JPS5844743B2 - Method for producing etched products using photoetching method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves coating a metal plate with a resin composition that can be cured by irradiating it with ultraviolet rays, irradiating it with ultraviolet rays to form a cured film in a desired shape, and then performing an etching treatment. The present invention relates to a method for producing an engraved product.

Generally, in the production of etched products, a coating of the desired shape is formed on a metal plate, and then an etching process is performed to remove the parts of the metal plate where the coating is not formed, and the unnecessary hardened coating parts are then etched with an alkaline solution. This is done by dissolving and removing.

The adhesion of the resin coating to the metal plate of the resins that can be used in the conventionally developed photoetching method is not sufficient, and during the etching process, phenomena such as peeling of the coating occur, resulting in the metal being damaged even in areas that do not require etching. In some cases, the plate surface is etched, making it difficult to obtain a desired etched product.

Therefore, the present inventors considered and investigated the use of ultraviolet irradiation as a means of drying the film as a method to improve this problem, and found that a solvent-free acrylic resin composition containing a specific amount of unsaturated acid. When a material is used, it quickly dries and hardens when exposed to ultraviolet rays, and the formed cured film has good adhesion to the metal plate, causing the above-mentioned problems during the etching process, and may peel off after the etching process. The present invention was completed based on the discovery that it is possible to manufacture a more excellent engraved product by easily removing the cured film using an alkaline solution.

The gist of the present invention is that the metal plate has a molecular weight of 200 to 2000, one or more acryloyl group or methacryloyl group per molecule, and an acid value of 30 to 300.
A resin composition consisting of 5 to 75% by weight of an unsaturated acid A of KOH/g, 95 to 25% by weight of another crosslinking polymerizable unsaturated compound B, and a photosensitizer is coated, and the desired amount is irradiated with ultraviolet rays. After forming a shaped hardened film,
A method for producing an etched product by a photo-etching method, characterized in that unnecessary metal plate surfaces are corroded and removed by etching with acid.

The unsaturated acid A, which is a component of the resin assembly used in carrying out the present invention, needs to have a molecular weight in the range of 200 to 2,000.

When an unsaturated acid with a molecular weight smaller than 200 is used, the cured film formed has insufficient adhesion to the metal plate and has poor etching resistance. The resulting resin composition is not preferred because it has an extremely high viscosity, which impedes workability, and it is difficult to form a cured film in the desired shape.

In addition, the acid value of the unsaturated acid must be 30 to 300 KOH/g, and a cured film formed using an unsaturated acid with an acid value lower than 30 has poor adhesion to metal plates and etching. This is not preferable because it tends to reduce the etching properties of the metal during processing.

Resin compositions obtained using unsaturated acids with a boric acid value higher than 300 have poor storage stability, and furthermore, the resistance of the cured film to etching liquids is poor, and the etching properties of metals are reduced, so these are not preferred. do not have.

The unsaturated acid used in the present invention must contain at least one acryloyl group or methacryloyl group, and unless such a compound is present, a dried cured film cannot be formed by the method of the present invention. .

Specific examples of unsaturated acids used in carrying out the present invention include the general formula % (wherein R1 is H or CH3, and R2 is C1~).

an alkylene group or a polyethylene glycol residue or a polypropylene gelicol residue having 10 or less repeating units,
R3 is -CH2CH2-, -CH=CH-sha
\/ C-CH2-2 = ≦ ≧ 7 ≦ C00H (indicates a group selected from It can be produced by reacting itaconic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, trimellitic acid, or anhydrides thereof.

Another type of unsaturated acid A refers to a hydroxyl group contained in a diacryloyl or methacryloyl compound obtained by addition-reacting an epoxy compound, which is a condensation product of bisphenol A and epichlorohydrin, with acrylic acid or methacrylic acid. Compounds produced by the addition reaction of the represented acid anhydrides, or acryloyloxyalkyl phosphate or methacryloyloxyalkyl phosphate, which is an addition reaction product of hydroxyalkyl acrylate or methacrylate and phosphoric anhydride or polyphosphoric acid. be.

Other cross-linking polymerizable unsaturated compounds used together with unsaturated acid A in carrying out the present invention are compounds that can form a dry film that is cross-linked and cured by irradiation with ultraviolet rays, and in particular contain at least one acryloyl group in the molecule. or methacryloyl group, and specific examples thereof include the following.

(I) (Meth)acrylic acid addition reaction products of polyexyl compounds (n) Polyfunctional polyester acrylates (G) Polyfunctional heptadumers and monoacrylates such as polyethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , 1.4-butanediol di(meth)acrylate, 1,
These include 6-hexanethiol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 2-hydroxypropyl(meth)acrylate, carpitol(meth)acrylate, and tetrahydrofurfuryl(meth)acrylate.

When carrying out the present invention, the unsaturated acid A is 5 to 75% by weight and the crosslinking polymerizable unsaturated compound is 895 to 25% by weight.
A cured film formed using a resin composition containing 5% by weight or less of an unsaturated acid has insufficient adhesion to the metal plate and has poor etching properties. If it exceeds 75% by weight, the storage stability of the resin composition decreases, which is undesirable. When carrying out the present invention, benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone, and Michler's ketone are added to the resin composition. , a photosensitizer such as jetoxyacetophene is added in a range of 1 to 10% by weight to obtain a wavelength of 200 to 800n71L, preferably 250 to 71L.
It is sufficient to irradiate near ultraviolet rays of 4501 m.

Furthermore, the resin composition of the present invention can be used as it is, but
Other appropriate additives such as pigments and dyes may be added and used as needed, but in order to achieve the purpose of the present invention more efficiently, extender pigments such as pallite powder, sedimentation It is preferable to add sulfuric acid, barium, barium carbonate, clay, silica powder, fine silicic acid, talc, etc. to the resin composition in a proportion of 70% by weight or less.

The production of the engraved product of the present invention involves printing the resin composition on the metal plate surface of a metal laminate, which is formed by providing a thin metal film of copper, copper alloy, Kovar, permalloy, etc., on an insulating substrate as a metal plate using a screen printing machine or Either print the desired shape using a gravure printing machine and irradiate it with ultraviolet rays to form a cured film, or apply the resin composition on the metal plate surface and irradiate it with ultraviolet rays through a mask that blocks ultraviolet rays into the desired shape. After removing the uncured resin portion and forming a hardened film, etching is performed using an acid bath or liquid such as nitric acid, hydrochloric acid, or ferric chloride as an etching solution to remove the parts that are not covered with the hardened film. Corrosion is removed from the metal plate, and the hardened film that is no longer needed is removed by dissolving it in an alkaline solution with a pH of 9 or higher, such as NaOH, KOH, ammonia, water or a water-soluble organic solvent solution of primary to tertiary amines. By doing so, an etched product can be obtained, and the portion from which the hardened film has been removed can be further protected by plating.

Since the resin compound used in the present invention is solvent-free, there is no concern about air pollution during the process of forming a cured film.
In addition, since it is an ultraviolet irradiation method, there is no thermal deformation of the substrate, and it can be dried and cured quickly.The formed cured film has good adhesion to the metal plate and good etching properties of the metal during the etching process. It is easy to remove the hardened film that requires post-peeling, and by etching a metal plate on which such a hardened film is formed, an excellent etched product can be obtained, and its industrial value is high. Very dog-like.

The present invention will be explained in more detail below using Examples.

Note that "Example Middle" means parts by weight.

Example 1 Adding succinic anhydride to 2-hydroxyethyl acrylate
t, = unsaturated acid obtained (acid value 260KOH■number/?)
30 parts, 10 parts of acryloyloxyethyl phosphate (acid value 265 KOH/g), 40 parts of acrylic acid adduct of epoxy resin (Shodyne 508, manufactured by Showa Denko), and 20 parts of carpitol acrylate. I got something.

Ink (2) was obtained by kneading 100 parts of this resin composition with 5 parts of benzoin methyl ether, 30 parts of talc, and 2 parts of phthalocyanine blue.

The ink (2) was printed in the desired shape on a copper laminate board using a 250 mesh screen printer, and then 80W/crf
The ink film was completely cured by irradiating it with ultraviolet rays for 8 seconds using an L high-pressure mercury lamp.

The copper laminate on which this cured ink film was formed was treated with dichloromethane.
The copper plate is immersed in saturated iron water for 24 hours to corrode and remove the portions of the copper plate that are not covered with the hardened ink film, and then the unnecessary hardened ink film is dissolved and removed using a NaOH solution with a pH of 9.5. I got a carved product.

The cured ink film formed on the surface of the copper laminate by the above method had excellent properties as shown in Appendix Table 1, making it possible to obtain highly accurate etched products.

Comparative Example 1 An epoxy resin (Shodine 508 Ink (2) was obtained in the same manner as in Example 1 using a resin composition consisting of 70 parts of an acrylic acid adduct (manufactured by Showa Denko Co., Ltd.) and 30 parts of carpitol acrylate.

A cured ink film was formed on the surface of the copper laminate board using this ink (2) in the same manner as in Example 1, and an etched product was obtained by removing the unnecessary hardened film portion by performing an elastin* treatment. .

As shown in Appendix Table 1, the cured ink film formed on the surface of the copper laminate by the above method has greater properties than the ink (■) using a resin composition containing an unsaturated acid. The width was poor and it was not possible to obtain a good etched product.

Example 2 50 parts of unsaturated acid obtained by adding ioo parts of succinic anhydride to 680 parts of acrylic acid adduct of epoxy resin (Shodyne 729, manufactured by Showa Denko), 10 parts of acryloyloxypropyl phosphate, and tetrahydrofuryl A resin composition consisting of 20 parts of furyl acrylate and 20 parts of carpitol acrylate was obtained.

6 parts of benzoin ethyl ether and 20 parts of talc were added to 100 parts of this resin composition.

This resin composition was applied onto the surface of a copper laminate, a negative film having a desired shape was overlaid thereon, and then 80W/
Ultraviolet rays were irradiated and exposed for 30 seconds using a C1rL high-pressure mercury lamp.

Thereafter, the unexposed areas were washed away with water to form a cured film faithful to the negative film.

Thereafter, etching treatment was performed in the same manner as in Example 1,
The copper in the areas not covered with the hardened film was removed by corrosion, and the unnecessary hardened film was removed to obtain an engraved product.

The cured film formed on the surface of the copper laminate by the above method had excellent adhesion and copper etching properties during etching treatment, and an etched product was obtained in which the fine structure was sufficiently etched.

Claims (1)

[Scope of Claims] 1 Unsaturated acid A5 having a molecular weight of 200 to 2000, having one or more acryloyl group or methacryloyl group in one molecule, and having an acid value of 30 to 300 KOH1rI9 several 1 g on the surface of the metal plate. A resin composition consisting of ~75% by weight, 95% to 25% by weight of other cross-linked polymerizable unsaturated compound B, and a photosensitizer is applied, and after irradiation with ultraviolet rays to form a cured film in the desired shape, acid 1. A method for producing an etched product using a photo-etching method, characterized in that unnecessary metal plate surfaces are corroded and removed by etching. 2. A method for producing an etched product for a printed wiring board by a photoetching method according to claim 1, wherein the metal plate surface is a metal thin film provided on an insulating substrate. 3. A method for producing an etched product for a printed wiring board by a photoetching method according to claim 1, characterized in that a resin composition containing an extender pigment is used.