JP7049051B2 - Resist residue remover, conductor pattern forming method using it, and substrate manufacturing method - Google Patents

Description

The present invention relates to a resist residue removing agent capable of removing a resist residue such as a tailing portion of a resist by a simple wet step in resist development of a printed wiring board or the like, a conductor pattern forming method using the resist residue removing agent, and a substrate manufacturing method.

The printed wiring board is manufactured by a photolithography method. In the photolithography method, a photosensitive resist layer is formed on a substrate, a pattern is exposed to polymerize and cure the exposed portion of the resist layer, and an unexposed portion is removed with a developing solution to form a resist pattern on the substrate. Then, after plating or etching to form a conductor pattern, the resist pattern is peeled off and removed to complete the conductor pattern.

The method for forming a conductor pattern is roughly classified into a subtractive method and an additive method, and a semi-additive method is used as a method for creating a fine and high-density pattern. In this method, a photosensitive resist layer formed on a seed copper thin film of a substrate is exposed and developed to form a resist pattern, and then plating is applied between the resist patterns to form a plated copper pattern, and the resist is peeled off. Then, the plated copper pattern and the seed copper thin film are simultaneously etched by flash etching.

In the resist developing step, if the developing time is too long, the resist swells and peeling from the substrate is likely to occur. Therefore, it usually tends to be terminated in a slightly insufficiently developed state, but if there is an undeveloped portion, hemming occurs at the boundary portion between the cured resist and the substrate, and resist deposits remain on the substrate surface in spots. Sometimes. When plating is performed in the state where such a hemming portion exists between the resist patterns, an undercut portion that looks like a scoop is formed at the bottom of the plating, and the contact area between the formed plated copper pattern and the copper thin film is reduced. Therefore, the interfacial adhesion strength between the copper thin film and the plated copper pattern is lowered, and the copper thin film and the plated copper pattern are easily peeled off. Similarly, when the resist deposits are scattered on the copper thin film, the adhesion strength is lowered. Even when the pattern is formed by etching in the subtractive method, the surface area of the copper foil exposed after development decreases if a hem portion or the like is present, so that etching removal may be insufficient.

In order to remove such a resist tailing portion and resist deposits, plasma treatment is performed as a plating pretreatment. Although the hemming portion of the resist and the resist deposits are removed by the plasma treatment, even the cured resist that remains normally as a resist pattern is denatured, and it may be difficult to peel off in the resist peeling step. In addition, an expensive plasma device is required, and in the manufacturing process, the plasma processing process, which is a dry process, is interposed between the development process, which is a wet process, and the plating process, so that the substrate can be continuously processed. However, the process becomes complicated and the production cost increases. Even in the formation of the solder resist pattern, the presence of the resist residue may cause a decrease in the adhesion of nickel / gold plating.

On the other hand, a method of removing a resist residue by washing with washing water containing polyvalent metal ions such as calcium ions and magnesium ions at a constant concentration is disclosed (Patent Document 1). However, it cannot be said that this method is sufficient in terms of the effect of removing the hemming portion of the resist.

Japanese Unexamined Patent Publication No. 2012-208356

An object of the present invention is to provide a technique capable of effectively removing a resist residue such as a resist tailing portion by a simple and continuous treatment without denaturing a normal resist pattern portion. ..

As a result of diligent research to solve the above problems, the present inventors treated the resist pattern with a solution containing a reducing agent or an anionic surfactant having a mercapto group or a sulfite group after resist development. The present invention has been completed by finding that resist residues such as hemming generated at the boundary between the cured resist and the substrate and resist deposits scattered on the surface of the substrate can be effectively removed.

That is, the present invention is a resist residue removing agent containing a compound selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant as an active ingredient.

Further, the present invention is a resist residue removing method characterized in that a resist layer formed on the surface of a substrate is exposed and developed to form a resist pattern, and the resist pattern is treated with the resist residue removing solution.

The present invention is also characterized in that a plating resist layer formed on the surface of a substrate is exposed and developed to form a plating resist pattern, and the plating resist pattern is treated with the resist residue removing liquid and then plated. This is a conductor pattern forming method.

Further, in the present invention, a plating resist layer formed on the surface of a substrate is exposed and developed to form a plating resist pattern, and the plating resist pattern is treated with the resist residue removing solution and then plated to form a conductor pattern. Next, it is a method for manufacturing a printed wiring board, which comprises peeling off the plated resist pattern.

Further, in the present invention, a solder resist layer is formed on the surface of a substrate on which a conductor pattern is formed, the solder resist layer is exposed and developed to form a solder resist pattern, and the resist pattern is treated with the resist residue removing solution. It is a method for forming a solder resist pattern, which is characterized by the above.

Further, the present invention is a resist developer containing a compound selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant.

By treating the resist pattern with the resist residue removing solution of the present invention, it is possible to remove resist residues such as the hemming portion of the boundary portion between the cured resist and the substrate and the resist deposits remaining on the surface of the substrate. By applying this removing liquid to the plating resist, the formation of the undercut portion of the conductor pattern formed by the plating process is suppressed, and the interfacial adhesion strength with the substrate is improved, so that the conductor pattern is prevented from peeling off. Can be done. Further, since this treatment can be performed in a simple wet process, continuous processing of the substrate is possible and the normal resist pattern is not denatured, so that the peelability is not impaired in the subsequent resist pattern peeling step. .. Further, when applied to a solder resist, it is possible to prevent a resist residue in a fine pad portion or the like and improve the adhesion of nickel / gold plating.

In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Example 1 and then a copper pattern was formed by electrolytic copper plating. In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing liquid of Example 2 and then a copper pattern was formed by electrolytic copper plating. In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing liquid of Example 3 and then a copper pattern was formed by electrolytic copper plating. In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Example 4 and then a copper pattern was formed by electrolytic copper plating. In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Example 5 and then a copper pattern was formed by electrolytic copper plating. In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing liquid of Example 6 and then a copper pattern was formed by electrolytic copper plating. In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing liquid of Example 7 and then a copper pattern was formed by electrolytic copper plating. In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing liquid of Example 8 and then a copper pattern was formed by electrolytic copper plating. In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Comparative Example 1 and then a copper pattern was formed by electrolytic copper plating. In Test Example 1, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Comparative Example 2 and then a copper pattern was formed by electrolytic copper plating. FIG. 2 is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Example 9 in Test Example 2 and then a copper pattern was formed by electrolytic copper plating. FIG. 2 is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing liquid of Example 10 in Test Example 2 and then a copper pattern was formed by electrolytic copper plating. In Test Example 2, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing liquid of Example 11 and then a copper pattern was formed by electrolytic copper plating. FIG. 2 is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Example 12 in Test Example 2 and then a copper pattern was formed by electrolytic copper plating. FIG. 2 is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Comparative Example 3 in Test Example 2 and then a copper pattern was formed by electrolytic copper plating. FIG. 2 is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Comparative Example 4 in Test Example 2 and then a copper pattern was formed by electrolytic copper plating. In Test Example 3, it is a cross-sectional photograph of a test piece in which a copper pattern is formed by electrolytic copper plating without treatment with a removing liquid after development. 3 is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Example 1 in Test Example 3 and then a copper pattern was formed by electrolytic copper plating. In Test Example 4, it is a cross-sectional photograph of a test piece in which a copper pattern is formed by electrolytic copper plating without treatment with a removing liquid after development. In Test Example 4, it is a cross-sectional photograph of a test piece in which a resist pattern was treated with the removing solution of Example 1 and then a copper pattern was formed by electrolytic copper plating.

The resist residue removing agent of the present invention (hereinafter, may be referred to as "removing liquid") contains a compound selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant as an active ingredient. .. In the present invention, the resist residue includes a hem portion at the boundary between the cured resist and the substrate generated when the photosensitive resist layer formed on the substrate is exposed and developed, and resist deposits remaining on the surface of the substrate. Is done. Further, the resist includes a plating resist, a solder resist and the like.

Among the above reducing agents, examples of the reducing agent having a mercapto group include thioglycolic acid, ammonium thioglycolate, thioglycolate such as monoethanolamine thioglycolic acid, cysteine, and the like, and one or two of these. The above can be used. Examples of the reducing agent having a sulfurous acid group include sodium metabisulfite, sodium sulfite, sodium hydrogen sulfite and the like, and one or more of these can be used. Of these, a reducing agent having a mercapto group and a carboxyl group, such as thioglycolic acid or a salt thereof, is suitable because an excellent resist residue removing effect can be obtained by short-time treatment. The concentration of the reducing agent having a mercapto group or a sulfite group is not particularly limited, but is preferably 0.05 to 20 g / L, preferably 0.1 to 15 g / L, from the viewpoint of the resist residue removing effect and the like. More preferred. When a reducing agent having a sulfurous acid group is used, it is preferable to use an organic acid or a salt thereof in combination from the viewpoint of the effect of removing resist residue and the like. Examples of the organic acid include citric acid, acetic acid, methanesulfonic acid and the like, and examples thereof include ammonium salt and sodium salt. The concentration of the organic acid or a salt thereof is not particularly limited, but is preferably 0.1 to 10 g / L, and more preferably 0.3 to 5 g / L.

The anionic surfactant is not particularly limited, and is, for example, an alkylbenzene sulfonic acid such as decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, and tetradecylbenzenesulfonic acid. Salts, fatty acid soaps such as sodium lauryl sulphate, sodium laureth sulphate, sodium cocoyl glutamate, sodium cocoyl methylalanine, sodium lauryl sulfosuccinate, α-olein sulfonates such as α-olefin sulfonate, polyoxyethylene tridecyl ether Examples thereof include polyoxyethylene alkyl ether phosphoric acid esters such as phosphoric acid esters and polyoxyethylene alkyl (C12,13) ether phosphoric acid esters, and one or more of these can be used. Of these, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium α-olefin sulfonate, polyoxyethylene tridecyl ether phosphate, and the like are suitable because they are excellent in the effect of removing the resist residue. The concentration of the anionic surfactant is not particularly limited, but is preferably 0.1 to 20 g / L, more preferably 1 to 15 g / L, from the viewpoint of the resist residue removing effect and the like.

When an anionic surfactant is used, the effect of removing the resist residue is improved by further adding an inorganic acid such as sulfuric acid or hydrochloric acid. The concentration of the inorganic acid is not particularly limited, but is preferably 1 to 20 g / L, more preferably 5 to 15 g / L.

The removing solution of the present invention is prepared by dissolving the reducing agent having a mercapto group or a sulfite group, an anionic surfactant, an inorganic acid or the like in water. As the water, it is preferable to use water from which impurities such as ion-exchanged water, pure water, and ultrapure water have been removed.

Further components such as calcium ion, magnesium ion, and aluminum ion can be added to the removing solution of the present invention as long as the effect of the present invention is not impaired.

The resist residue removing method of the present invention is characterized in that a resist layer formed on the surface of a substrate is exposed and developed to form a resist pattern, and the resist pattern is treated with the resist residue removing agent of the present invention described above. And. Examples of the resist include a plating resist, a solder resist and the like.

The resist pattern formation of the plated resist can be performed according to a known method. Examples of the substrate include a copper-clad laminate, a substrate in which build-up resin is laminated and electroless copper plating is applied, and a substrate in which a thin electrolytic copper plating (strike copper plating) of about 1 um is applied. A liquid photosensitive resist is applied and dried, or the photosensitive dry film resist is heat-bonded to the substrate using a laminator to form a resist layer on the substrate.

Next, the substrate on which the resist layer is formed is exposed to active light through a photomask. The exposure amount can be set as appropriate.

Further, the latent image formed on the resist layer by exposure is made into a visible image by using a developing solution. As the developing solution, an aqueous solution of sodium carbonate, potassium carbonate or the like is used, and development is performed by immersing the substrate in the developing solution or spraying it with a spray or the like. By development, the unexposed portion of the resist layer is removed to form a resist pattern.

The resist pattern thus formed is treated with a resist residue removing solution containing a compound selected from the group consisting of the reducing agent having a mercapto group or a sulfite group and an anionic surfactant. By this treatment, it is possible to remove resist residues such as a tailed portion generated at the boundary portion between the cured resist and the substrate and resist deposits remaining on the substrate surface. In the present invention, the treatment of the resist pattern with the resist residue removing liquid also includes the treatment of the substrate surface between the resist patterns.

Examples of the treatment with the resist residue removing liquid include a method of immersing the substrate on which the resist pattern is formed in the resist residue removing liquid, or spraying the resist residue removing liquid onto the substrate by spraying or the like. The treatment temperature is preferably 15 to 30 ° C., more preferably 20 to 25 ° C. from the viewpoint of preventing the dry film pattern from peeling off due to excessive treatment for removing the resist residue. In the case of spraying, the treatment time is preferably about 5 to 60 seconds, more preferably about 10 to 30 seconds. In the case of spray, the pressure is preferably 0.02 MPa to 0.2 MPa, more preferably 0.05 MPa to 0.15 MPa.

As described above, after the treatment with the resist residue removing liquid is performed, a conductor pattern is formed by performing plating or etching treatment on the surface of the substrate exposed by development.

Examples of the plating method include copper sulfate plating and the like. Etching may be performed according to a conventional method using an acidic etching solution such as cupric chloride-hydrochloric acid aqueous solution or sulfuric acid-hydrogen peroxide.

After the plating or etching is completed, the resist pattern is peeled off using an alkaline stripping solution containing sodium hydroxide or the like or an organic amine-based stripping solution. The resist pattern portion is not denatured by the treatment with the resist residue removing liquid, and the peelability is not deteriorated. Through the above steps, a conductor pattern can be formed on a circuit board such as a printed wiring board.

A solder resist pattern is further formed on the substrate on which the conductor pattern is formed as described above, if necessary. The resist residue removing liquid of the present invention can also be applied to a solder resist. Solder resist pattern formation can be performed according to a known method. A liquid solder resist is applied and dried on the surface of the substrate on which the conductor pattern is formed, or a dry film having a solder resist layer is heat-bonded to the substrate using a laminator, and the solder resist is placed on the substrate on which the conductor pattern is formed. Form a layer.

Next, the substrate on which the resist layer is formed is exposed to active light through a photomask. The exposure amount can be set as appropriate.

By developing after exposure, the unexposed portion of the solder resist layer is removed to form a solder resist pattern. As the developing solution, an aqueous solution of sodium carbonate, potassium carbonate or the like is used, and development is performed by immersing the substrate in the developing solution or spraying it with a spray or the like.

The solder resist pattern thus formed is treated with a resist residue removing solution containing a compound selected from the group consisting of the reducing agent having a mercapto group or a sulfite group and an anionic surfactant. By this treatment, it is possible to remove resist residues such as a tailed portion generated at the boundary portion between the cured resist and the substrate and resist deposits remaining on the substrate surface.

Examples of the treatment with the resist residue removing liquid include a method of immersing the substrate on which the solder resist pattern is formed in the resist residue removing liquid, or spraying the resist residue removing liquid onto the substrate by spraying or the like. The treatment temperature is preferably 15 to 30 ° C., more preferably 20 to 25 ° C. from the viewpoint of preventing the dry film pattern from peeling off due to excessive treatment for removing the resist residue. The treatment time is preferably about 5 to 60 seconds, more preferably about 10 to 30 seconds. In the case of spray, the pressure is preferably 0.02 MPa to 0.2 MPa, more preferably 0.05 MPa to 0.15 MPa.

As described above, after the treatment with the solder resist residue removing liquid, washing with water, drying, and curing treatment are performed. After that, as the surface treatment of the substrate, nickel plating, gold plating, tin plating or organic rust prevention treatment is performed on the pad portion and the like. If the solder resist residue remains on a minute pad or the like, problems such as a decrease in the adhesiveness of the plating occur. However, by treating with the resist residue removing agent of the present invention, such a decrease in the adhesiveness of the plating can be caused. It can be suppressed.

Further, in the present invention, for a resist containing a compound selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant instead of the treatment with the above removing agent or together with the treatment with the removing agent. By developing with a developing solution, the resist residue can be removed or prevented.

An aqueous solution of sodium carbonate, potassium carbonate or the like is used as the developing solution, and the developing solution for resist of the present invention was further selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant. Contains compounds. Among the above reducing agents, examples of the reducing agent having a mercapto group include thioglycolic acid, ammonium thioglycolate, thioglycolate such as monoethanolamine thioglycolic acid, cysteine, and the like, and one or two of these. The above can be used. Examples of the reducing agent having a sulfurous acid group include sodium metabisulfite, sodium sulfite, sodium hydrogen sulfite and the like, and one or more of these can be used. Of these, a reducing agent having a mercapto group and a carboxyl group, such as thioglycolic acid or a salt thereof, is suitable because an excellent resist residue removing effect can be obtained by short-time treatment. The concentration of the reducing agent having a mercapto group or a sulfite group in the developer for resist of the present invention is not particularly limited, but is preferably 0.05 to 20 g / L from the viewpoint of the resist residue removing effect and the like, and is preferably 0.1. More preferably, it is ~ 15 g / L. When a reducing agent having a sulfurous acid group is used, it is preferable to use an organic acid or a salt thereof in combination from the viewpoint of the effect of removing resist residue and the like. Examples of the organic acid include citric acid, acetic acid, methanesulfonic acid and the like, and examples thereof include ammonium salt and sodium salt. The concentration of the organic acid or a salt thereof is not particularly limited, but is preferably 0.1 to 10 g / L, and more preferably 0.3 to 5 g / L.

The anionic surfactant is not particularly limited, and is, for example, an alkylbenzene sulfonic acid such as decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, and tetradecylbenzenesulfonic acid. Salts, fatty acid soaps such as sodium lauryl sulphate, sodium laureth sulphate, sodium cocoyl glutamate, sodium cocoyl methylalanine, sodium lauryl sulfosuccinate, α-olein sulfonates such as α-olefin sulfonate, polyoxyethylene tridecyl ether Examples thereof include polyoxyethylene alkyl ether phosphoric acid esters such as phosphoric acid esters and polyoxyethylene alkyl (C12,13) ether phosphoric acid esters, and one or more of these can be used. Of these, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium α-olefin sulfonate, polyoxyethylene tridecyl ether phosphate, and the like are suitable because they are excellent in the effect of removing the resist residue. The concentration of the anionic surfactant is not particularly limited, but is preferably 0.1 to 20 g / L, more preferably 1 to 15 g / L, from the viewpoint of the resist residue removing effect and the like.

The resist residue removing method of the present invention is characterized in that a resist layer formed on the surface of a substrate is exposed and then developed with the resist developer of the present invention to form a resist pattern. Examples of the resist include a plating resist, a solder resist and the like.

The resist pattern formation of the plated resist can be performed according to a known method. Examples of the substrate include a copper-clad laminate, a substrate in which build-up resin is laminated and electroless copper plating is applied, and a substrate in which a thin electrolytic copper plating (strike copper plating) of about 1 um is applied. A liquid photosensitive resist is applied and dried, or the photosensitive dry film resist is heat-bonded to the substrate using a laminator to form a resist layer on the substrate.

Next, the substrate on which the resist layer is formed is exposed to active light through a photomask. The exposure amount can be set as appropriate.

Further, the latent image formed on the resist layer by exposure is made into a visible image by using the above-mentioned developer for resist of the present invention. Development is performed by immersing the substrate in the developer or spraying it with a spray or the like. By development, the unexposed portion of the resist layer is removed to form a resist pattern. By developing with the developer for resist of the present invention, it is possible to remove or prevent resist residues such as a tailing portion that may occur at the boundary portion between the cured resist and the substrate and resist deposits that may remain on the surface of the substrate. can.

The resist pattern thus formed may be further treated with the resist residue removing solution, if necessary. Examples of the treatment method using the resist residue removing liquid include a method of immersing the substrate on which the resist pattern is formed in the resist residue removing liquid, or a method of spraying the resist residue removing liquid onto the substrate by spraying or the like. The treatment temperature is preferably 15 to 30 ° C., more preferably 20 to 25 ° C. from the viewpoint of preventing the dry film pattern from peeling off due to excessive treatment for removing the resist residue. In the case of spraying, the treatment time is preferably about 5 to 60 seconds, more preferably about 10 to 30 seconds. In the case of spray, the pressure is preferably 0.02 MPa to 0.2 MPa, more preferably 0.05 MPa to 0.15 MPa.

As described above, a conductor pattern is formed on the surface of the substrate exposed by development by plating or etching.

Examples of the plating method include copper sulfate plating and the like. Etching may be performed according to a conventional method using an acidic etching solution such as cupric chloride-hydrochloric acid aqueous solution or sulfuric acid-hydrogen peroxide.

After the plating or etching is completed, the resist pattern is peeled off using an alkaline stripping solution containing sodium hydroxide or the like or an organic amine-based stripping solution. The resist pattern portion is not denatured by the treatment with the resist residue removing liquid, and the peelability is not deteriorated. Through the above steps, a conductor pattern can be formed on a circuit board such as a printed wiring board.

A solder resist pattern is further formed on the substrate on which the conductor pattern is formed as described above, if necessary. Solder resist pattern formation can be performed according to a known method. A liquid solder resist is applied and dried on the surface of the substrate on which the conductor pattern is formed, or a dry film having a solder resist layer is heat-bonded to the substrate using a laminator, and the solder resist is placed on the substrate on which the conductor pattern is formed. Form a layer.

Next, the substrate on which the resist layer is formed is exposed to active light through a photomask. The exposure amount can be set as appropriate.

After exposure, the unexposed portion of the solder resist layer is removed by developing with the developer for resist of the present invention, and a solder resist pattern is formed. Development is performed by immersing the substrate in a developing solution or spraying it with a spray or the like. By developing with the developer for resist of the present invention, it is possible to remove or prevent resist residues such as a tailing portion that may occur at the boundary portion between the cured resist and the substrate and resist deposits that may remain on the surface of the substrate. can.

The solder resist pattern thus formed may be further treated with the resist residue removing solution, if necessary. Examples of the treatment with the resist residue removing liquid include a method of immersing the substrate on which the solder resist pattern is formed in the resist residue removing liquid, or spraying the resist residue removing liquid onto the substrate by spraying or the like. The treatment temperature is preferably 15 to 30 ° C., more preferably 20 to 25 ° C. from the viewpoint of preventing the dry film pattern from peeling off due to excessive treatment for removing the resist residue. The treatment time is preferably about 5 to 60 seconds, more preferably about 10 to 30 seconds. In the case of spray, the pressure is preferably 0.02 MPa to 0.2 MPa, more preferably 0.05 MPa to 0.15 MPa.

As described above, after the treatment with the solder resist residue removing liquid, washing with water, drying, and curing treatment are performed. After that, as the surface treatment of the substrate, nickel plating, gold plating, tin plating or organic rust prevention treatment is performed on the pad portion and the like. If the solder resist residue remains on a minute pad or the like, problems such as deterioration of plating adhesion occur. However, by developing with the developer for resist of the present invention, such deterioration of plating adhesion and the like can be caused. It can be suppressed.

Next, examples and the like will be shown and the present invention will be described in more detail, but the present invention is not limited thereto.

Test Example 1
Resist residue removal effect confirmation test (1)
A dry film (manufactured by Asahi Kasei Co., Ltd., UFG-258 (for SAP), 25 um thickness) was laminated on a copper-clad laminate (a substrate in which copper foil GTS-MP35um was laminated on MCL-E-67 manufactured by Hitachi Kasei Co., Ltd.). A resist having a line / space (L / S) of 8/8 μm is exposed by a photomask with an exposure amount of 60 mJ / cm ² and then spray-developed with a 1% sodium carbonate aqueous solution at 25 ° C. for 45 seconds. A test piece having a pattern was prepared.
The test piece was treated with a removal solution prepared by dissolving the components shown in Table 1 in water, washed with water, and dried with a hand dryer for about 1 minute. The treatment was a spray treatment at 0.1 MPa for 15 seconds. After the treatment, electrolytic copper plating (copper sulfate plating CU-BRITE VL manufactured by JCU) was applied to form a copper pattern. Then, the resist pattern was treated with an organic amine solution (JCU resist stripping solution RS-083) at 40 ° C. for 1.5 minutes to strip the resist pattern. A sulfuric acid-hydrogen peroxide solution (flash etching SAC manufactured by JCU) was used as the etching solution, and flash etching was performed at 30 ° C. for 2 minutes. The cross section of each test piece was observed, and the presence or absence of undercut (a gouge at the hem of the copper pattern) was evaluated. The results are also shown in Table 1. Micrographs of cross sections of each test piece are shown in FIGS. 1 to 10.

From the above results, it is shown that by treating the resist pattern with the removing liquids of Examples 1 to 8, the hemming portion of the resist is removed and the formation of undercut of the copper pattern formed thereafter is suppressed. rice field.

Test Example 2
Resist residue removal effect confirmation test (2)
Test Example 1 was used as the removal liquid, which was prepared by dissolving the components shown in Table 2 below in water, and the treatment method was immersion treatment for 2 minutes (the test piece was shaken in the removal liquid). The resist removal effect confirmation test was conducted in the same manner as above. The results are also shown in Table 2. Micrographs of cross sections of each test piece are shown in FIGS. 11 to 16.

From the above results, it is shown that by treating the resist pattern with the removing liquids of Examples 9 to 12, the hemming portion of the resist is removed and the formation of undercut of the copper pattern formed thereafter is suppressed. rice field.

Test Example 3
As a dry film, RY3625 (25um thickness) manufactured by Hitachi Kasei Co., Ltd. was used, and treated with the removing solution of Example 1 in the same manner as in Test Example 1 except that the line / space (L / S) was 20/20 μm. The presence or absence of undercut was evaluated. Micrographs of cross sections of the test pieces are shown in FIGS. 17 (unprocessed) and 18.

Test Example 4
NIT3025U (25um thickness) manufactured by Nichigo Morton Co., Ltd. was used as a dry film, and treated with the removing solution of Example 1 in the same manner as in Test Example 1 except that the line / space (L / S) was 30/30 μm. The presence or absence of undercut was evaluated. Micrographs of cross sections of the test pieces are shown in FIGS. 19 (unprocessed) and 20.

The resist residue removing agent of the present invention is excellent in the effect of removing the resist residue of the resist pattern, and is therefore useful in the manufacture of printed wiring boards and the like.

Claims (14)

A resist residue removing solution containing 0.05 to 20 g / L of a reducing agent having one or two mercapto groups selected from the group consisting of ammonium thioglycolate and monoethanolamine thioglycolate. The resist residue removing solution according to claim 1, further containing an organic acid or a salt thereof. One or more anionic surfactants 1 to 20 g / L and inorganic acids selected from the group consisting of alkylbenzene sulfonates, fatty acid soaps, α-olein sulfonates and polyoxyethylene alkyl ether phosphate esters. Containing resist residue removing solution (excluding those containing a polymer or fluorinated hydride or a salt thereof). A resist layer formed on the surface of a substrate is exposed and developed to form a resist pattern, and the resist pattern is treated with the resist residue removing solution according to any one of claims 1 to 3 . Residue removal method. The plating resist layer formed on the surface of the substrate is exposed and developed to form a plating resist pattern, and the plating resist pattern is treated with the resist residue removing solution according to any one of claims 1 to 3 , and then plated. A method for forming a conductor pattern, which comprises processing. The plating resist layer formed on the surface of the substrate is exposed and developed to form a plating resist pattern, and the plating resist pattern is treated with the resist residue removing solution according to any one of claims 1 to 3 . A method for manufacturing a printed wiring board, which comprises plating to form a conductor pattern, and then peeling off the plated resist pattern. The solder resist layer is formed on the surface of the substrate on which the conductor pattern is formed, the solder resist layer is exposed and developed to form a solder resist pattern, and the resist pattern is described in any one of claims 1 to 3 . A method for forming a solder resist pattern, which comprises treating with a resist residue removing solution of the above. The solder resist layer is formed on the surface of a substrate on which a conductor pattern is formed, the solder resist layer is exposed and developed to form a solder resist pattern, and the resist pattern is described in any one of claims 1 to 3 . A method for producing a printed wiring board, which comprises treating with a resist residue removing solution of the above, and then performing nickel / gold plating, tin plating or organic rust prevention treatment. The plating resist layer formed on the surface of the substrate is exposed and developed to form a plating resist pattern, and the plating resist pattern is treated with the resist residue removing solution according to any one of claims 1 to 3 , and then plated. A method for preventing undercut generation of a conductor pattern, which is characterized by processing. A plating resist layer formed on the surface of a substrate is exposed and developed to form a plating resist pattern, and the plating resist pattern is a compound selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant. A method for forming a conductor pattern, which comprises treating with a resist residue removing liquid containing the above-mentioned material and then plating. A compound selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant, in which a plating resist layer formed on the surface of a substrate is exposed and developed to form a plating resist pattern. A method for producing a printed wiring board, which comprises treating with a resist residue removing liquid containing a resist residue, then plating to form a conductor pattern, and then peeling off the plated resist pattern. A solder resist layer is formed on the surface of the substrate on which the conductor pattern is formed, and the solder resist layer is exposed and developed to form a solder resist pattern, and the resist pattern is formed into a reducing agent and an anion having a mercapto group or a sulfite group. A method for forming a solder resist pattern, which comprises treating with a resist residue removing solution containing a compound selected from the group consisting of a sex surfactant. A solder resist layer is formed on the surface of the substrate on which the conductor pattern is formed, and the solder resist layer is exposed and developed to form a solder resist pattern, and the resist pattern is formed into a reducing agent and an anion having a mercapto group or a sulfite group. A method for producing a printed wiring board, which comprises treating with a resist residue removing solution containing a compound selected from the group consisting of sex surfactants, and then performing nickel / gold plating, tin plating or organic rust prevention treatment. A plating resist layer formed on the surface of a substrate is exposed and developed to form a plating resist pattern, and the plating resist pattern is a compound selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant. A method for preventing undercut formation of a conductor pattern, which comprises performing a plating treatment after treating with a resist residue removing liquid containing the above.

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