JPS607707B2 - Manufacturing method for composite metal parts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a composite metal part consisting of a nickel layer pattern and iron, and more specifically, the present invention relates to a method for manufacturing a composite metal part consisting of a nickel layer pattern and iron. The present invention relates to a method for manufacturing composite metal parts that prevents stains from forming on the surface of a pattern.

The present invention is particularly suitable for manufacturing nickel-iron composite metal parts having fine patterns that require precision, such as the mesh of a crab light display tube grid or the shadow mask of a color television cathode ray tube.

The present inventors previously reported in Tokuiso Sho 51-143476 ``Method for manufacturing composite metal plates'' that a pattern made of nickel or nickel alloy was formed on the surface of iron or steel, and an aqueous solution containing ferric sulfate and sulfuric acid was applied. We proposed a method for manufacturing composite metal parts such as shadow masks and grids by selectively etching iron or steel.

According to this method, an aqueous solution containing ferric sulfate easily etches iron and steel, but has excellent selective etching properties in that it does not attack nickel, making it possible to manufacture composite metal materials with extremely high precision. can. However, when the pattern consists of only a nickel layer, the surface of the nickel layer, which had a beautiful silvery white color before etching, often develops a gray-brown stain pattern or discoloration due to etching, which impairs commercial value. Furthermore, if the pattern consists of only a nickel alloy layer, depending on the type of nickel alloy, such as a nickel-tin alloy or a nickel-adjacent alloy, the above-mentioned stain pattern will not occur, but nickel alloys generally Since it is brittle, it has the disadvantage that the nickel alloy part, which has a fine structure like the mesh of a grid, is easily damaged during the manufacturing process or during use. The present invention aims to solve the above-mentioned drawbacks of the previously proposed invention, and an object of the present invention is to use nickel that has a beautiful surface and is highly flexible (that is, not brittle). The present invention provides a composite metal part made of nickel-iron having a layer pattern.

That is, the present invention includes the steps of depositing a pattern made of a nickel layer on the surface of an iron plate, and depositing a thin layer of at least one of a nickel-tin alloy, a nickel-phosphorus alloy, or chromium on the nickel layer pattern. Provided is a method for manufacturing a composite metal part, comprising a step of selectively removing iron in the deposited and non-adhered portions of the pattern using an etching solution mainly composed of ferric sulfate having a PHI or less. It is something to do.

The present invention will be explained in detail below.

The iron plate used in the present invention is not limited to a pure iron plate, but also a steel plate such as a low carbon steel plate.

A suitable range for the thickness of the iron plate is determined depending on the type of composite metal part, and for example, in the case of a crab light display tube grid or a shadow mask, a preferable range is 0.1 to 0.3 m. There are various methods for applying a nickel layer pattern to the surface of an iron plate, such as plating and cladding methods, and there are no particular restrictions. However, when a precise pattern is required, such as a grid mesh, the photosensitive method described below can be used. A method of plating using a transparent resin film gives preferable results.

In other words, to explain an example of a grid, after forming a photosensitive resin film on both sides of an iron plate by a coating-adhesion method or a film adhesion method, the frame and mesh of the grid are finally formed as shown in Fig. 1. Place a negative mask with a pattern on one side of the iron plate, and place a negative mask with a pattern that will become the frame of the grid on the other side of the iron plate, as shown in Figure 2, so that the patterns that will become the frame are exactly facing each other. Place emphasis on

Next, the photosensitive resin film overlaid with the negative mask is exposed to ultraviolet rays, and then developed, the resin film in the pattern portion is removed and the iron surface corresponding to the pattern is exposed.

Next, the exposed iron surface portion is plated with nickel to deposit a pattern made of a nickel layer. As the nickel plating method, an electroplating method, an ion plating method, an electroless plating method, etc. can be adopted.

The electroplating method, which is the simplest method, will be explained below, but the plating method of the present invention is not limited to the electroplating method. For nickel electroplating, a known nickel sulfate bath, nickel chloride bath, nickel borofluoride bath, nickel sulfamate bath, or a mixture of these nickel baths is used.

As additives to these cases, inorganic substances such as boric acid and ammonium chloride, or small amounts of bit inhibitors such as sodium dodecylbenzenesulfonate and sodium dodecyl sulfate can also be used. However, sodium naphthalene sulfonate,
It is not preferable to add brighteners or flea stress relievers such as saccharin, butynediol, gelatin, propargyl alcohol, formalin, and thiourea. This is because in these cases, the nickel plating layer is also likely to be corroded by the solution containing ferric sulfate as a main ingredient, resulting in loss of selectivity and properties. The reason for this is not clear, but the nickel plating layer obtained from coatings containing brighteners and dew stress relievers contains sulfur (usually 0.02% by weight or less), so it may be related to this phenomenon. it is conceivable that. There is no particular limit to the thickness of the nickel plating layer, but it is usually 10~
Gives favorable results within the range of 60 mountains. In order to obtain beautiful composite metal parts without stain patterns, a nickel-tin alloy,
It is important to deposit a thin layer of either nickel-phosphorous alloy or chromium.

The thickness of the thin layer is usually about 0.5 to 5 mm thick to give preferable results. That is, if the thickness is less than 0.5 mm, the stain resistance is insufficient, while if the thickness exceeds 5 mm, no particular improvement in stain resistance is observed. The composition of the nickel-tin alloy layer is 20-8% by weight of nickel and 80-2% by weight of tin.
Also, the phosphorus content in the nickel-phosphorus alloy layer is about 8 to 15
Preferred results can be obtained with weight percentages.

The formation of the nickel-tin alloy layer consists of nickel chloride, tin chloride,
Electroplating is performed using a known plating grade containing fluoride as a main component, or tin plating is performed on the nickel plating layer using a known bath, and then 180 to 30,000
This is done by heating and diffusion treatment.

The nickel-phosphorus alloy layer can be formed using known methods such as electroplating mainly consisting of nickel sulfate and Nickelin B-1 (manufactured by Okuno Pharmaceutical Co., Ltd.), or electroless plating mainly consisting of nickel chloride and sodium hypophosphite. This can be done using Kikyu et al.

The chromium can be deposited by electroplating using a known Sargent method or by ion plating. If a composite metal material with a black pattern on the surface is desired, a known black chrome plating bath may be used. Next, by removing the photosensitive resin film with a caustic soda solution or the like, an intermediate composite metal part made of nickel-iron with the iron surface exposed between the nickel patterns as shown in the cross-sectional view of FIG. 3 is obtained.

In FIG. 3, reference numerals 1 and 3 correspond to the grid frame portions made of nickel, 2 a mesh made of nickel, 4 an iron plate, and 5 a nickel-tin alloy, nickel-phosphorus alloy, or chromium plating layer. To selectively carve the exposed iron surfaces described above to form the final nickel-iron composite metal part shown in FIG. It is important to use an etching solution containing the main ingredient. The dissolution reaction by ferric sulfate is according to the following equation.

Fe2 (S04) 30FeichijoeS04...
...[1] That is, ferric sulfate reacts with iron to become ferrous sulfate.

Since this etching solution usually uses sulfuric acid for pH adjustment, its composition consists of ferric sulfate, reaction products of ferrous sulfate and sulfuric acid, and a corrosion inhibitor added as necessary.

A suitable amount of total iron ions, including ferrous and ferric ions, is approximately 5 to 15% of the weight of the etchant, and the ratio of ferric ions to total iron ions is 30% or more. It is preferable.

This is because if the ratio of ferric ions is less than 30%, the etching rate decreases, making it impractical. Also, the P of the etchant
It is important that H is 1 or less.

When the pH exceeds 1, oxides generated by etching, etc.
This is because it adheres to the iron surface and is difficult to remove, and the etched surface becomes rough, side etching increases, and the etching speed decreases. The concentration of free sulfuric acid in the etching solution is PHI and 5 days/so, and for the above reason, free sulfuric acid of 5 days/so or more is required, but if this becomes more than 200 days/so, the etched surface will become rough again. This is not preferable because it may cause uneven etching or uneven etching.

Therefore, the preferred free sulfuric acid concentration is between 5 and 200 units/sleeve.
The temperature of the etching solution is preferably in the range of 30 to 55 degrees.

If the temperature is higher than 55 oC, corrosion of the nickel layer will occur, and side etching will become large.
As described above, the present invention provides a nickel-iron composite metal part having a fine nickel pattern with excellent precision by utilizing the excellent selective etching properties of an aqueous solution mainly composed of ferric sulfate. Furthermore, by utilizing the excellent stain resistance of nickel-tin alloy, nickel-phosphorus alloy, or GLOHM to ferric sulfate solution, it is possible to provide a composite metal part with a beautiful surface and a pattern. I can do it. Examples will be described below.

[Example 1] A film-like photosensitive resin with a thickness of 25 mm is attached to a low carbon steel plate with a thickness of 0.17 mm, and a frame pattern including a mesh of 25 mm in a line as shown in Fig. 1 is formed on one side. A patterned negative mask having only a frame as shown in FIG. 2 was superimposed on the other side so that the front and back sides matched, and the negative mask was exposed with an arc lamp and developed with a 1% sodium carbonate solution.

Then, on the exposed low carbon steel surface, apply a semi-gloss bath containing wattage (nickel sulfate 270 times/day, nickel chloride 45 times/day, boric acid 30 days/day), and saccharin 0.5 day/time added thereto. , and as a brightening agent, three types of specimens pre-plated with nickel to a skin thickness of 25 mm were added to each of the brightening baths to which Ni Conc3cc/So, Duplal (Comicc/So) manufactured by Schering was added. Created. The surface of each of these is plated with a nickel-tin alloy (nickel chloride 300 m/m, stannous chloride 509 m/m, sodium fluoride 28 m/m, acidic ammonium fluoride 35 m/m).
evening/evening), nickel-phosphorus alloy plating grade (nickel sulfate 3
00 evening/So, Okuno Pharmaceutical Nikkelin B-1, 200cc
/ so) and surgical bath (chromic acid 250 t/d,
Using either sulfuric acid (2.5 am/so), 0.25 to 1 Am for nickel-tin, 0.3 to 3 Am for nickel-phosphorous, and
The chromium was post-plated to a thickness of 0.1 to lAw.
In addition, some parts are tin-plated on the nickel layer (tinn sulfate 50%).
Multi/so, sulfuric acid 100/day, cresol sulfonic acid 1
Tin plating was carried out to a thickness of 1 skin using 00 m/z, 8 naphthol 1 m/m, gelatin 2 m/m). after that,
The photosensitive resin was removed with a 10% caustic soda solution, and the tin-plated sample was heated at 100 to 300 oo for 30 minutes to form a nickel-tin alloy layer. Further, using a solution containing 45% by weight of ferric sulfate and sulfuric acid added so as to have a pH of 0.2, the surface of the atomized steel was etched at a temperature of 45 qo using a spray type etching device. For comparison, after the phenomenon occurred, without nickel plating, we plated only nickel-tin, nickel-phosphorus, or chromium with each of the above plating grades to a thickness of 25 cm, and then peeled off the photosensitive resin. After that, etching was performed under the same conditions as above. The degree of discoloration on the surface of the plating layer after etching is rated as ○ for no discoloration, △ for slight discoloration, × for marked discoloration, and ○ for mesh with no line breakage, and ○ for some line breakage. Table 1 shows the results of evaluation: △ indicates that no mesh remains, and × indicates that no mesh remains. Table 1 Evaluation of Etching Results From Table 1, on the nickel plating layer with poor luster (Watt Yu nickel plating), either nickel-tin, nickel-phosphorus, or chromium was applied to a thickness of approximately 0.5 mounds or more. By applying a thin layer of plating to the surface and etching it with a solution mainly consisting of ferric sulfate and sulfuric acid, the plated layer is clean and has no lines, making it possible to create products such as crab light display tube grids, which have a frame and mesh integrated. It is clear that composite metal parts can be obtained.

In addition, if only nickel-tin, nickel-phosphorus, or chromium plating is used, these plating layers are fragile and the mesh will break, making it impossible to leave the mesh behind. It turns out that for the first time, it is possible to manufacture composite metal parts with fine patterns. [Example 2] A film-like photosensitive resin with a thickness of 17 mm was pasted on a low carbon steel plate with a thickness of 0.15 mm, and a shadow with a large number of rectangular holes arranged at equal pitches was formed on one side as shown in Fig. 5. A negative film having a mask pattern is layered on the other side with a negative film having square holes larger than the square holes at the same pitch as the pattern, so as to match the hole pitch of the film, and exposed to light using an arc lamp;
It was developed with a 1% by weight sodium carbonate solution.

Then add 15 watts of nickel onto the exposed steel surface.
On top of that, use either nickel-tin alloy plating, nickel-phosphorus alloy plating, or Sargent plating to a thickness of 0.25 to 3
plating a nickel-scale alloy plating layer with a thickness of 1 to 5 mounds and a chrome plating layer with a thickness of 0.1 to 2 m.
The photosensitive resin was peeled off using wt% caustic soda to produce an intermediate material for a shadow mask whose partial sectional view is shown in FIG.
In Figure 6, 6 is a nickel plating layer, 7 is a nickel plating layer, and 7 is a nickel plating layer.
Tin, nickel-phosphorus or chromium layer, 8 indicates low carbon steel plate. Next, etching was carried out under the same conditions as in Example 1 to obtain a shadow mask whose partial sectional view is shown in FIG. As a result, those without thin layer plating will have significant discoloration around the hole due to etching, and thinner ones with nickel-tin of 0.25 mm, nickel-phosphorus of 1 mm, and chromium of 0.1 mm will have slight discoloration. Although discoloration occurred, when the thickness was above these values, a clean plated surface without stains was obtained even after etching. For comparison, after development, the exposed steel surface was plated with 15 μm each of nickel-tin, nickel-phosphorus, and chromium, the photosensitive resin was peeled off with caustic soda, and etched under the same conditions as above.
Since these plating layers alone are fragile, the plating layer around the hole was locally detached, resulting in a hole with poor shape and accuracy. Therefore, the nickel layer and nickel - tin, nickel -
By forming a shadow mask pattern using a combination of thin layers of phosphorus or chromium, and etching the iron with a solution mainly consisting of ferric sulfate and sulfuric acid, a shadow mask with excellent hole precision and a beautiful surface can be created for the first time. can get. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 are plan views of a negative mask pattern for producing a light display grid, FIG. 3 is a partial sectional view of an intermediate product for a light display grid according to the present invention, and FIG. 5 is a plan view of a negative mask pattern for producing a shadow mask, FIG. 6 is a partial sectional view of a shadow mask intermediate product according to the present invention, and FIG. 7 is a partial sectional view of a crab optical display tube grid according to the present invention. 1 shows a partial cross-sectional view of a shadow mask according to the invention; FIG.

1, 2, 3, 6...Nickel layer, 5,7...Nickel-tin alloy, nickel-phosphorus alloy or chromium layer, 9,10...Iron.

Figure 1 Figure 2 Figure 3 Kanmu map Figure 5 *Figure 6 Figure 7

Claims (1)

[Claims] 1. A step of depositing a pattern made of a nickel layer on the surface of an iron plate, a step of depositing a thin layer of at least one of a nickel-tin alloy, a nickel-phosphorus alloy, or chromium on the nickel layer pattern, and the above-mentioned steps. A method for manufacturing a composite metal part, comprising the step of selectively removing iron in a portion of the pattern to which the pattern is not adhered using an etching solution mainly composed of ferric sulfate having a pH of 1 or less.