JPH02141589A - Etching promoting additive - Google Patents

Abstract

PURPOSE:To improve the finishing property and etching effect of an etchant by adding a promoter consisting of a specified org. compd. to the etchant for various metals and alloys consisting of an aq. soln. of ferrous chloride or cuprous chloride. CONSTITUTION:From 0.05 to 2.5wt.% of the etching promoter consisting essentially of an alkanesulfonic acid a hydroxyl group-contg. alkanesulfonic acid, their salts, acetylene alcohol or an acetylene alcohol-alkylene oxide adduct, polyethylene glycol, and an org. phosphorus compd. is added to the aq. soln. of ferrous chloride or cuprous chloride as the etchant to be used for etching iron, steel, stainless steel, Fe-Ni-based alloys, Fe-Ni-Co-based alloys, and a copper-based alloy material. The etchant added with the etching promoter exhibits excellent dissolution stability, inhibition of forming, finishing property and etching efficiency in its spray etching.

Description

[Detailed description of the invention] [Industrial application field]

In the present invention, it is added to an aqueous solution of ferric chloride or cupric chloride, that is, an etchant, to produce an etching effect.

[Conventional technology]

With the rapid development of industrial and electrical equipment, etching technology is required to meet a wide range of demands and to respond to even higher precision processing. Etching is performed by chemically dissolving iron, stainless steel, iron-nickel alloys, iron-nickel-cobalt alloys, and copper materials using a ferric chloride or cupric chloride aqueous solution (etchant), and the etchant concentration Φ It is widely known that temperature conditions, etching speed, and finish quality are closely related.

[Problem to be solved by the invention]

However, in such conventional etching processing, there are restrictions on equipment and etchant, and it is extremely difficult to obtain an environment with a good balance between etching conditions, etching speed, and finish quality, and it is difficult to manage the balance. It is known that cars require a lot of effort. In other words, in order to improve the etching speed (efficiency) at the usual etching site, the etchant concentration is lowered to improve the finish quality and improve efficiency.
In order to improve the finish, there are cases where the etchant concentration is increased to reduce etching efficiency. The object of the present invention is to provide a well-balanced improvement in etching speed (efficiency) and workability under a wide range of etching conditions.

[Means to solve the problem]

The present invention has been made by paying attention to such conventional problems. That is, an etching characterized by having as essential components: (1) alkanesulfonic acid, a hydroxyl group-containing alkanesulfonic acid, or a salt thereof; (2) acetylene alcohol or an acetylene alcohol alkylene oxide adduct; (c) polyethylene glycol and an organic phosphorus compound. It is a promoting additive. (Requirements constituting the means) In the alkanesulfonic acids, hydroxyl group-containing alkanesulfonic acids, or salts thereof used in the present invention, the alkali/sulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and butanesulfonic acid. The hydroxyl group-containing alkanesulfonic acids include 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, 1-hydroxypropane-2=sulfonic acid, 3-hydroxypropane-1-sulfonic acid, etc. The salts are alkali metal, amine, and ammonium salts, and these salts constitute one component of the additive, either alone or in combination. Acetylene alcohol is an unsaturated alcohol with an acetylene bond in the molecule, including propargyl alcohol,
Examples include butyne diol, and the acetylene alcohol alkylene oxide additive refers to a mixture of these acetylene alcohols with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, alone or in combination. Acetylene alcohol or its alkylene oxide adduct, used alone or in combination, constitutes a component of the additive. What is polyethylene glycol? Molecular weight 200-20,000
Although some are commercially available, in this application, molecular weight is 200-1000, more preferably molecular weight is 200.
~600 is effective and constitutes one component of the additive, either alone or in combination. The organic phosphorus compound is an organic phosphorus compound having a chelating function, typified by hydroxyethane diphosphone and nitrilotrimethylene phosphone, and is used alone or in combination to form a component of the additive. Further, the additives having the above four essential components are used by adding 0.05 to 2.5% by weight to an aqueous solution of ferric chloride or cupric chloride. If the amount added is less than 0.05% by weight or more than 2.5% by weight, it will be difficult to obtain a homogeneous and stable liquid, and the effect will also be impractical.

[Effect]

The additive of the present invention exhibits excellent effects in etching treatment, as shown in the following examples (examples of use). The nature of this effect is unknown, but it is likely that the four essential components have some kind of synergistic effect with each other. In any case, the additive composed of four essential components is an excellent etching promoting additive.

【Example】

Hereinafter, the embodiments and effects of the invention will be illustrated by Examples and Comparative Examples, but these are, of course, for illustrative purposes and do not limit the scope of the inventive idea. 1-3 and 1-6 Invention additives and comparative additives were manufactured according to the formulations shown in Table 1 below. (Hereinafter, blank spaces) 1 to 3 and 1 to 6 Using the additives of the above production examples and comparative production examples, the following tests were conducted and evaluated. The results are shown in Table-2. (2) Evaluation of dissolution stability 0.25% of each etching accelerating additive was added to ferric chloride etchant (32°Be), and dissolution stability at 40°C was evaluated according to the following criteria. (Criteria) o: Stable dissolution ∆ partial dispersion ×: Separation 2, foaming evaluation Add 0.5% of each etching accelerator additive to cupric chloride etchant (33°Be) and collect 50ml into a 100ml Nessler tube. do. After holding at 45°C, it was shaken vigorously 100 times/30 seconds, and the foaming pattern after 20 seconds was evaluated based on the following criteria. (Standard) O: Less than 5 m1 Δ: 5 m1 to 20 m
Sentence ×: Separation 3, Etching Effect (1) (Gloss) Stainless steel (SUS304, carbon content 0.05%) was added to a ferric chloride aqueous solution (42°Be) with 2.0% etching accelerator additive 45 ℃ etchant 2.0Kg/
, j. After spraying for 10 minutes, the coating was washed with water, air-dried, and visually compared with glossiness, which was evaluated based on the following criteria. (Criteria) 0 Excellent O Good Δ Acceptable 1.0Kg with added 40℃ etchant
/cmi, after spraying for 40 seconds, washing with water, and air drying, the following evaluation items were numerically evaluated. The smaller the number, the better the performance. Surface roughness evaluation (comparison of φ core uniformity in μm) 5. Etching effect (3) (etching speed) Draw a specified pattern on 4270 material and add to cupric chloride aqueous solution (45°Be) to promote etching. After spraying with a 45° C. etchant containing 2.0% agent at 1.5 kg/ai for 5 minutes, washing with water and air drying, the following evaluation items were numerically evaluated. The larger the number, the better the performance. Etching depth evaluation (compare depth at 11.m) 6. Etching effect (4) (etching factor) Draw a prescribed pattern on pure iron material, and draw a ferric chloride aqueous solution (4.
45 with 1.0% etching accelerating additive added to °Be)
℃ etchant 1. ．． After spraying at 5 kg/d for 5 minutes, the etching factor was evaluated using the calculation formula: after being washed with water and air-dried, it was left to stand. The larger the number, the better the performance. E f = 2 X d / (w − w t ) (In the formula, d is the etching depth, W is the etching width, and Wl is the resist slit width.) (The following is a blank space) Table 2 The knee 2 etch promoting additive of the present invention is Evaluation, Nol~N01
It must be good in all of 6, showing excellent properties in dissolution stability, foaming property, and etching effect. On the other hand, Comparative Additive 4.5.6 shows impractical performance in dissolution stability, foaming property, and gloss, and Comparative Additive 1.2.3 is particularly glossy because it does not consist of component 1). The results are that the surface roughness characteristics are particularly poor because the 2) component (2) is not included, and the etching speed is particularly poor because the component (3) is not included. From the above results, it became clear that the comparative additives did not achieve the desired effect.

【Effect of the invention】

By using the etching accelerating additive of the present invention,
In commonly used spray etching methods, we use etching accelerator additives that contribute to finer etching processes and faster etching processes, which have excellent dissolution stability, suppression of foaming that causes operational problems, finish quality, and etching efficiency. Can be provided.

Claims (1)

[Scope of Claims] 1. (a) alkanesulfonic acid, hydroxyl group-containing alkanesulfonic acid, or salts thereof (b) acetylene alcohol or acetylene alcohol alkylene oxide adduct (c) polyethylene glycol and (d) organic phosphorus compound An etching accelerating additive characterized by being an essential ingredient. 2. A method for promoting etching, which comprises adding 0.05 to 2.5% by weight of the additive according to claim 1 to an aqueous solution of ferric chloride or cupric chloride.