KR100312286B1 - Electrolytic polishing composition for copper or copper alloy substrate and iron-nickel alloy substrate - Google Patents

Abstract

PURPOSE: Provided is an electrolytic polishing composition for copper or copper alloy substrate and iron-nickel alloy substrate, which has superior polishing property without erosion attack to substrate to be polished. CONSTITUTION: The electrolytic polishing composition comprises (a) 50 to 900 g/L of phosphoric acid, (b) 10 to 400 g/L of methane sulfonate, (c) 10 to 200 g/L of one or more organic acid selected from Na2HPO4, K2HPO4, sulfuric acid, ammonium sulfate, citric acid, potassium or their mixtures, (d) 0.01 to 50 g/L of stabilizer selected from glycerine, ethyleneglycol, ethanol amine, triethylenetetramine, thioacetamide, thiourea, isopropyl alcohol or their mixtures, (e) and 0.001 to 5 g/L of surfactant selected from sodium lauryl sulfate, triethanolamine lauryl sulfate, naphthalene-1-sulfonic acid(alpha)potassium, N,N-diethyl-1,3-diaminopropane, beta-naphthol ethoxylate, polyethylene monocetyl ether or their mixtures.

Description

ELECTROLYTIC POLISHING COMPOSITION FOR COPPER OR COPPER ALLOY SUBSTRATE AND IRON-NICKEL ALLOY SUBSTRATE}

The present invention relates to an electrolytic polishing composition for electropolishing copper or copper alloy materials and iron-nickel alloy materials.

In general, the plating process of an electronics industry device made of copper or copper alloy material and iron-nickel alloy material such as semiconductor leadframe, printed circuit board and connector is performed in the following order.

Electrolytic degreasing step → washing step → electrolytic polishing step → washing step → acid or alkali deposition step → washing step → plating step

In the electrolytic polishing step, electrolytic polishing before plating on copper or copper alloy material or iron-nickel alloy material, the surface of the material is polished and smoothed to obtain excellent and uniform plating. to be.

Devices manufactured in the electronics industry, such as lead frames, made of copper or copper alloys and iron-nickel alloys, produce fine burs on the lead frames. The adhesion decreases, the current resistance increases, and the corrosion resistance falls, and the lifetime of a semiconductor falls.

In order to overcome this problem, many electrolytic abrasives have been developed and used, but most of them contain phosphoric acid and sulfuric acid, so that the current density range to make the surface smooth and glossy, and copper or copper alloy materials and iron -Nickel alloy material is not well polished and there are many problems such as low production efficiency due to long polishing time by electrolysis.

Accordingly, an object of the present invention is to provide an electropolishing composition which has a short polishing time in electropolishing copper or copper alloy material and iron-nickel alloy material, and makes the surface smooth and glossy without impairing the material. To provide.

In order to achieve the above object, the present invention contains 50 to 900 g / l phosphoric acid, 10 to 400 g / l methanesulfonic acid, 10 to 200 g / l at least one organic acid, 0.01 to 50 g / l stabilizer and 0.001 to 5 g / l surfactant. It provides an electrolytic polishing composition.

Hereinafter, the present invention will be described in more detail.

The electropolishing compositions of the present invention can be used in electronic devices such as semiconductor leadframes, printed circuit boards, connectors, etc., made of copper or copper alloy materials, and iron-nickel alloy materials such as alloy 42. It is also suitable for use in reel to reel plating equipment.

In the electropolishing composition of the present invention, phosphoric acid is used at a concentration of 50 to 900 g / l, preferably 200 to 800 g / l, and methanesulfonic acid is used at a concentration of 10 to 400 g / l, preferably 100 to 300 g / l. do.

Sources of organic acids that can be used in the electropolishing compositions of the present invention include, for example, salts such as phosphate series, sulfate series, citrate salts, or mixtures thereof, and specifically, sodium hydrogen phosphate, potassium hydrogen phosphate, sulfuric acid, and ammonium sulfate. , Citric acid, potassium citrate or mixtures thereof are preferred. The organic acid salt is used at a concentration of 10 to 200 g / l, preferably 20 to 150 g / l.

Stabilizers that can be used in the electrolytic polishing composition of the present invention include mainly glycerin-based, amine-based, amide-based, imine-based, urea-based salts or mixtures thereof, and glycerin, ethylene glycol, ethanolamine, and triethylene. Preference is given to tetraamine, thioacetamide, thiourea, isopropyl alcohol or mixtures thereof. The stabilizer is used at a concentration of 0.01 to 50 g / l, preferably 0.02 to 30 g / l.

Surfactants that can be used in the electrolytic polishing composition of the present invention include sulfonic acid series, ethoxyl series, amino series or mixtures thereof, and sodium lauryl sulfate, triethanolamine lauryl sulfate, naphthalene-1-sulfonic acid ( Alpha) sodium, N, N-diethyl-1,3-diaminopropane, beta-naphthol ethoxylate, polyethylene monocetyl ether or mixtures thereof are preferred. The surfactant is used at a concentration of 0.001 to 5 g / l, preferably 0.01 to 3 g / l.

The phosphoric acid, methanesulfonic acid, organic acid, stabilizer and surfactant are sequentially dissolved in distilled water to prepare an electrolytic polishing composition of the present invention.

In the electropolishing composition of the present invention prepared above, the material to be polished as the anode (+), that is, copper or copper alloy material and iron-nickel alloy material, and platinum, stainless steel mesh or plate as the negative electrode (-) are immersed, Current is applied to allow the material to be polished. At this time, the temperature is 20 to 35 ℃, the applied voltage is preferably 5 to 10V.

The electropolishing composition of the present invention has the following characteristics:

(1) Burs are polished with no erosion to copper or copper alloys and iron-nickel alloys to give the surface a glossy smooth state;

(2) The polishing time is 20 seconds to 1 minute, which is shorter than the existing 20 to 30 minutes, which is efficient and suitable for reel to reel equipment.

The present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited only to the following examples.

Example 1

The following components were sequentially dissolved in distilled water to prepare an electrolytic polishing composition.

Phosphoric Acid 760 g / ℓ

Methanesulfonic acid 120 g / l

Ammonium Sulfate 35 g / L

Glycerin 20 g / ℓ

Ethanolamine 3 g / ℓ

Triethanolamine lauryl sulfate 0.03 g / L

Using the composition prepared above as an electrolyte, the material was polished for 40 seconds under conditions of a temperature of 28 ° C. and an applied voltage of 8V. As a result, the surface glossiness of the raw material was excellent and was kept smooth.

Example 2

The following components were sequentially dissolved in distilled water to prepare an electrolytic polishing composition.

Phosphoric Acid 750 g / ℓ

150 g / l methanesulfonic acid

Citric Acid 35 g / ℓ

Glycerin 25 g / ℓ

Triethylenetetraamine 5 g / L

Naphthalene-1-sulfonic acid (alpha) sodium 0.05 g / L

Using the composition electrolyte prepared above, the material was polished for 40 seconds under conditions of a temperature of 28 ° C. and an applied voltage of 8V. As a result, the surface glossiness of the raw material was excellent and was kept smooth.

Example 3

The following components were sequentially dissolved in distilled water to prepare an electrolytic polishing composition.

Phosphoric Acid 560 g / ℓ

Methanesulfonic acid 230 g / ℓ

Sodium hydrogen phosphate 70 g / ℓ

Thioacetamide 0.05 g / L

Polyethylene monocetyl ether 0.02 g / l

Using the composition electrolyte prepared above, the material was polished for 40 seconds under conditions of a temperature of 28 ° C. and an applied voltage of 8V. As a result, the surface glossiness of the raw material was excellent and was kept smooth.

Electrolytic polishing of copper or copper alloy materials and iron-nickel alloys using the electrolytic polishing compositions of the present invention containing phosphoric acid, methanesulfonic acid, one or more organic acids, stabilizers and surfactants provides no erosion at all. The polished smooth state is achieved, and the polishing time is shorter and more efficient than when the conventional polishing composition is used.

Claims (7)

An electrolytic polishing composition containing 50 to 900 g / l phosphoric acid, 10 to 400 g / l methanesulfonic acid, 10 to 200 g / l at least one organic acid, 0.01 to 50 g / l stabilizer and 0.001 to 5 g / l surfactant. The method of claim 1, The organic acid is sodium hydrogen phosphate, potassium hydrogen phosphate, sulfuric acid, ammonium sulfate, citric acid, potassium citrate or a mixture thereof. The method of claim 1, The stabilizer is glycerin, ethylene glycol, ethanolamine, triethylenetetraamine, thioacetamide, thiourea, isopropyl alcohol or a mixture thereof. The method of claim 1, The surfactant is sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium naphthalene-1-sulfonic acid (alpha), N, N-diethyl-1,3-diaminopropane, beta-naphthol ethoxylate, polyethylene monocetyl Ether or mixtures thereof. Dipping a copper or copper alloy material or an iron-nickel alloy material as an anode (+), and a platinum or stainless steel mesh or plate as an anode (-), and subjecting it to current to polish the material. Electrolytic polishing method of copper or copper alloy material or iron-nickel alloy material comprising a. The method of claim 5, Copper or copper plating alloy material and iron-nickel alloy material is a semiconductor lead frame, connector or printed circuit board. The method of claim 5, Method using reel to reel equipment.