TWI242608B - Etching agent for copper or copper alloy and etching method therefor - Google Patents

Abstract

An object of the present invention is to provide an etching agent for smoothening the surface of copper under a mild condition, and to provide an etching method for smoothening the surface. To achieve the above object, an etching agent for copper or a copper alloy is provided. The etching agent for copper or a copper alloy consists of an aqueous solution containing hydroxyl amine, an oxidizer, ammonium salt, and an azole compound.

Description

1242608 V. Description of the invention d) Technical guide ^ 彳: It is about an etchant and an etching method that can etch the surface of copper or copper alloy (hereinafter referred to as copper) to a thousand slips. Prior art 1 " A coin engraving agent for forming a smooth copper surface, for example, as disclosed in Japanese Patent No. 58-2 1 0 28, contains oxalate, hydrogen peroxide, hydrazine and benzo An acidic aqueous solution of triazole. In addition, U.S. Patent No. 5 6 3 0 9 < 50 0 discloses an acidic aqueous solution containing sulfuric acid, hydrogen peroxide, and a hydrogen peroxide stabilizer. Ask the temporal, but ’. The etchant of Japanese Patent Laid-Open No. 5 8 — 2 丨 〇 2 8 has: ΐ5 2 C is processed at a high temperature, and A is liable to precipitate insoluble copper faults. ^ ° Question. In addition, the etchant of U.S. Patent No. 563 0 950 has problems such as controlling sulfuric acid concentration or hydrogen peroxide concentration in a narrow range of f, and it is easy to cause sudden boiling when the concentration of excessive chlorine is too high. In order to solve the disadvantages of the prior art, the object of the present invention is an etching method that can smoothen the copper surface under mild conditions and make the surface smooth. After making in-depth research, I-dealer, Ming found that if the surface is made of contact with hydroxylamine, oxidant, ammonium salt, and salicylate (az〇ie), the copper surface can be smoothed. The i-fluid is the invention consisting of: (1) an aqueous solution containing an aqueous amine, oxidant, ammonium salt, and azole compound 1242608-V. Description of the invention (2) Copper or copper alloy etchant . (1) A method of etching the surface to bring the surface containing hydroxylamine, an oxidizing agent, copper or a copper alloy into contact with an aqueous solution of salivary compounds, and a detailed description of the present invention is as follows. /. The hydroxylamine-based agents used in the present invention decompose and retain steel in solution: the liquid remains alkaline and inhibited. Examples include ethanolamine, N, and ': as specific examples thereof butylethanolamine, N, N- J-based ethanolamine, ^ ethyl ethanol sentences such as 〇 一 ～ 甘, 一 ethanolethanolamine, N w--^ Zhizhi, IV, (Ethyl) ethoxyethanolamine, etc.

: Glycoldiol amine, N-butyl: Private type, diethanolamine I amine, propanolamine, isopropanolamine, ~ ethanolamine diethanolamine, = oxygen aqueous solution. "-Ethylhexaki" and other alcohols: = Among the above-mentioned hydroxylamines, the ability to retain copper with mono-, mono-, and tri-ethanol amines of 8 or less is 8 ethanolamine, diethanolamine, triethanolamine, etc. Easy to take? Loquat solution is better because it has more than the above-mentioned hydroxylamine. It is easy to obtain and cheap. It can also be used in combination with the concentration of hydroxylamine in the etchant. 5 ~ 30% is better. ~ 40% (% by weight, the same below) The above-mentioned concentration of 1 ~ 40% is high, and the amount of copper which is difficult to be dissolved by the oxidant is 0 cents. The amount of copper used in the present invention is from the cost aspect. The components in the solution are examples of complex 2 systems that oxidize copper and promote its dissolution to acid salts (sodium salt, potassium salt, etc.). Examples include gas acid, gas gas, and gas. Gas acid salt (sodium salt, unloading ^ mm C: \ 2D-CODE \ 9l-08 \ 911H830.ptd page 5 1242608 V. Description of the invention (3), etc.), hypogas acid, hypochlorite (sodium salt Among potassium, potassium salts, salts with gaseous acid, gaseous acid salt, soil & dish in the above oxidants are more stable in the solution. Due to the oxidant. ^ The concentration of the oxidant in the two or more kinds of the above-mentioned nicking agents can also be used in combination. The concentration is preferably 1% to 15%, and more preferably 5% to 10%. It can accelerate the etching speed. Moreover, the oxidant itself is difficult to decompose, and from a cost point of view: Good. The ammonium salt used in the present invention is a component that promotes the dissolution of copper. As a specific example, two: may ::: ammonium, ammonium bromide, Ammonium sulfate, persulfuric acid, i] Niu Chu · Dialic acid-ammonium chloride, diammonium phosphate, triammonium phosphate, ammonium dioxalate, ammonium, ammonium adipate, ammonium lactate. Syrian, citric acid Among the above-mentioned ammonium salts, chlorinated chloride, evolved zinc chloride, diammonium phosphate, triammonium phosphate, and ammonium citrate are preferred; =, phosphoric acid: the reactivity of the chemical agent is low, which can improve the safe mouth of the solution for them And the above-mentioned ammonium salt on the milk. The female "raw". It is also possible to use two kinds together. The concentration of the ammonium salt in the etchant is preferably 10%. When the concentration is 1 ~ 10%, the speed of money engraving will not Too fast, ~% 2 ^ slow, more moderate, so it will not cause uneven depth, '^ surface. Nine J Valley is easy to get flat Copper Solution: The salivary compound of Π is a component that inhibits the dissolution of copper in the vertical direction and promotes the dissolution of copper in the water direction. Misal 1, Misal, 2-butyl benzo. Miwa, 2-phenethylbenzisal, p-aminobenzo flavor Page 6 C: \ 2D-00DE \ 91-08 \ 9ini830.ptd 1242608 V. Description of the invention (4) Imidazoles such as azole, 2-weiyl benzimid, etc., 1, 2, 4-trisal, 3-amino-1, 2, 4, 4-tri °, 1, 2, 3 -Benzene trisigma sitting, 1-benzyl trisigma sitting, tertyl benzotrisigma sitting, etc., three 17 sittings, 5 -phenyl-1 stilbene sitting, 5-fluorenyl- Four sigma sitting classes of 1 Η-four sigma sitting, 5-amino-1 Η-tetra sauing sitting, etc., benzo 塞 sigma sitting, 2-base benzo sigma sigma sitting and so on. Among the aforementioned azole compounds, imidazole, 1-vinylimidazole, 1,2,4-tri ° sitting, 3-amino-1, 2, 4-tri ° sitting, 1-tribenzyltri-11 sitting, Tetrafluorene, 5-fluorenyl-1fluorene-tetrazole, 5-amino-1fluorene-tetrazole, and other azole compounds without aromatic substituents are preferred because they are easily soluble in solution and make the copper surface smooth Works well. These azole compounds may be used in combination of two or more kinds. 2%。 The concentration of the azole compound in the etchant is preferably 0. 1 ~ 2%, more preferably 0. 4 ~ 1. 2%. In the case where the concentration is 0.1 to 2%, a smooth copper surface is easily obtained. The etchant of the present invention is alkaline, and the pH value is usually in the range of 10 to 12. Various additives may be further added to the after-cutting agent of the present invention. For example, a surfactant may be added in order to make the I-cutting more uniform. By dissolving the above components in water, the etchant of the present invention can be easily adjusted. The water is preferably water from which ionic substances and impurities have been removed, such as ion-exchanged water. The copper surface treated with the etchant of the present invention is not particularly limited, and may be, for example, a surface of a copper foil, an electroless copper plating film, an electrolytic copper plating film, a copper sprayed film, or the like. The above-mentioned copper surface is preferably a clean surface that has been cleaned by an aqueous solution of sodium hydroxide or the like, or acid-washed by sulfuric acid or hydrochloric acid.

C: \ 365 \ 91111830.ptd Page 7 1242608 V. Description of the invention (5) As a method of making the present invention-^ using the spray method, spray # ^ "touch the copper surface, dry it. , Immersion method, etc., and then washed with water Example: For the insect insecticide% ^ it f I,,] fj „^ ^ $: ^ ^ ^ ^, 30 to 120 seconds. The UL contact area is preferably the same as the "etching amount (etching depth)" standard. The smoothness is usually different. Generally, the surface of the copper surface is etched using the etchant of the present invention, which can improve the copper surface. Smoothness. Therefore, when the upper surface is larger, or if you want to obtain a smooth surface, the unevenness of the treated surface (silver engraving depth). When the surface is the same for a thousand months, you can also increase the last name engraving volume. The copper surface is etched very smoothly by using the last name etcher of the present invention to etch the copper surface. The etchant of the present invention is advantageous for pretreatment of metal plating such as nickel plating, gold plating, silver plating, tin plating, etc., and can improve The flat metal of the key metal. Also, it is beneficial to the pre-treatment of sticking the photoresist when the copper circuit pattern of the printed circuit board is formed by the photolithography method. Examples <Examples 1 to 6 and Comparative Examples 1 to 2> The ingredients shown in Table 1 were mixed to prepare an etchant. Next, the copper-clad laminate for printed circuit boards was immersed in a 5% aqueous hydrochloric acid solution for a immersion time of 15 seconds, and then washed with water, dried, and washed. Clean copper surface. Spray below at 25 ° C 1 shown in the etchant, time is 3 seconds billion, name engraved 2 // m, and then washed with water, and dried. Then, from the solubility

C: \ 2D-C0DE \ 91-08 \ 91111830.ptd page &amp; page 1242608 V. Description of the invention (6) Second, the money is engraved 2 // m, then washed and dried. Then, the value of the last name was calculated based on the weight, surface area, and specific gravity of the dissolved copper. The smoothness of the treated copper surface was evaluated using gloss. The gloss is obtained by measuring a 20-degree specular gloss in accordance with JIS Z 874 1 using a portable gloss meter PG-1M manufactured by Nippon Denshoku Industries Co., Ltd. The results are shown in Table 1. &Lt; Comparative Example 1 &gt; As in Example 1, an etchant was prepared and etched, but the copper surface was hardly engraved. Table 1 shows the glossiness of the obtained surface. <Comparative Example 2> As in Example 1, an etchant was prepared and the copper surface was etched. Table 1 shows the gloss of the obtained surface.

C: \ 2D-C0DE \ 91-08 \ 91111830.ptd Page 9 1242608 V. Description of the invention (7) [Table 1] Example No. Composition (% by weight) Gloss Diethanolamine 10 Sodium hypochlorite 10 1 Ammonium sulfate 6 82.0 Bu Vinyl imidazole 0.8 Ion-exchanged water 73.2 Monoethanolamine 6 Sodium hypochlorite 10 2 Ammonium sulfate 5 76.6 1-Vinyl imidazole 0.8 7 Ion-exchanged water 78.2 Diethanolamine 10 Sodium hypochlorite 10 3 Ammonium citrate 6 91.3 1-Vinyl imidazole 0.6 Ion-exchanged water 73.4 Two Ethanolamine 10 sodium hypochlorite 10 4 ammonium sulfate 5 83.4 benzimidazole 1 ion-exchanged water 74 monoethanolamine 15 5 sodium chlorate 15 89.6

C: \ 2D-OODE \ 91 -08 \ 91111830.ptd Page 10 1242608 V. Description of the invention (8) Table 1

C: \ 2D-C0DE \ 91-08 \ 91111830.ptd ammonium chloride 4 benzimidazole 1 ion-exchanged water 65 6 monoethanolamine 10 sodium chlorate sulfuric acid Table 5 5-methyl-1H-tetrazole 1.2 ion-exchanged water 68 8 87.9 Comparative Example I Sodium diethanolamine hypochlorite 1Q 1-vinylimidazole 0.8 Ion-exchanged water 79.2 24.4 Comparative Example 2 Diethanolamine 10 Sodium hypochlorite IQ Ammonium sulfate 6 Ion-exchanged water 74 6.3 Page 11

Page i 1242608 Case No. 91118830 Λ_η Correction Λ 92. 12.; | 3 Alternatives V. Description of the invention (9) — As shown in Table 1, by using the etchant of the present invention, the copper surface can be etched to have a thickness of 7 Smooth surface with a gloss of 6.6 or more. <Examples 7 to 1 4> The copper surface was treated in the same manner as in Example 1 except that the etchant shown in Table 2 was used, and the smoothness of the copper surface after the treatment was evaluated. The results are shown in Table 2.

(3: \ Total file \ 91 \ 91 丨 11830 \ 911 1 1830 (replacement)-1. mouth "Page 12 1242608 Case No. 91118830 A_ Revision 92, 12. 2 3 Replacement page V. Description of invention (10) 2 Example No. Composition (% by weight) Gloss Example 7 N-fluorenylethanolamine 10 Hypochlorous acid 15 Ammonium sulfate 5 Benzimidazole 1 Ion-exchanged water 79 88.0 Example 8 Propanolamine 1 Chlorous acid 15 Amine sulfonic acid Ammonium 4 1,2,4-triazole 2 Ion-exchanged water 78 83.5 Example 9 28% ammonia 40 potassium nitrite 15 Ammonium lactate 1 Tetramium 0.1 Ion-exchanged water 43.9 92.0 Example 1 0 Propanolamine 15 Chloric acid 1 Sulfate 4 Tetrazole 1 Ion-exchanged water 79 81.5 Example 11 28% ammonia 20 20 Chloric acid 10 Ammonium citrate 1 10 Benzimidazole 2 Ion-exchanged water 58 85.9 Example 12 N-ethylethanolamine 30 Chlorous acid 7 Lactic acid Ammonium 6 1,2,4 · Triazole 2 Ion-exchanged water 55 79.9 Example 13 Diethanolamine 20 Sodium nitrosate 3 Ammonium sulfamate 8 1 · Vinyl imidazole 1.5 Ion-exchanged water 67.5 93.4 Example 14 N-fluorenyl group Ethanolamine 28 Sodium hypochlorite 15 Ammonium chloride 4 1,2,3-benzotriazole 2 Ion-exchanged water 51 84.9 ti

C: \, total file \ 91 \ 911 1 1830 \ 9111 1830 (replacement) -1 ^ "Page 13 1242608 Case No. 9Π11830 Amendment 92. 12, 2 3 Replacement page V. Description of the invention (11) (Effect of the invention) The invention can provide a #etching agent that can smooth the copper surface under mild conditions, and a #etching method that can smooth the surface.

C: \ Total file \ 91 \ 911 11830 \ 91111830 (replace) -1.ptc Page 14 1242608 92, 12. 2 3 Replace page Case No. 91118830 Rev.

C: \ master file \ 91 \ 911 11830 \ 911 1 1830 (replace) -l.ptc page 15

Claims (1)

I2426Q &amp; -vie * No. 91118830 Λ_ Amendment 丨 Charge 94. (5. Λ 4h 1 ί5 Ben—six L on-car please special 44 range-circle 1. A copper or copper alloy residual agent, which consists of: 1 ~ 40% by weight is selected from monoethanolamine, diethanolamine, propanolamine and ammonia; 1 ~ 15% by weight is selected from sodium gas, potassium gas, chlorous acid, sodium chlorite, potassium chlorite , Hypochlorous acid, sodium hypochlorite, and hypooxidant oxidants; 1 to 10% by weight of an ammonium salt selected from ammonium sulfate, ammonium sulfamate, ammonium lactate, ammonium chloride, and ammonium citrate; and% 0.1 ~ 2% by weight of an aqueous solution selected from the group consisting of sigma compounds, triple compounds, and tetra compounds. 2. A method of etching copper or copper alloys, which contains: 1 ~ 40 1% to 15% by weight is selected from the group consisting of monoethanolamine, diethanolamine, propanolamine, and ammonia; 1 to 15% by weight is selected from the group consisting of sodium chlorate, potassium gas acid, nitrosic acid, sodium chlorite, potassium chlorite, hypoxia acid, An oxidant of sodium hypophosphite and potassium hypophosphite; 1 ~ 10% by weight is selected from sulfuric acid record, amine acid record, ammonium lactate, ammonium chloride, lemon An ammonium salt of ammonium acid; and an aqueous solution of 0.1 to 2% by weight of a salivary compound selected from the group consisting of a miso compound, a three-degree compound, and a four-sigma compound is in contact with the surface of copper or a copper alloy, and the surface is smoothed 0 匸: \ Total file \ 91 \ 91111830 \ 911 11830 (replace)-2.ptc page 16