TW508374B - Etching solution for nickel or nickel alloy, and etching method - Google Patents

Abstract

The subject of the present invention is to produce an etching solution for nickel or a nickel alloy in which the etching rate of the nickel or a nickel alloy is high, also, the erosion of the other metals such as copper and a copper alloy in particular is extremely small, and moreover, side etching is hardly occurred. In an etching solution in which, from the material in which nickel or a nickel alloy and the other metals are coexistent, the nickel or nickel alloy is selectively etched, this etching solution for nickel or a nickel alloy is composed of an aqueous solution containing (A) nitric acid of 5 to 5 weight %, (B) sulfuric acid of 0.5 to 40 weight %, (C) the main oxidizer selected from peroxide, nitrate and an aromatic nitro compound of 0.1 to 20 weight % and (D) chlorine ions of 0.0001 to 0.5 weight %.

Description

374 friends, description of the invention α) [Detailed description of the invention] [Technical field to which the invention belongs] The present invention relates to a device capable of selectively etching nickel or a nickel alloy composed of nickel or a nickel alloy and other metals. Composite material method of engraving, =. The etching solution of the present invention can be particularly used for the manufacture of electronic parts such as semi-finished products such as / (, and face engraving.), Strippers, printed circuit boards [previous technology] for electrodes and wiring including flexible substrates for TAB and BGA packages 、 Electrode of semiconductor products ^ = Shovel for forming nickel coating on printed circuit board electroplating and electroless plating ^ ^ The nickel coating formed by the part is formed by the etching solution. ::: When it is not needed and many wiring Drawers of multiple types of metal: Because the above-mentioned electricity is required to not attack metals other than nickel. S mouth, so the nickel coating is peeled off, for example, printed cloth bad oxygen resin impregnated board based on semi-additive method, polyimide In the clothes manufacturing process, “is after the break of the electrolytic glass ore bromine and the deposition” on the insulating substrate with no plating: line plating steel to form a copper circuit on nickel "inverse pattern of the road" followed by ς J strips the exposed nickel. Used in this case; two strips the plated material and does not etch the copper circuit with neodymium. 7 The nickel etching solution used is required [: Qiangang Steel and nickel-stripping liquid for shoe engraving as a booster. Has been revealed not to contain nitric acid, will be opened thousands 6-5 745 No. 7 organic-based organic compounds in a flat acidic solution containing traitors and 'Yukkaihei 9' reveals an etchant composed of 'night without tooth ions'_228 〇75Publication 89117064.ptd $ 4Page 5. Description of the Invention (2) Industry #Diamond Oxide and other oxidants, aromatic Nitrogenated Character 720 ^^ = aqueous solution composed of engraving liquid machine dyes and market desires $ :::: η ′ 亚 未 undempressed copper invasion #, Yu et al. Nickel etchant, which suppresses copper corrosion more,

^ In order to overcome the shortcomings of the prior art, the present invention is based on the following: # I 虫 刻 速 #, and other metals =, recording or recording. , The engraving solution of nickel or nickel alloy, and the rice carving method for its purpose "Eight books of the Ming Dynasty to provide 5 丨 丨 ir 丨 gold money engraving solution, and ㈣ &. Carved nickel or nickel alloy [means to solve the problem] The present inventors and others are committed to examining the shortcomings of the above-mentioned prior art. Α, the following structure to overcome gold: hair: 2: =: alloy money engraving speed is fast And other liquids, which are selected by the name of nicked nickel or nickel alloy with little invasion of sulfur, sulphuric acid 0.5 ~ ', (c ^ acid 5/55% (the same as the following for weight%), and the product selected The main Λ = acid salt and aromatic nitro compound 臬 or 合金 alloy recording night… the second etching solution: ratio. 疋 compound 0. 01 ~ 6% aqueous solution of nickel or nickel alloy material. The invention is Regarding the presence of nickel or nickel alloy mixed with other metals, contacting the aforementioned aqueous solution, and selectively etching nickel or nickel alloy 89117064.ptd page 5 508374 5. Etching method of invention description (3). ] Hereinafter, the components of the etching solution of the present invention will be described in detail. Moreover, the degree of the auxiliary solution is 5 ~ 55% If the temperature is less than 5%, nickel will be converted and it will not occur in the present invention. It is used in combination. Because of this, the remaining nickel speed becomes Q · 1 ~ 10%, and more preferably money engraving. The effect of speed is not feared and cannot be etched. The etchant of the present invention uses peroxides and species. In the present invention, nitric oxide 1J, the preferred etching method etches oxygen with nitric acid & sulfur 1 ~ 5% c The sufficient salt used in the process is enough to dissolve the nickel oxidized by the main oxidant and also promote the oxidation of nickel. The nitrate is 10 ~ 40%, more preferably 20 ~ 30%. The front speed becomes slower, If it exceeds 55%, it will dissolve nickel, and dissolve nickel. Nitric acid, sulfuric acid, and sulfuric acid can also be used. Therefore, the concentration of acid is 0.5 to 40%, preferably less than 0. · 5%, then increase the record 'if more than 40% will passivate nickel and the main emulsifier is the component that oxidizes nickel, and at least one peroxy compound in the aromatic nitro compound can be listed with y ， 锐 ，， ^ 手 # 于 斤】 For example, hydrogen peroxide, sodium peroxide, phenylhydrazone, and the like.

For example, the stone salt can be exemplified in Example 4 woven dinitrate nickel. Monoammonium acid, sodium sulphate, potassium nitrate, sodium succinate: Examples of phosphonium compounds include nitrobenzoic acid, nitrobenzylbenzylphenol, and salts thereof. 4 includes, for example, sodium nitrobenzylsulfonate and sodium zirconate.

^ yj〇 ^ / 4 V. Description of the invention (4) 0 5 The main ~ t chemical agent ^ The agricultural degree is 0.1 ~ 20%, preferably 0 · 1 ~ 5%, more preferably the speed change ^, river If the ratio is less than 0.1%, the oxidizing power is insufficient and the recorded time is more than 20%, and the corrosion of copper and the like becomes larger. The chloride ion used in the former'd engraving solution is a component that suppresses dissolution of copper and the like. A trip to the brain? For example, hydrochloric acid, aniline hydrochloride, guanidine hydrochloride, ethylamine hydrochloride, etc. are preferred. Emulsions such as sodium chloride, sodium chloride, zinc chloride, copper chloride, and nickel chloride are preferred. The concentration of the dry ion η / "f chloride ion is 0 · 0 0 01 ~ 0 · 5%, preferably 0 · 0 0 01 ~. 2 is more preferably 0 · 0 0 0 1 ~ 0 · 0 0 5% . The above-mentioned concentration is less than 0.0 0 0 1%. The corrosion of copper is increased, and if it exceeds 0.5%, the etching rate of nickel will be greatly changed. Furthermore, when the etchant of the present invention is used in pattern etching, It is preferable to add a pyridine compound to the release of parasites. For example, in the manufacture of printed circuit boards based on the semi-additive method, electroless nickel plating or the like is used as the head plating, and nickel is etched after electroplating copper to form a circuit. In the case, if a pyridine compound is used, The etching solution of the invention can hardly cause sub-etching (dissolution of nickel in the lower part of copper). The "bipyridine compound" mentioned in J refers to a compound in which pyridine and its hydrogen atom are substituted by a halogen atom, an amine group, a hydroxyl group, an alkyl group, an aralkyl group, a vinyl group, and a hexyl group. Specific examples include 2-chloropyridine, 3-bromopyridine, 3-fluoropyridine, 2, 6-dichloropyridine, 2-aminopyridine, 2, 3-diaminopyridine, 3- Hydroxypyridine, 2,4-difluorenyl, bipyridine, 2, 4, 6-trimethylpyridyl =, 2-hydroxymethyl pipyridine, 2- (2-hydroxydiethyl) pyridine, 2_ Vinylpyridine, 2-vinylpyridine, 4- (3-phenylpropyl) pyridine, 4-benzylpyridyl u-pyridine

The concentration of the above-mentioned roaring bite compound is 0.01 6 ° / 〇, and Chejiao 4 soil 'is more preferably G.1 ~ U. The aforementioned concentration is less than 1%, G] ~ 3%, and the effect is small. Even if the surface is too thick, the effect is not seen even if it is engraved by the surname. ° 'The amount added is added to the nickel etching solution of the present invention, and can be added as needed. For example, in order to promote the dissolution of nickel, ii ions such as ions other than ions can be added, and τ 裎, 加, bromide, iodine, and phosphine can be added to the material to be treated. Non-ionic surfactants and For the wettability of water-soluble solvents, the etching solution of the present invention can be easily prepared by mixing and stirring the above-mentioned exchanged water. The method of using the etching solution of the present invention does not include a method of impregnating the material to be treated, and the method of etching, etc. can be exemplified as the contact time between the etching solution and the material to be treated :: method, etc. The “type of material” is suitable for the thickness of the etched brocade, etc .: The second pendulum can be selected according to the processing example. tExamples 1 to 7 and the ratio 轫 Mix the ingredients shown in Table 1 and Table 2—the etching sound is bismuth, and the temperature is 4 ° to modulate the silver engraving solution. The obtained liquid Ni 2 was investigated as described below, and the copper surface was visually observed for the presence or absence of k color. Results are shown in Tables i and 2. (Determination of the Nickel Surveillance Speed) 40 · χ 〇 · 3_ Nickel Plate (Specific Gravity 8.845) w5 ^ _ :: Medium :: Set for 3 minutes * Take * 'and according to the following formula, change the weight of the recording plate, nose out Etching speed.

\\ 312 \ 2D-CODE \ 89-ll \ 89117064.ptd

508374 V. Description of the invention (6) 10000 (weight of nickel plate before processing (g)-weight of nickel plate after processing (g)) Peeling speed (" m / min) = -— " ~ 一 8. 845 X 3 (minutes) X 32 · 48 (cm2) (Measurement of copper invasion speed) 40mm X 40mm X 0.3mm copper plate (specific gravity 8.92) was left to stand for 3 minutes in 25 ° C I insect solution Take out and calculate the invasion speed from the weight change of the copper plate according to the following formula. 10000 (weight of copper plate before processing (g)-weight of copper plate after processing (g)) Invasion speed (" m / minute) =-8. 92 X 3 (minutes) X 32. 48 (cm2)

\\ 312 \ 2D-CODE \ 89-ll \ 89117064.ptd Page 9 508374 V. Description of the invention (7) Composition of example number (wt%) Nickel peeling speed (β m / min) Copper erosion speed (β m / min) Changes on copper surface 1 Nitric acid (67.5%) 50.0 Sulfuric acid (62.5%) 10.0 Hydrogen peroxide (35%) 1.0 Sodium chloride 0.001 Ion exchange water 38.99 5.38 0.04 No change 2 Nitric acid (67.5%) 50.0 Sulfuric acid (62.5%) 10.0 Hydrogen peroxide (35%) 2.0 Ammonium chloride 0.005 Ion-exchanged water 37.995 5.49 0.05 No change 0 Nitric acid (67.5%) 50.0 Sulfuric acid (62.5%) 10.0 Sodium meta-nitrobenzenesulfonate 7.0 Sodium chloride 0.01 Ion exchange water 32.99 5.26 0.05 No change 4 Nitric acid (67.5%) 30.0 Sulfuric acid (62.5%) 10.0 Hydrogen peroxide (3 5%) 1.0 Chlorin chloride 0.001 Ion exchange water 58.99 4.67 0.05 No change 5 nitric acid (67.5%) 30.0 sulfuric acid (62.5%) 10.0 hydrogen peroxide P 5%) 1.0 sodium chloride 0.05 PEG 400 2.0 ion-exchanged water 56.95 4.22 0.05 no change 6 nitric acid (67.5%) 30.0 sulfuric acid (62.5%) ) 10.0 Hydrochloric acid (35%) 0.5 Sodium m-nitrobenzenesulfonate 8.0 Ion-exchanged water 51.5 1.28 0.05 No change 7 Nitric acid (67.5%) 30.0 1 Sulfuric acid (62.5%) 10.0 Hydrochloric acid (35./ ) 0.5 PEG-400 0.1 1〇.〇 potassium ion-exchanged water 0.04 49.4 1.31 No change (Note) PEG 400 is polyethylene glycol of average molecular weight 400

89117064.ptd Page 10 508374 V. Description of the invention (8) Table 2

Example No. Composition (wt%) Nickel peeling speed (β m / min) Copper erosion speed (β m / min) Changes in copper surface Comparative Example 1 Nitric acid (67.5%) 4.0 Sulfuric acid (62.5%) 10.0 Hydrogen peroxide (35 %) 1.0 Sodium chloride 0.001 Ion-exchanged water 84.9 0.34 0.05 No change Comparative Example 2 Nitric acid (67.5%) 85.0 Sulfuric acid (62.5%) 10.0 Hydrogen peroxide (35%) 1.0 Ammonium chloride 0.001 Ion exchange Water 3.99 0.05 0.642 Discoloration and red and black Comparative Example 3 Nitric acid (67.5%) 50.0 Sulfuric acid (62.5%) 10.0 Hydrogen peroxide (35%) 1.0 Ion exchange water 39.0 5.38 0.656 Discoloration and red and black Comparative Example 4 Nitric acid (67.5% ) 50.0 Sulfuric acid (62.5%) 10.0 Hydrogen peroxide (35%) 1.0 PEG 400 0.1 Ion-exchanged water 38.9 5.37 0.741 Discoloration and red and black (Note) PEG 400 is a polyethylene glycol with an average molecular weight of 40089117064.ptd page 11 V. Description of the invention (9) Low concentration of nitric acid will not change the appearance of copper. The etching speed is relatively slow, and in the case of the present etchant (Comparative Example 丨) is 6 / ^, and the state of the liquid is almost impossible to peel (Comparative Example 2) is to make the nickel pure 4) Although the etching speed of nickel is fast, ^ In the case of lice ions (Comparative Example 3 and implementation, the etching of copper is large. The ingredients shown in Table 3 are mixed, and the production rate, copper erosion rate, and copper Nai Yi etching solution. The nickel etching results of the obtained solution are shown in Table 3 The colorless cross-color was investigated in the same manner as in Example 1. After coating on the polyimide substrate, a copper electrode with a thickness of 0.5 // m was formed by using electroplated nickel to form a resist. Mirror inverse: ^ Secondly, the test substrate is formed with electrical bond copper in an etching solution of 25 t, and the main coat is used as a test substrate. The cross section of the microscope is observed at 400 times, and the copper and apricot are removed after the bell. , Cut off and show the results in Table 3.-Secondary etching of nickel in copper pattern.

508374 V. Description of the invention (ίο) Table 3 Example number composition (% by weight) Nickel peeling speed (β m / min) Copper erosion speed (β m / min) Appearance of side-etched copper surface 8 Nitric acid (67.5%) 50.0 fcW (62.5%) 10.0 Hydrogen peroxide (35%) 1.0 Sodium chloride 0.01 2-Chloro-Hou D 疋 1.0 Ion-exchanged water 37.99 5.27 0.04 Μ y \\\ No change 9 Nitric acid (67.5%) 50.0 Sulfuric acid (62.5%) 10.0 Hydrogen peroxide (35%) 2.0 Ammonium chloride 0.005 2-Amine-Amine 2.0 Ion-exchanged water 35.995 5.33 0.05 te No change 10 Nitric acid (67.5%) 50.0 Sulfuric acid (62.5%) 10.0m -Sodium nitrobenzene sulfonate 7.0 Sodium chloride 0.001 3-hydroxypyridine 4.0 Ion exchange water 28.99 5.12 0,05 4a No change 11 Nitric acid (67.5%) 30.0 Sulfuric acid (62 · 5%) 10.0% Hydrogen oxide (35%) 1.0 Ammonium chloride 〇〇〇 2-Chlorodine 0.2 Ion exchange water 58.79 4.66 0.05 M j \\\ No change drawing 11! 1 89117064.ptd Page 13 508374 5. Description of the invention (11) As shown in Table 3, the etching solution of the present invention is nickel with a high etching speed, and the corrosion of copper is very small, and the appearance of copper is not changed. Also, no dissolution was observed in the copper pattern (side I worm). [Effects of the Invention] According to the present invention, it is possible to provide an etching solution for nickel or a nickel alloy which has a fast etching rate of nickel or a nickel alloy and has little erosion of metals other than copper, especially copper and copper alloys. Furthermore, according to the present invention, a nickel etching solution of nickel or a nickel alloy which hardly causes sub-etching can be provided.

89117064.pul page 14 508374 Schematic description 89117064.ptd page 15

Claims (1)

Sixth, the scope of the patent application: Metal mixture :: 'Ye, which is made of nickel or nickel alloy and other saki, and is made of 40% by weight of nickel or nickel alloy. () 5 to 55 weight of nitric acid %, (B) sulphuric acid 0.5 to ^) Over-rolled products, nitrates and aromatic nitro compounds selected 〇 / P family dagger agent 0.1 to 20% by weight and (〇 chloride ion. 〇〇〇1 ～ 0.5 重量 / 0 的 水〉 谷 液。 Lihua 2 into the L application and the remainder of the solution described in the first item of the patent scope, which contains ... chemical compounds 0 · 〇ι ~ 6 %% by weight. Person 3:? F carved *, characterized by mixing nickel or nickel alloys with other metals. Fendan "» material, containing (A) 5 to 55% by weight nitric acid, (B) 0.5 sulfuric acid = 重 里 (C) The main emulsifier from peroxide, nitrate and aromatic nitro compound 0. i ~ 20% by weight and (1)) chloride ion 〇 · 〇〇〇〇1〜〇. 5 重 $ % Aqueous solution. 4. According to the etching method described in item 3 of the scope of patent application, the soybean solution contains 0.01 to 6% by weight of a pyridine compound. Hachijo, don't 迮 ^ 合