равномерно смачиваться водой.The surface cleaning quality is assessed by external examination. The surface must be clean, without any traces of grease, tarnishing, or discoloration. The surface should be evenly wetted with water.
После очистки поверхности изделия, производят горячее лужение или нанесение других гальванических покрытий.After cleaning the surface of the product, hot tinning or other galvanic coatings are applied.
Проверяют качество сцепления покрытия с металлом согласно ГОСТ 9.302-88.Check the quality of adhesion of the coating to the metal in accordance with GOST 9.302-88.
Примеры, показывающие процесс травления, приведены в таблице.Examples showing the etching process are shown in the table.
Как видно из таблицы, скорость травления изделия из меди (примеры №№1-5), по сравнению с прототипом (пример №13) выше в 1,74-1,80 раза.As can be seen from the table, the etching rate of a copper product (examples No. 1-5), compared to the prototype (example No. 13), is 1.74-1.80 times higher.
Снижение концентрации ортофосфорной кислоты ниже заявляемой (пример №6) уменьшает скорость травления изделия из-за недостатка ортофосфорной кислоты.A decrease in the concentration of orthophosphoric acid below the claimed one (example No. 6) reduces the etching rate of the product due to a lack of phosphoric acid.
Увеличение концентрации ортофосфорной кислоты выше заявляемой (примеры №7 и №8) не оказывает заметного влияния на скорость травления.An increase in the concentration of phosphoric acid above the claimed one (examples No. 7 and No. 8) does not have a noticeable effect on the etching rate.
Уменьшение концентрации гидрохинона ниже заявляемой (пример №9) или уменьшение концентрации поливинилового спирта ниже заявляемой (пример №10) значительно уменьшает скорость травления.A decrease in the concentration of hydroquinone below the claimed one (example No. 9) or a decrease in the concentration of polyvinyl alcohol below the claimed one (example No. 10) significantly reduces the etching rate.
Увеличение концентрации поливинилового спирта (пример №11) или увеличение концентрации гидрохинона (пример №12) выше заявляемой незначительно влияет на скорость травления.An increase in the concentration of polyvinyl alcohol (example No. 11) or an increase in the concentration of hydroquinone (example No. 12) above the claimed one insignificantly affects the etching rate.
Скорость травления меди (г/м2⋅с) определяют по убыли массы изделия по формуле:The copper etching rate (g / m 2 ⋅s) is determined by the loss of the product weight according to the formula
где m1 и m2- соответственно начальная и конечная масса изделия, r;where m 1 and m 2 - respectively, the initial and final weight of the product, r;
S - площадь поверхности медного изделия, 52⋅10-4 м2;S is the surface area of a copper product, 52⋅10 -4 m 2 ;
τ - время, 15 с.τ - time, 15 s.
Преимущества заявляемого раствора, по сравнению с прототипом, заключаются в повышении скорости травления, раствор стабилен в течение 30 суток, высокое качество очистки поверхности, отсутствие газовыделения. Раствор содержит в своем составе значительно меньше компонентов.The advantages of the proposed solution, in comparison with the prototype, are to increase the etching rate, the solution is stable for 30 days, high quality surface cleaning, no gas release. The solution contains significantly fewer components.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2020101878A RU2729265C1 (en) | 2020-01-16 | 2020-01-16 | Solution for chemical etching of copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2020101878A RU2729265C1 (en) | 2020-01-16 | 2020-01-16 | Solution for chemical etching of copper |
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| RU2729265C1 true RU2729265C1 (en) | 2020-08-05 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1505983A1 (en) * | 1987-07-10 | 1989-09-07 | Ивановский Химико-Технологический Институт | Composition for removing scale from metal surface |
| RU2061101C1 (en) * | 1994-01-10 | 1996-05-27 | Молохина Лариса Аркадьевна | Solution fo simultaneous pickling and degreasing of metals |
| RU2105085C1 (en) * | 1994-02-04 | 1998-02-20 | Всероссийский научно-исследовательский институт авиационных материалов | Composition for removing atmosphere corrosion products from surface of stainless steel |
| WO2002050331A2 (en) * | 2000-12-20 | 2002-06-27 | Seiko Epson Corporation | Surface treatment method for ornamental parts and ornamental parts produced by the method |
| KR20170011828A (en) * | 2015-07-24 | 2017-02-02 | 동우 화인켐 주식회사 | Etchant composition and manufacturing method of an array substrate for liquid crystal display |
-
2020
- 2020-01-16 RU RU2020101878A patent/RU2729265C1/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1505983A1 (en) * | 1987-07-10 | 1989-09-07 | Ивановский Химико-Технологический Институт | Composition for removing scale from metal surface |
| RU2061101C1 (en) * | 1994-01-10 | 1996-05-27 | Молохина Лариса Аркадьевна | Solution fo simultaneous pickling and degreasing of metals |
| RU2105085C1 (en) * | 1994-02-04 | 1998-02-20 | Всероссийский научно-исследовательский институт авиационных материалов | Composition for removing atmosphere corrosion products from surface of stainless steel |
| WO2002050331A2 (en) * | 2000-12-20 | 2002-06-27 | Seiko Epson Corporation | Surface treatment method for ornamental parts and ornamental parts produced by the method |
| KR20170011828A (en) * | 2015-07-24 | 2017-02-02 | 동우 화인켐 주식회사 | Etchant composition and manufacturing method of an array substrate for liquid crystal display |
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