Resist remover and method for forming substrate material with conductor pattern using the same

Abstract

To provide a resist remover not including a tetramethylammonium hydroxide or an amine compound as a constituent, while having performance equivalent to resist removers including those as a constituent, and also to provide a method for forming a substrate material having a conductor pattern using the same.SOLUTION: A resist remover is used for removal of a resist pattern for circuit formation. The resist remover includes alkali metal hydroxide of 0.05 to 5 mol / L, aromatic alcohol and / or alcohol being glycol of 0.05 to 8 mol / L, a cyclic compound of 0.005 to 1.0 mol / L, and a balance water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist remover and a method for forming a substrate material having a conductor pattern using the same. [Background technology]

[0002] The following methods are known for forming substrate materials (also referred to as "circuit boards") with conductor patterns, such as printed wiring boards. First, a dry film photoresist (hereinafter simply referred to as "dry film resist") is thermocompression bonded (laminated) onto the substrate material, and then exposed to light through a photomask. Uncured portions are removed with a developer to form a resist pattern. This is then immersed in a copper plating bath, and a copper plating film is formed on the exposed portions of the substrate material by plating. Next, the resist pattern is removed with a resist remover to obtain a substrate material with a conductor pattern.

[0003] Here, sodium hydroxide aqueous solution has conventionally been used as the resist remover. However, as the pitch of the conductor pattern (also referred to as "circuit" or "metal wiring") in a substrate material with a conductor pattern becomes narrower, it becomes difficult to remove the resist pattern with a resist remover containing sodium hydroxide aqueous solution. In order to form narrow-pitch metal wiring on a substrate material, it is necessary to increase the resolution of the resist. However, if the resolution of the resist is increased, the resist after curing will have higher adhesion to the surface of the substrate material and will become highly cross-linked. Furthermore, if the distance between adjacent conductor patterns becomes narrower, the aspect ratio of the resist pattern will increase, so it is necessary to further increase the penetration of the resist remover into the cured resist.

[0004] To address this issue, a resist stripper containing tetramethylammonium hydroxide (TMAH), a quaternary ammonium salt, and an amine compound has been released onto the market. However, this resist stripper is also subject to a new problem: tetramethylammonium hydroxide is designated as a toxic substance due to its strong acute toxicity, and amine compounds contain nitrogen, so the wastewater standards for these compounds are set relatively low. This means that the resist stripper may not be usable in some factories.

[0005] As a resist remover that does not contain "tetramethylammonium hydroxide and an amine compound," Patent Document 1 discloses "a remover composition comprising benzyl alcohol, an anionic surfactant, an alkaline agent such as sodium hydroxide, and water." [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2-166459

[0007] However, since the stripping liquid composition of Patent Document 1 contains a surfactant, it may foam during use and fail to stably remove the resist pattern. Summary of the Invention [Problem to be solved by the invention]

[0008] The invention of the present application aims to provide a resist remover that does not contain tetramethylammonium hydroxide or an amine compound as ingredients but has performance equivalent to that of a resist remover that contains these ingredients, and a method for forming a substrate material with a conductive pattern using the same. [Means for solving the problem]

[0009] A. Resist remover according to the present application The resist remover according to the present application is used to remove a resist pattern for forming a circuit, and is characterized in that the components of the resist remover are 0.05 mol / L to 5 mol / L of an alkali metal hydroxide, 0.05 mol / L to 8 mol / L of an alcohol which is an aromatic alcohol and / or a glycol, 0.005 mol / L to 1.0 mol / L of a cyclic compound, and the remainder being water.

[0010] The alkali metal hydroxide contained in the resist remover according to the present application is preferably one or more selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide, the alcohol is preferably one or more selected from phenoxyethanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, triethylene glycol, and diethylene glycol monobutyl ether, and the cyclic compound is preferably one or more selected from α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and 24-crown-8-ether.

[0011] The resist remover according to the present application preferably contains 0.001 mol / L to 0.7 mol / L of an inhibitor made of a nitrogen compound and / or a sulfur compound.

[0012] When the resist remover according to the present application contains an inhibitor, the inhibitor is preferably one or more selected from benzimidazole, benzotriazole, 1H-tetrazole, 5-amino-1H-tetrazole, 2-mercaptobenzimidazole, and 1-phenyl-5-mercapto-1H-tetrazole.

[0013] B. Method for forming a substrate material with a conductor pattern using the resist remover according to the present application The method for forming a substrate material having a conductive pattern according to the present application uses the resist remover described above and is characterized by including the following steps A to C. Step A: A resist pattern is applied to the surface of a substrate material to obtain a substrate material with a resist pattern. Step B: The surface of the substrate material with the resist pattern obtained in step A is plated to obtain a substrate material with a metal film. Step C: The surface of the substrate material with the metal coating obtained in step B is brought into contact with the resist remover to remove the resist pattern, thereby obtaining a substrate material with a conductor pattern made of a metal coating. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a resist remover that does not contain tetramethylammonium hydroxide or an amine compound, which are environmentally harmful substances, but has performance equivalent to that of a resist remover that does contain these substances as ingredients.The use of this resist remover makes it possible to form a substrate material with a relatively narrow-pitch conductor pattern while reducing the environmental impact. DETAILED DESCRIPTION OF THE INVENTION

[0015] A. Resist remover according to the present application The resist remover according to the present application is used to remove resist patterns for circuit formation. The resist remover is characterized by containing 0.05 mol / L to 5 mol / L of alkali metal hydroxide, 0.05 mol / L to 8 mol / L of an alcohol that is an aromatic alcohol and / or glycol, 0.005 mol / L to 1.0 mol / L of a cyclic compound, and the remainder being water. Note that these values are stated excluding inevitable impurities.

[0016] In the present application, "resist stripping" refers to the removal of a resist pattern in the process of forming a substrate material with a conductor pattern, such as a printed wiring board. More specifically, it refers to stripping a resist pattern formed on a substrate material from the surface of the substrate material after forming a metal film on the exposed surface of the substrate material. A resist stripper refers to a chemical solution used to strip the resist pattern from the surface of the substrate material. The type of substrate material is not particularly limited, and examples include insulating substrates made of epoxy resin, polyimide resin, phenolic resin, etc., and substrates with a metal seed layer, such as a copper layer with a thickness of 1 μm or less, provided on the surface of these insulating substrates.

[0017] The resist remover according to the present application can be suitably used in the stripping of resist patterns used in the formation of substrate materials with relatively narrow-pitch conductor patterns, where the distance between adjacent metal coatings that form the conductor patterns is approximately 5 μm to 15 μm. The resist material used to form the resist pattern is preferably a negative or positive dry film photoresist. Dry film photoresists are photocurable, making them suitable for forming substrate materials with relatively narrow-pitch conductor patterns, and are less likely to leave resist residues on the substrate material when stripped with the resist remover according to the present application. The resist remover according to the present application, having the above-described composition, does not contain tetramethylammonium hydroxide or amine compounds, which are environmentally harmful substances, but has resist stripping performance equivalent to that of a material containing these compounds.

[0018] The resist remover according to the present application contains an alkali metal hydroxide in an amount of 0.05 mol / L to 5 mol / L. This alkali metal hydroxide is the main component of the resist remover. There are no particular limitations on the type of alkali metal hydroxide, and one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like may be used. Here, an alkali metal hydroxide content of less than 0.05 mol / L is undesirable because it tends to be difficult to strip the resist pattern from the surface of the substrate material. On the other hand, an alkali metal hydroxide content of more than 5 mol / L is undesirable because it tends to reduce the ability to strip the resist pattern from the surface of the substrate material. Furthermore, an alkali metal hydroxide content of more than 5 mol / L is undesirable because the resist remover may corrode the surface of the substrate material or the metal coating formed thereon (the portion that becomes the conductive pattern when the resist pattern is removed), depending on the components of the substrate material or the metal coating formed thereon (the portion that becomes the conductive pattern when the resist pattern is removed).

[0019] The resist remover according to the present application contains 0.05 mol / L to 8 mol / L of an alcohol that is an aromatic alcohol and / or a glycol. The aromatic alcohol and / or the glycol alcohol is an auxiliary agent in the resist remover. When the resist remover contains the alcohol, the permeability of the cured resist is improved, and the resist pattern can be removed from the surface of the substrate material in a shorter time.

[0020] The type of alcohol is not particularly limited, and one or more of aromatic alcohols such as phenoxyethanol, benzyl alcohol, and phenethyl alcohol, and glycols such as ethylene glycol, triethylene glycol, and diethylene glycol monobutyl ether may be used. Here, if the alcohol content is less than 0.05 mol / L, the effect of improving the permeability of the cured resist tends to be insufficient, which is undesirable. On the other hand, if the alcohol content exceeds 8 mol / L, the effect of improving the permeability of the cured resist tends to be insufficient, and dissolution in water, which is the solvent, tends to be difficult, which is undesirable.

[0021] The resist remover according to the present application contains a cyclic compound at 0.005 mol / L to 1.0 mol / L. This cyclic compound is an auxiliary agent in the resist remover. When the resist remover contains a cyclic compound, it can remove a resist pattern from the surface of a substrate material without leaving any resist residue on the substrate material. Furthermore, since cyclic compounds have the function of encapsulating other compounds (or other components) within their structure, their combined use with the aforementioned aromatic alcohols and / or glycol alcohols can enhance the ability to remove a resist pattern from the surface of a substrate material. Therefore, when the resist remover contains a cyclic compound, it can efficiently and easily remove a resist pattern used in a process for forming a substrate material with a relatively narrow-pitch conductor pattern, which has high adhesion to the surface of the substrate material and forms highly cross-linked structures.

[0022] The type of cyclic compound is not particularly limited, and one or more of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and 24-crown-8-ether may be used. Here, a cyclic compound content of less than 0.005 mol / L is not preferred because the combined use with an aromatic alcohol and / or glycol alcohol tends to result in a failure to enhance the ability to strip a resist pattern from the surface of a substrate. On the other hand, a cyclic compound content of more than 1.0 mol / L is not preferred because the combined use with an aromatic alcohol and / or glycol alcohol does not result in an improvement in the ability to strip a resist pattern from the surface of a substrate, and also tends to make dissolving the cyclic compound in water, a solvent, difficult. Furthermore, the cyclic compound content in the resist stripper according to the present application is more preferably 0.005 mol / L to 0.5 mol / L. When the content of the cyclic compound is within this range, the resist remover tends to be easier to prepare, and the manufacturing cost of the product can also be reduced.

[0023] The resist remover according to the present application contains water as a solvent for dissolving the above-mentioned components. There are no particular limitations on the type of water, and pure water such as ion-exchanged water or distilled water or tap water can be used, but in order to perform resist stripping more stably and with good reproducibility, it is preferable to use pure water such as ion-exchanged water or distilled water.

[0024] Furthermore, the resist remover according to the present application preferably contains as a component an inhibitor (also referred to as a corrosion suppressant or anticorrosive agent) consisting of a nitrogen compound and / or a sulfur compound. When the resist remover contains an inhibitor, when a substrate material having a resist pattern and a metal coating film (a portion that will become a conductor pattern by removing the resist pattern) on its surface is brought into contact with the resist remover and the surface of the substrate material is treated with the resist remover, the metal components such as copper, tin, nickel, and gold that make up the metal coating film can be prevented from being dissolved (corroded) by the resist remover.

[0025] There are no particular limitations on the type of compound that can be used as the inhibitor. It is sufficient to use one or more nitrogen compounds such as benzimidazole, benzotriazole, 1H-tetrazole, and 5-amino-1H-tetrazole, and sulfur compounds such as 2-mercaptobenzimidazole and 1-phenyl-5-mercapto-1H-tetrazole. The inhibitor content is preferably 0.001 mol / L to 0.7 mol / L. These values are based on the assumption that unavoidable impurities are not included. An inhibitor content of less than 0.001 mol / L is undesirable because it tends to fail to prevent the dissolution (corrosion) of metal components on the substrate material by the resist remover. On the other hand, an inhibitor content exceeding 0.7 mol / L is undesirable because it simply wastes resources without improving the effect of preventing the dissolution (corrosion) of metal components on the substrate material by the resist remover.

[0026] The resist remover according to the present application may be produced by a conventionally known method. For example, predetermined amounts of an alkali metal hydroxide, an alcohol which is an aromatic alcohol and / or a glycol, and a cyclic compound may be added to water at a temperature of about 20°C to 60°C, and the mixture may be mixed using a commercially available stirring device.

[0027] B. Method for forming a substrate material with a conductor pattern using the resist remover according to the present application The method for forming a substrate material having a conductive pattern according to the present application uses the resist remover described above and is characterized by including the following steps A to C.

[0028] Step A: A resist pattern is applied to the surface of a substrate material to obtain a substrate material with a resist pattern.

[0029] While any conventionally known method may be employed for this step A, and there are no particular limitations on the processing conditions, etc., the resist material used to apply the resist pattern is preferably a dry film photoresist. Because dry film photoresists are photocurable, they are suitable for forming substrate materials with relatively narrow-pitch conductor patterns, and when stripped with the resist stripper of the present application, resist residues are unlikely to remain on the substrate material. For example, a negative or positive dry film photoresist is first thermocompression-bonded (laminated) to the surface of a substrate material such as an insulating substrate made of epoxy resin, polyimide resin, or phenolic resin, or a substrate with a metal seed layer (hereinafter simply referred to as a "substrate with a metal seed layer") in which a metal seed layer such as a copper layer with a thickness of 1 μm or less is provided on the surface of such an insulating substrate, followed by exposure through a photomask. Next, a commercially available developer is contacted with the uncured portions by spraying, immersion, or the like, and the uncured portions are removed, thereby forming a resist pattern on the surface of the substrate material with a distance between adjacent resist patterns of approximately 5 μm to 15 μm.

[0030] Step B: The surface of the substrate material with the resist pattern obtained in the above step A is plated to obtain a substrate material with a metal film.

[0031] Any conventionally known method may be used in step B, and there are no particular limitations on the treatment conditions, etc. For example, the surface of the substrate material may be immersed in a commercially available electroplating solution or electroless plating solution to bring the surface into contact with the solution, thereby forming a metal plating film on the substrate material.

[0032] Step C: The surface of the substrate material with the metal coating obtained in the above-mentioned step B is brought into contact with the resist remover of the present application, thereby removing the resist pattern and obtaining a substrate material with a conductor pattern made of the metal coating.

[0033] Here, examples of methods for treating the surface of the substrate material with the resist remover in step C include spraying and immersion. The treatment time for the surface of the substrate material with the resist remover in step C is preferably 10 seconds to 10 minutes. Treatment times shorter than 10 seconds tend to result in an insufficient effect of removing the resist pattern from the surface of the substrate material, which is undesirable. Treatment times longer than 10 minutes are undesirable because they do not improve the effect of removing the resist pattern from the surface of the substrate material and can reduce product productivity. Furthermore, the liquid temperature of the resist remover in step C is preferably 15°C to 70°C. Liquid temperatures lower than 15°C tend to reduce the ability to remove the resist pattern from the surface of the substrate material, which is undesirable. Liquid temperatures higher than 70°C are undesirable because they do not improve the ability to remove the resist pattern from the surface of the substrate material and may corrode the surface of the substrate material or the metal coating film (the portion that becomes the conductor pattern when the resist pattern is removed) formed thereon, which is undesirable.

[0034] If the substrate material used in the above-mentioned step A is a substrate with a metal seed layer, a substrate material with a conductor pattern made of a metal film can be obtained in step C by removing the resist pattern and then selectively removing the metal seed layer exposed on the surface by etching. More specifically, for example, a commercially available flash etching solution can be brought into contact with the surface of the substrate material after the resist pattern has been removed by spraying, immersion, or the like, to remove the unnecessary metal seed layer exposed on the surface of the substrate material.

[0035] Next, the invention of the present application will be specifically explained by showing examples, but the invention of the present application is not limited to these examples. [Example]

[0036] Sodium hydroxide (Fujifilm Wako Pure Chemical Industries, Ltd.), phenoxyethanol (2-phenoxyethanol, Fujifilm Wako Pure Chemical Industries, Ltd.), and α-cyclodextrin (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to 25°C deionized water and mixed using a magnetic stirrer and stirring bar to prepare a resist remover containing 0.5 mol / L sodium hydroxide, 0.2 mol / L phenoxyethanol, 0.2 mol / L α-cyclodextrin, and the remainder water. Note that these values do not include unavoidable impurities. Next, two epoxy resin substrates were prepared, and a negative dry film resist (LDF525F, Nikko Materials Co., Ltd., 25 μm thick) was placed on each of these substrates.

[0037] For one of these substrate materials, a mask substrate for forming a test circuit pattern was placed on the photoresist material, and light from the h-line of a mercury lamp (wavelength 405 nm, light intensity 95 mJ / cm) was applied using a direct exposure device (FDi-3M manufactured by Oak Manufacturing Co., Ltd.). 2Then, a developer solution (aqueous sodium carbonate solution with a concentration of 1% by mass) at 30°C was sprayed onto the substrate material at 0.15 MPa for 38 seconds to remove the photoresist material from the unexposed areas, followed by development and rinsing with water, to obtain a substrate material having a line and space (L / S) resist pattern (a resist pattern with a width and interval of 8 μm) on its surface.

[0038] Next, for the other substrate material, a mask substrate for forming another test circuit pattern was placed on the photoresist material, and similarly, light from the h-line of a mercury lamp (wavelength 405 nm, light intensity 95 mJ / cm) was irradiated using a direct exposure device (FDi-3M manufactured by Oak Manufacturing Co., Ltd.). 2 Then, a developer solution (aqueous sodium carbonate solution with a concentration of 1% by mass) at 30°C was sprayed onto the substrate material at 0.15 MPa for 38 seconds to remove the photoresist material in the unexposed areas, followed by development and rinsing with water, to obtain a substrate material having a line and space (L / S) resist pattern (a resist pattern with a width and interval of 20 μm) on its surface.

[0039] Next, these two substrate materials with resist patterns were each immersed in an acidic degreasing agent (Melplate CL-2000 manufactured by Meltex Inc.), rinsed with water, and acid-cleaned with 10% by mass sulfuric acid. These substrate materials were each immersed in a copper sulfate plating solution (Lucent Copper PVF manufactured by Meltex Inc.), rinsed with water, and substrate materials with copper coatings on their surfaces were obtained by electroless plating. These substrate materials were then immersed in a resist remover containing the above-mentioned components at 25°C for 3.5 minutes (3 minutes 30 seconds) to remove the resist patterns, and then rinsed with water to obtain a "substrate material having on its surface a conductive pattern with a width and spacing of both 8 μm (L / S 8 μm)" and a "substrate material having on its surface a conductive pattern with a width and spacing of both 20 μm (L / S 20 μm)."

[0040] When the two substrate materials with conductive patterns obtained by the method of Example 1 were observed under an electron microscope, it was found that the resist patterns formed on the substrate materials had been completely removed from the surface of the substrate materials, and no resist residue was present. The test results of Example 1 are shown in Table 1. In Table 1, those in which the dry film resist (DFR) had good strippability (those in which the resist pattern had been completely removed from the surface of the substrate material and no resist residue was present) were indicated as "Good," and those in which the dry film resist had insufficient strippability (those in which at least a portion of the resist pattern remained on the surface of the substrate material) were indicated as "Poor." Table 1 also lists the composition of the resist remover used in the test and the immersion time of the substrate material in the resist remover (treatment time of the substrate material surface). [Example]

[0041] Example 2 differs from Example 1 only in that the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 4 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 2 are shown in Table 1. [Example]

[0042] [Tests on the concentration and type of alkali metal hydroxides] Example 3 differs from Example 1 only in that the sodium hydroxide concentration was changed from 0.5 mol / L to 0.1 mol / L and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 3 are shown in Table 1. [Example]

[0043] Example 4 differs from Example 1 only in that the sodium hydroxide concentration was changed from 0.5 mol / L to 1 mol / L, 0.11 mol / L benzyl alcohol was used instead of 0.2 mol / L phenoxyethanol, 0.01 mol / L β-cyclodextrin was used instead of 0.2 mol / L α-cyclodextrin, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 1.5 minutes (1 minute 30 seconds). Therefore, the test conditions and evaluation method are not described here. The test results of Example 4 are shown in Table 1. [Example]

[0044] Example 5 differs from Example 1 only in that the sodium hydroxide concentration was changed from 0.5 mol / L to 5 mol / L and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 5 are shown in Table 1. [Example]

[0045] Example 6 differs from Example 1 only in that potassium hydroxide with a concentration of 5 mol / L was used instead of sodium hydroxide with a concentration of 0.5 mol / L, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 6 are shown in Table 2. The reagent (potassium hydroxide) used was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Example]

[0046] Example 7 differs from Example 1 only in that lithium hydroxide with a concentration of 0.1 mol / L was used instead of sodium hydroxide with a concentration of 0.5 mol / L, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 7 are shown in Table 2. The reagent (lithium hydroxide monohydrate) used was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Example]

[0047] [Alcohol concentration test] Example 8 differs from Example 1 only in that the concentration of phenoxyethanol was changed from 0.2 mol / L to 0.1 mol / L and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 3 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 8 are shown in Table 1. [Example]

[0048] Example 9 differs from Example 1 only in that the phenoxyethanol concentration was changed from 0.2 mol / L to 5 mol / L and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 2.5 minutes (2 minutes 30 seconds). Therefore, the test conditions and evaluation method are not described here. The test results of Example 9 are shown in Table 1. [Example]

[0049] [Test for types of alcohol] Example 10 differs from Example 1 only in that 0.2 mol / L benzyl alcohol was used instead of 0.2 mol / L phenoxyethanol, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 3 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 10 are shown in Table 3. The reagent (benzyl alcohol) used was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Example]

[0050] Example 11 differs from Example 1 only in that phenethyl alcohol with a concentration of 0.2 mol / L was used instead of phenoxyethanol with a concentration of 0.2 mol / L, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 3 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 11 are shown in Table 3. The reagent (phenethyl alcohol) used was manufactured by Kanto Chemical Co., Inc. [Example]

[0051] Example 12 differs from Example 1 only in that 0.2 mol / L ethylene glycol was used instead of 0.2 mol / L phenoxyethanol, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 12 are shown in Table 4. The reagent (ethylene glycol) used was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Example]

[0052] Example 13 differs from Example 1 only in that 0.2 mol / L triethylene glycol was used instead of 0.2 mol / L phenoxyethanol. Therefore, the test conditions and evaluation methods are not described here. The test results of Example 13 are shown in Table 4. The reagent (triethylene glycol) used was manufactured by Tokyo Chemical Industry Co., Ltd. [Example]

[0053] Example 14 differs from Example 1 only in that 0.2 mol / L diethylene glycol monobutyl ether was used instead of 0.2 mol / L phenoxyethanol, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 3 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 14 are shown in Table 4. The reagent (diethylene glycol monobutyl ether) used was manufactured by Tokyo Chemical Industry Co., Ltd. [Example]

[0054] [Test for types of cyclic compounds] Example 15 differs from Example 1 only in that β-cyclodextrin at a concentration of 0.2 mol / L was used instead of α-cyclodextrin at a concentration of 0.2 mol / L. Therefore, the test conditions and evaluation methods are not described here. The test results of Example 15 are shown in Table 5. The reagent (β-cyclodextrin) used was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Example]

[0055] Example 16 differs from Example 1 only in that 0.2 mol / L of γ-cyclodextrin was used instead of 0.2 mol / L of α-cyclodextrin, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 4 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 16 are shown in Table 5. The reagent (γ-cyclodextrin) used was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Example]

[0056] Example 17 differs from Example 1 only in that 0.2 mol / L of 18-crown-6-ether was used instead of 0.2 mol / L of α-cyclodextrin, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 3 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Example 17 are shown in Table 5. The reagent (18-crown-6-ether) used was manufactured by Tokyo Chemical Industry Co., Ltd. Comparative Example

[0057] [Comparative Example 1] Comparative Example 1 differs from Example 1 only in that the sodium hydroxide concentration was changed from 0.5 mol / L to 0.01 mol / L and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Comparative Example 1 are shown in Table 6.

[0058] Comparative Example 2 Comparative Example 2 differs from Example 1 only in that the sodium hydroxide concentration was changed from 0.5 mol / L to 8 mol / L and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Comparative Example 2 are shown in Table 6.

[0059] Comparative Example 3 Comparative Example 3 differs from Example 1 only in that a resist remover containing 0.2 mol / L phenoxyethanol, 0.2 mol / L α-cyclodextrin, and the remainder being water was used instead of a resist remover containing 0.5 mol / L sodium hydroxide, 0.2 mol / L phenoxyethanol, 0.2 mol / L α-cyclodextrin, and the remainder being water, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Comparative Example 3 are shown in Table 6.

[0060] Comparative Example 4 Comparative Example 4 differs from Example 1 only in that a resist remover containing 0.2 mol / L of α-cyclodextrin and the remainder being water (a resist remover consisting of an aqueous α-cyclodextrin solution with a concentration of 0.2 mol / L) was used instead of a resist remover containing 0.5 mol / L of sodium hydroxide, 0.2 mol / L of phenoxyethanol, 0.2 mol / L of α-cyclodextrin, and the remainder being water, and in that the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Comparative Example 4 are shown in Table 6.

[0061] Comparative Example 5 Comparative Example 5 differs from Example 1 only in that a resist remover containing 0.2 mol / L phenoxyethanol and the remainder water (a resist remover consisting of an aqueous phenoxyethanol solution with a concentration of 0.2 mol / L) was used instead of a resist remover containing 0.5 mol / L sodium hydroxide, 0.2 mol / L phenoxyethanol, 0.2 mol / L α-cyclodextrin, and the remainder water, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Comparative Example 5 are shown in Table 6.

[0062] Comparative Example 6 Comparative Example 6 differs from Example 1 only in that a resist remover containing 0.5 mol / L sodium hydroxide, 0.2 mol / L phenoxyethanol, 0.2 mol / L α-cyclodextrin, and the remainder being water was replaced with a resist remover containing 0.5 mol / L sodium hydroxide, 0.2 mol / L α-cyclodextrin, and the remainder being water, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Comparative Example 6 are shown in Table 6.

[0063] Comparative Example 7 Comparative Example 7 differs from Example 1 only in that a resist remover containing 0.5 mol / L sodium hydroxide, 0.2 mol / L phenoxyethanol, 0.2 mol / L α-cyclodextrin, and the remainder being water was replaced with a resist remover containing 0.5 mol / L sodium hydroxide, 0.2 mol / L phenoxyethanol, and the remainder being water, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Comparative Example 7 are shown in Table 6.

[0064] [Comparative Example 8] Comparative Example 8 differs from Example 1 only in that a resist remover containing 0.5 mol / L sodium hydroxide, the remainder being water (a resist remover consisting of a 0.5 mol / L aqueous sodium hydroxide solution) was used instead of a resist remover containing 0.5 mol / L sodium hydroxide, 0.2 mol / L phenoxyethanol, 0.2 mol / L α-cyclodextrin, and the remainder being water, and the immersion time of the substrate material in the resist remover was changed from 3.5 minutes to 5 minutes. Therefore, the test conditions and evaluation method are not described here. The test results of Comparative Example 8 are shown in Table 6.

[0065] [Table 1]

[0066] [Table 2]

[0067] [Table 3]

[0068] [Table 4]

[0069] [Table 5]

[0070] [Table 6]

[0071] [Comparison between Examples and Comparative Examples] As can be seen from the above test results, in Examples 1 to 17, which used "a resist remover containing 0.05 mol / L to 5 mol / L of alkali metal hydroxide, 0.05 mol / L to 8 mol / L of an alcohol which is an aromatic alcohol and / or glycol, 0.005 mol / L to 1.0 mol / L of a cyclic compound, with the remainder being water," the dry film resist peelability was good for both "those with a width and spacing of 8 μm (L / S is 8 μm)" and "those with a width and spacing of 20 μm (L / S is 20 μm)," and the resist pattern was completely removed from the surface of the substrate material, with no resist residue remaining. As a result, it was possible to properly form both a "substrate material having a conductive pattern on its surface with a width and spacing of both 8 μm (L / S 8 μm)" and a "substrate material having a conductive pattern on its surface with a width and spacing of both 20 μm (L / S 20 μm)."

[0072] On the other hand, in Comparative Examples 1 and 2, which used "resist removers with alkali metal hydroxide concentrations outside the range of 0.05 mol / L to 5 mol / L," and Comparative Examples 3 to 5, which used "resist removers that do not contain alkali metal hydroxide as a main component," the dry film resist strippability was insufficient for both "a width and spacing of 8 μm (L / S of 8 μm)" and "a width and spacing of 20 μm (L / S of 20 μm)," and at least a portion of the resist pattern remained on the surface of the substrate material. As a result, it was not possible to properly form either "a substrate material having on its surface a conductive pattern with a width and spacing of 8 μm (L / S of 8 μm)" or "a substrate material having on its surface a conductive pattern with a width and spacing of 20 μm (L / S of 20 μm)."

[0073] In Comparative Examples 6 and 7, which used "resist removers that do not contain auxiliary agents, such as aromatic alcohol and / or glycol alcohol, or cyclic compounds as ingredients," the dry film resist had good removability for "those with a width and spacing of both 20 μm (L / S of 20 μm)," but the dry film resist had insufficient removability for "those with a width and spacing of both 8 μm (L / S of 8 μm)." As a result, it was not possible to properly form a substrate material having a relatively narrow-pitch "conductor pattern on its surface with a width and spacing of both 8 μm (L / S of 8 μm)." Furthermore, in Comparative Example 8, which used "a resist remover that does not contain auxiliary agents, such as aromatic alcohol and / or glycol alcohol, and cyclic compounds as ingredients," the dry film resist had good removability for "those with a width and spacing of both 20 μm (L / S of 20 μm)," but the dry film resist had insufficient removability for "those with a width and spacing of both 8 μm (L / S of 8 μm)." As a result, it was not possible to properly form a substrate material having a conductor pattern on its surface with a relatively narrow pitch, with both a width and spacing of 8 μm (L / S of 8 μm). [Industrial Applicability]

[0074] The resist remover according to the present application can be suitably used when forming substrate materials with conductor patterns, such as relatively narrow-pitch printed wiring boards, used in semiconductor integrated circuits, etc., while reducing the environmental impact.

Claims

1. A resist stripper used to remove a resist pattern for forming a circuit, comprising: The resist remover is characterized in that its components are 0.05 mol / L to 5 mol / L of alkali metal hydroxide, 0.05 mol / L to 8 mol / L of alcohol which is an aromatic alcohol and / or glycol, 0.005 mol / L to 1.0 mol / L of a cyclic compound, and the remainder is water.

2. The alkali metal hydroxide is at least one selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide; the alcohol is at least one selected from phenoxyethanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, triethylene glycol, and diethylene glycol monobutyl ether; 2. The resist remover according to claim 1, wherein the cyclic compound is at least one selected from α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and 24-crown-8-ether.

3. 3. The resist remover according to claim 1, comprising 0.001 mol / L to 0.7 mol / L of an inhibitor comprising a nitrogen compound and / or a sulfur compound.

4. 4. The resist remover according to claim 3, wherein the inhibitor is at least one selected from the group consisting of benzimidazole, benzotriazole, 1H-tetrazole, 5-amino-1H-tetrazole, 2-mercaptobenzimidazole, and 1-phenyl-5-mercapto-1H-tetrazole.

5. A method for forming a substrate material having a conductor pattern using the resist remover according to claim 1 or 2, A method for forming a substrate material having a conductor pattern, comprising the following steps A to C: Step A: A resist pattern is applied to the surface of a substrate material to obtain a substrate material with a resist pattern. Step B: The surface of the substrate material with the resist pattern obtained in step A is plated to obtain a substrate material with a metal film. Step C: The surface of the substrate material with the metal coating obtained in step B is brought into contact with the resist remover to remove the resist pattern, thereby obtaining a substrate material with a conductor pattern made of a metal coating.

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