Composition for removing photoresist and method for removing photoresist

Abstract

According to the present invention, it is possible to provide a composition for removing a photoresist for forming a copper-containing pattern after the formation of the pattern, the composition comprising an alkaline agent, an ammonium ion source, and an azole compound, the alkaline agent comprising at least one selected from the group consisting of an alkanolamine, a quaternary ammonium hydroxide, and an inorganic base.

Description

Technical Field

[0001] The present invention relates to a composition for removing a photoresist, a method for removing a photoresist using the composition for removing a photoresist, and the like. Background Art

[0002] In recent years, miniaturization and high functionality of electronic devices have been progressing, and miniaturization and high functionality are also required for printed circuit boards used for such electronic devices.

[0003] In order to manufacture a printed circuit board or the like that meets such expectations, the following method is adopted. For example, a metal layer called a seed layer is formed on an insulating layer having copper wiring in part, a photoresist layer is formed on the surface thereof, after exposure and development to form a resist pattern, copper plating is performed in the pattern opening, and then the photoresist and the seed layer are removed to form a circuit pattern that becomes a connection terminal portion of the copper wiring.

[0004] As described above, in the manufacturing method of a printed circuit board or the like, a photoresist removal step is mostly included, and in the photoresist removal step, an aqueous solution having various components is usually used (Patent Document 1, etc.).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2020 / 022491 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] In the conventional manufacturing process of a printed circuit board or the like, there are sometimes cases where the removal of the photoresist cannot be performed quickly and sufficiently. If the photoresist can be removed quickly and surely, the productivity of the printed circuit board can be improved.

[0010] In addition, in the step of removing the photoresist, if a conventional treatment liquid, particularly a highly reactive treatment liquid for efficiently removing the photoresist, is used, there is also a possibility of damaging components such as copper plating.

[0011] From the above viewpoints, a method is being sought that has excellent performance in removing a photoresist as part of the manufacturing process of a printed circuit board or the like and can surely protect copper-containing components such as copper plating.

[0012] Solutions to the Problems

[0013] The present invention includes, for example, the following aspects.

[0014] [1] A composition for removing a photoresist used to form a pattern containing copper after the pattern is formed, the composition comprising:

[0015] Alkaline agent, ammonium ion source and azole compound,

[0016] The alkali agent includes one or more selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic bases.

[0017] [2] The composition according to [1] above, wherein the etching rate of copper is less than 0.05 μm / min.

[0018] [3] The composition according to [1] above, wherein the ammonium ion source comprises at least one of ammonia and an ammonium salt of an organic acid.

[0019] [4] The composition according to [3] above, wherein the ammonium ion source comprises an ammonium salt of an aromatic organic acid.

[0020] [5] The composition according to [3] above, wherein the ammonium ion source comprises at least any one of ammonium benzoate, diammonium phthalate, and ammonium formate.

[0021] [6] The composition according to [1] above, wherein the azole compound comprises at least any one of an imidazole compound, a benzimidazole compound, and a pyrazole compound.

[0022] [7] The composition according to [1] above, further comprising an organic solvent.

[0023] [8] The composition according to [1] above, wherein the composition comprises, based on the total amount of the composition:

[0024] 3.0 to 50% by mass of the above-mentioned alkali agent,

[0025] 0.1 to 20% by mass of the above-mentioned ammonium ion source, and

[0026] 0.001 to 1.0 mass % of the above-mentioned azole compound.

[0027] [9] The composition according to [1] above, wherein the composition is water-soluble.

[0028]

[10] The composition according to [1] above, wherein the composition does not contain a chelating agent or a sulfur-containing organic acid.

[0029]

[11] The composition according to [1] above, wherein the pattern is a circuit pattern that is formed on an insulating layer having a copper wiring at least partially and serves as a connection terminal portion of the copper wiring.

[0030]

[12] A method for removing a photoresist, comprising: a photoresist removal step of bringing the composition described in any one of [1] to

[11] above into contact with a photoresist for forming a pattern containing copper.

[0031]

[13] The photoresist removal method according to

[12] above, wherein the pattern is a circuit pattern that is formed on an insulating layer having at least a portion of a copper wiring and serves as a connection terminal portion of the copper wiring.

[0032]

[14] A method for manufacturing a printed circuit board, a semiconductor element or a semiconductor package, comprising: a photoresist removal step of contacting the composition described in any one of [1] to

[11] above with a photoresist for forming a pattern containing copper.

[0033]

[15] A method for manufacturing a printed circuit board, a semiconductor element or a semiconductor package according to

[14] above, wherein the pattern is a circuit pattern formed on an insulating layer having at least a portion of copper wiring and serving as a connection terminal portion of the copper wiring.

[0034] Effects of the Invention

[0035] According to the present invention, it is possible to provide a photoresist removing composition or the like which can efficiently remove a photoresist and reliably protect a copper-containing member such as copper plating in a printed wiring board. DETAILED DESCRIPTION

[0036] The composition of the present invention is suitable for removing a photoresist after forming a pattern containing copper, and contains at least a predetermined alkaline agent, an ammonium ion source, and an azole compound.

[0037] [I. Composition]

[0038] The composition is preferably water-soluble, that is, at least a portion of the composition is preferably soluble or suspendable in water, and more preferably can be uniformly mixed with water in any proportion.

[0039] Furthermore, it is preferred that at least a part of the components other than water contained in the composition be soluble in water, and it is more preferred that the components other than water contained in the composition be uniformly miscible with water.

[0040] <I-1.(A) Alkali agent>

[0041] The composition preferably contains 3.0 to 50% by mass of (A) a base agent (hereinafter also referred to as component (A)) based on the total mass of the composition. The content of the base agent in the composition is more preferably 4.0 to 40% by mass, further preferably 5.0 to 30% by mass or 6.0 to 35% by mass, and particularly preferably 7.0 to 15% by mass, 8.0 to 20% by mass or 9.0 to 12% by mass, etc., based on the total amount of the composition.

[0042] In the composition containing component (A), the removability of the photoresist is good, and in addition, it is considered to have an effect of suppressing damage to a circuit pattern containing copper, a copper alloy, etc. in a connection terminal portion of a copper wiring.

[0043] (A) The base agent preferably contains any one selected from (A-1) alkanolamines, (A-2) quaternary ammonium hydroxides, and (A-3) inorganic bases, more preferably contains two of these, and particularly preferably contains (A-1) to (A-3) all.

[0044] (A-1) Alkanolamine

[0045] The type of (A-1) alkanolamine that can be contained as component (A) in the composition is not particularly limited, and examples thereof include monoalkanolamines, dialkanolamines, trialkanolamines, and alkylated products thereof (N-alkylated products, O-alkylated products).

[0046] As the alkanolamine (A), for example, 2-aminoethanol (monoethanolamine), N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, 1-amino-2-propanol (isopropanolamine), N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-aminopropan-1-ol, N-ethyl-2-aminopropan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentan-1-ol, 2-aminohexan-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2-(2-aminoethoxy)ethanol, etc. can be preferably cited. These can be used alone, or two or more of them can be used in combination.

[0047] Among these, as the alkanolamine, one or more selected from the group consisting of 2-aminoethanol (monoethanolamine) and 1-amino-2-propanol are preferred.

[0048] The content of the alkanolamine is preferably 1.0 to 50% by mass, more preferably 1.5 to 45% by mass, 1.5 to 42% by mass, 2.0 to 30% by mass or 2.0 to 15% by mass, still more preferably 3.0 to 12% by mass, particularly preferably 4.0 to 8.0% by mass or 5.0 to 9.0% by mass, etc., based on the total amount of the composition.

[0049] (A-2) Quaternary ammonium hydroxide

[0050] The types of (A-2) quaternary ammonium hydroxide that can be contained as the component (A) in the composition are not particularly limited, and for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, triethylmethylammonium hydroxide, ethyltrimethylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, triethyl(2-hydroxyethyl)ammonium hydroxide can be cited. These can be used alone, or two or more of them can be used in combination.

[0051] Among these, as the quaternary ammonium hydroxide, one or more selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and triethylmethylammonium hydroxide are preferred.

[0052] The content of the quaternary ammonium hydroxide is preferably 0.3 to 12% by mass, more preferably 0.5 to 10% by mass, still more preferably 1.0 to 8.0% by mass, and particularly preferably 1.5 to 5.0% by mass or 2.0 to 6.0% by mass, etc., based on the total amount of the composition.

[0053] (A-3) Inorganic base

[0054] The type of the (A-3) inorganic base that can be contained as the component (A) in the composition is not particularly limited, and examples thereof include alkali metal compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and potassium silicate; alkaline earth metal compounds such as magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, calcium silicate, and magnesium silicate; transition metal compounds such as copper hydroxide and iron hydroxide; ammonia, etc.

[0055] Among these, as the inorganic base, potassium hydroxide, sodium hydroxide, etc. are preferred.

[0056] The content of the inorganic base is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, still more preferably 0.05 to 2.0% by mass, and particularly preferably 0.1 to 0.5% by mass or 0.2 to 1.0% by mass, etc., based on the total amount of the composition.

[0057] <I-2. (B) Ammonium ion source>

[0058] The composition preferably contains 0.1 to 20% by mass of the (B) ammonium ion source (hereinafter also referred to as the component (B)) based on its total mass. The content of the ammonium ion source in the composition is more preferably 0.15 to 10% by mass, still more preferably 0.20 to 5.0% by mass, and particularly preferably 0.25 to 2.5% by mass, 0.50 to 3.0% by mass, or 0.25 to 2.0% by mass, etc., based on the total amount of the composition.

[0059] The composition containing the component (B) is considered to have the effect of improving the removability of the photoresist.

[0060] The type of the ammonium ion source contained as the component (B) in the composition is not particularly limited, and examples thereof include ammonium salts such as ammonia and ammonium halide salts (ammonium chloride, ammonium bromide, ammonium iodide, etc.), organic acid ammonium salts, and inorganic acid ammonium salts. As the ammonium ion source, organic acid ammonium salts are preferred, and as the organic acid ammonium salts, ammonium salts of aromatic organic acids, ammonium salts of fatty acids, etc. can be cited.

[0061] As the ammonium salt of an aromatic organic acid, for example, mono-, di-, and tri-ammonium salts of aromatic carboxylic acids having 6 to 30 carbon atoms can be mentioned. Specific examples include ammonium salts of benzoic acid, phthalic acid, salicylic acid, etc., that is, ammonium benzoate, di-ammonium phthalate, ammonium salicylate, etc.

[0062] In addition, as the ammonium salt of a fatty acid, mono-, di-, and tri-ammonium salts of saturated or unsaturated fatty acids having 1 to 20 carbon atoms, etc., can be mentioned. Specific examples include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, tridecanoic acid, palmitic acid, stearic acid; ammonium salts of unsaturated fatty acids such as acrylic acid, methacrylic acid, oleic acid, linoleic acid, linolenic acid, etc.

[0063] As the ammonium ion source, one kind or two or more kinds can be used. Component (B) in the composition preferably contains 30% by mass or more of the ammonium salt of an aromatic organic acid or the ammonium salt of a fatty acid based on the total amount of the ammonium ion source, more preferably contains 50% by mass or more of the ammonium salt of an aromatic organic acid or the ammonium salt of a fatty acid, still more preferably contains 70% by mass or more of the ammonium salt of an aromatic organic acid or the ammonium salt of a fatty acid, and particularly preferably contains 90% by mass or more of the ammonium salt of an aromatic organic acid or the ammonium salt of a fatty acid. It is more preferable that only the ammonium salt of an aromatic organic acid or the ammonium salt of a fatty acid is contained as the ammonium ion source in the composition.

[0064] <I-3. (C) Azole compound>

[0065] The composition preferably contains 0.001 to 1.0% by mass of the (C) azole compound (hereinafter also referred to as component (C)) based on its total mass. The content of the azole compound in the composition is more preferably 0.005 to 0.80% by mass, still more preferably 0.01 to 0.60% by mass or 0.015 to 0.70% by mass, and particularly preferably 0.02 to 0.40% by mass, 0.025 to 0.50% by mass, or 0.03 to 0.30% by mass, etc.

[0066] The composition containing component (C) is considered to protect the metal layer containing copper or a copper alloy and has the effect of reducing the etching rate of copper.

[0067] The azole compound in the composition preferably contains at least any one of a triazole compound, an imidazole compound, a benzimidazole compound, and a pyrazole compound.

[0068] As the triazole compound, as long as it is a compound having a triazole ring, there is no particular limitation, and any triazole such as 1,2,3-triazole or 1,2,4-triazole, a triazole having a substituent with 10 or less carbon atoms, a triazole such as tolyltriazole in which an aromatic ring is fused to the triazole ring, triazole salts thereof, etc. can be mentioned.

[0069] As an imidazole compound, there is no particular limitation as long as it is a compound having an imidazole ring, and examples thereof include imidazole, imidazole derivatives having a substituent with 10 or less carbon atoms, such as 1-alkylimidazoles like 1-methylimidazole, 4-alkylimidazoles like 4-methylimidazole, mercaptoimidazoles like 2-mercaptoimidazole, and imidazolium salts thereof.

[0070] As a benzimidazole compound, there is no particular limitation as long as it is a compound having a benzimidazole skeleton, and examples thereof include benzimidazole, benzimidazole derivatives having a substituent with 10 or less carbon atoms, such as 1-alkylbenzimidazoles, 2-alkylbenzimidazoles, 7-alkylbenzimidazoles, and benzimidazolium salts thereof.

[0071] In addition, as pyrazole compounds, examples include pyrazole, pyrazoles having a substituent with 10 or less carbon atoms, 1-alkylpyrazoles like 1-methylpyrazole, 3-alkylpyrazoles like 3-methylpyrazole, 4-alkylpyrazoles like 4-methylpyrazole, 5-alkylpyrazoles like 5-methylpyrazole, and pyrazole salts thereof.

[0072] <I-4. Water>

[0073] The composition preferably contains water. There is no particular limitation on the type of water contained in the composition, and it is preferably obtained by removing metal ions, organic impurities, particles, etc. through distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc., more preferably pure water, and particularly preferably ultrapure water.

[0074] The content of water in the composition is preferably 20% by mass or more, more preferably more than 20% by mass, more preferably in the range of 20 - 99% by mass, further preferably 40 - 97% by mass, still further preferably 60 - 95% by mass, and particularly preferably 70 - 95% by mass, based on the total amount of the composition. The composition with the water content adjusted in this way improves the reactivity with the photoresist and the removability of the photoresist.

[0075] <I-5. Other Components>

[0076] Within the range that does not hinder the above effects, the composition may also contain other minor components as needed. Examples of other components include solvents, pH adjusters, surfactants, defoamers, etc.

[0077] In addition, carbonate ions, carbonates that generate carbonate ions, bicarbonates, etc. can also be added to the composition. If carbonate ions, etc. are added to the composition, the corrosion resistance of copper can be improved. Specific examples of carbonates and bicarbonates include salts of ammonium ions, salts of alkali metals or alkaline earth metals, etc., and ammonium carbonate salts such as tetramethylammonium carbonate can also be added to the composition.

[0078] The content of the minor component in the composition is preferably 10% by mass or less, more preferably 5.0% by mass or less, still more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, or 1.5% by mass or less, based on the total amount of the composition.

[0079] In addition, the content of each component of the salt that generates carbonate ions in the composition is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, or 1.5% by mass or less.

[0080] In addition, the composition is preferably a solution, and preferably does not contain solid particles such as abrasive particles.

[0081] In the composition, for example, organic solvents such as ether compounds and alcohols are preferably added. When a specified solvent is used, it is considered that there is an effect of improving the solubility of the photoresist in the composition and enhancing the removability.

[0082] Specific examples of ethers among the preferred organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, phenyl glycol = ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and the like.

[0083] In addition, specific examples of alcohols among the preferred organic solvents include aromatic alcohols such as benzyl alcohol, salicyl alcohol, anisyl alcohol, anise alcohol, gentisyl alcohol, catechol, vanillyl alcohol, veratryl alcohol, syringyl alcohol, cumyl alcohol, phenethyl alcohol, and the like.

[0084] The content of the solvent is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, still more preferably 0.2 to 5.0% by mass, and particularly preferably 0.3 to 3.5% by mass or 0.4 to 4.0% by mass, etc., based on the total amount of the composition.

[0085] In addition, there are also components that are preferably not added to the composition. Examples of components not desired in the composition include chelating agents and sulfur-containing organic acids.

[0086] If a composition containing a chelating agent is used to remove the photoresist, there is a possibility that the remaining chelating agent will cause adverse effects in the flash etching process of copper etching or the like. This is because if a chelating agent adheres to the surface of copper, it will interfere with the etching process.

[0087] In addition, when an organic acid containing a sulfur atom is used as a component of the composition, sulfur-containing compounds can cause odor generation and a decrease in the stability of the composition.

[0088] Therefore, in the composition of the present invention, it is preferable that neither a chelating agent nor a sulfur-containing organic acid is contained.

[0089] <I-6. Method for Preparing the Composition>

[0090] For the composition of the present invention, the components (A), (B), (C), water, and other components as required are added, and it is preferably prepared by stirring until it becomes completely homogeneous. When manufacturing the composition, the order of addition and mixing of the respective components is not particularly limited. For example, a certain amount of water can be added to any of the components (A) such as (A-1) to (A-3), and other components except water can be prepared as a concentrate, and they can be mixed when using the composition. It is also possible to transport any component in such a concentrated state, that is, in a state without water, and add water to prepare the composition.

[0091] <I-7. Properties of the Composition>

[0092] The range of the pH of the composition of the present invention is not particularly limited. The pH value of the composition in one mode is 8 or more, preferably 10 or more, more preferably 11 or more. The pH value can be measured by a general method using a pH meter.

[0093] According to the composition of the present invention, damage to copper and copper alloys can be inhibited. Therefore, the etching rate of copper evaluated by the specific method described below after the examples can be inhibited to 0.050 μm / minute or less. More preferably, the etching rate of copper evaluated by the specific method described below is 0.040 μm / minute or less, further preferably 0.030 μm / minute or less, and particularly preferably 0.020 μm / minute or 0.015 μm / minute or less.

[0094] According to the composition of the present invention, a photoresist can be effectively removed. Therefore, the value of L.P. (lifting point) regarding the stripping speed evaluated by the specific method described below after the examples can be 100 seconds or less. More preferably, the value of L.P. evaluated by the specific method described below is 90 seconds or less, further preferably 85 seconds or less, and particularly preferably 80 seconds or less or 75 seconds or less.

[0095] <I-8. Mode of Use of the Composition>

[0096] There is no particular limitation on the temperature of the composition used for removing the photoresist. The temperature is preferably 10 to 70 °C, more preferably 20 to 65 °C, and further preferably 25 to 60 °C. By using the composition within such a temperature range, the removability of the photoresist becomes good, and the compositional change of the composition can be suppressed, making it easy to maintain the photoresist removal conditions.

[0097] There is no particular limitation on the treatment time of the photoresist based on the composition. It is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and may also be 30 to 240 seconds. The treatment time is the time for the composition to contact the photoresist, and it can be appropriately selected according to various conditions such as the surface state of the photoresist to be removed, the concentration of the composition, the temperature, and the treatment method.

[0098] There is no particular limitation on the method of bringing the composition of the present invention into contact with the photoresist. For example, methods such as bringing the composition of the present invention into contact with the photoresist to be removed by dropping (single-wafer spin processing) or spraying atomization, or immersing the photoresist to be removed in the composition of the present invention can be used. Any method can be adopted in the present invention.

[0099] <II. Method for Removing Photoresist>

[0100] The method for removing the photoresist of the present invention includes a photoresist removal step, which brings the composition of the present invention into contact with the photoresist used for forming a copper-containing pattern. Hereinafter, the method for removing the photoresist will be described.

[0101] The composition of the present invention is, for example, suitable for removing the photoresist of a copper-containing circuit pattern used to form a connection terminal portion of the copper wiring on at least a part of an insulating layer having copper wiring after the formation of the circuit pattern.

[0102] Here, the "insulating layer having copper wiring at least in part" is not particularly limited as long as it is an insulating layer with copper wiring buried in the surface or inside, and examples include printed circuit boards, package substrates for mounting semiconductor elements, and silicon insulating layers of semiconductor wafers.

[0103] In addition, the "copper-containing circuit pattern that becomes the connection terminal portion of the copper wiring" refers to, for example, the connection terminal portion of the copper wiring provided in the insulating layer and used for electrical connection with other components.

[0104] In one embodiment of the present invention, the connection terminal portion is the connection terminal portion of the copper wiring in a printed circuit board. Further, in one embodiment of the present invention, the connection terminal portion is the connection terminal portion of the copper wiring in a package substrate for mounting a semiconductor element. Further, in one embodiment of the present invention, the connection terminal portion is the connection terminal portion of the copper wiring in a semiconductor element.

[0105] <III. Manufacturing method of printed wiring, etc.>

[0106] The manufacturing method of the printed wiring, etc. of the present invention includes: a photoresist removing step of bringing the composition of the present invention into contact with a photoresist for forming a pattern containing copper. In addition to printed circuit boards, the photoresist removing step in the manufacturing methods of semiconductor elements and semiconductor packages can also suitably use the composition of the present invention.

[0107] For example, the composition of the present invention can be suitably used for removing, in the manufacturing process of a printed circuit board (such as a package substrate for mounting a semiconductor element), a photoresist for forming a copper-containing circuit pattern that forms a connection terminal portion of the copper wiring on at least a part of an insulating layer having copper wiring after the formation of the circuit pattern.

[0108] In addition, the composition of the present invention can be suitably used for removing, in the manufacturing process of a semiconductor element, a photoresist for forming a circuit pattern containing copper and at least one selected from the group consisting of tin and tin alloys that forms a connection terminal portion of the copper wiring on at least a part of an insulating layer having copper wiring after the formation of the circuit pattern.

[0109] Examples of the photoresist for a printed circuit board include a composition containing a binder polymer, a photopolymerizable monomer, a photopolymerization initiator, and other additives.

[0110] Examples of the binder polymer include a polymer obtained by copolymerizing at least one of methacrylic acid and acrylic acid as essential components and various vinyl monomers such as methacrylate, acrylate, and styrene.

[0111] Examples of the photopolymerizable monomer preferably include at least one of methacrylate and acrylate.

[0112] Examples of the photopolymerization initiator include at least one selected from the group consisting of benzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-ethylanthraquinone, benzoin, benzoin methyl ether, 9-phenylacridine, benzoyl dimethyl ketal, and benzoyl diethyl ketal. In addition, a two-component system composed of hexaarylbiimidazole and a hydrogen donor (2-mercaptobenzoxazole, N-phenylglycine) can also be used.

[0113] In addition, as other additives, thermal polymerization initiators, dyes, etc. can be cited.

[0114] As the photoresist that can be used for semiconductor elements, a combination of a phenol-formaldehyde resin (collectively referred to as "novolak resin") and a naphthoquinone diazide compound as a photosensitive component, etc. can be preferably cited.

[0115] In addition, as the resist disposed between metal wirings, dry film resists, liquid resists, etc. can be cited. Among these, the resist is preferably a dry film resist. As the dry film resist, there is no particular limitation, and it is preferably formed of a photosensitive resin. As the photosensitive resin, a negative photosensitive resin and a positive photosensitive resin can be cited.

[0116] As the negative photosensitive resin, there is no particular limitation, and azide-based photosensitive resins, diazo-based photosensitive resins, alkyne-based low molecular weight photosensitive resins, alkene-based low molecular weight photosensitive resins, insolubilizing polymer-based photosensitive resins, chromic acid-based photosensitive resins can be cited. These negative photosensitive resins can be used alone or in combination of two or more.

[0117] As the positive photosensitive resin, there is no particular limitation, and quinone diazide-based photosensitive resins, solubilizing polymer-based photosensitive resins, etc. can be cited. These positive photosensitive resins can be used alone or in combination of two or more.

[0118] Among these, the dry film resist is preferably formed of a negative photosensitive resin. The negative photosensitive resin becomes insoluble in the developer due to the exposure treatment during pattern formation, so the exposed part (the part where the negative photosensitive resin is cured) remains as the dry film resist. Here, the curing of the negative photosensitive resin during exposure, especially the surface part exposed during exposure, is easy to proceed, and the surface part of the obtained dry film resist can particularly have a dense structure. Therefore, depending on the composition, there are cases where even if it is desired to remove the dry film resist, the composition is difficult to penetrate into the inside of the dry film resist. In addition, depending on the composition, the resist removal ability is insufficient, so there are cases where the dry film resist is not removed. As a result, it sometimes takes time to remove the dry film resist.

[0119] In contrast, the composition of the present invention easily penetrates into the dry film resist, so the dry film resist can be quickly peeled off and removed.

[0120] Examples

[0121] (Production of samples for peelability evaluation)

[0122] The sample for peelability evaluation was prepared as follows. First, electroless copper plating was performed on a copper-clad laminate (manufactured by Mitsubishi Gas Chemical Company, Inc., CCL-HL832NS(MT-FL) 0.1 mm tC / C) to form a copper thin film (thickness: 1.0 μm). A dry film resist (manufactured by Showa Denko K.K., RD-3025, thickness: 25 μm) was attached to the surface of this copper thin film, and a circuit mask pattern was applied thereon, followed by exposure and development. Electroplated copper (thickness: 17 μm) was performed on the circuit pattern openings formed by exposing and developing the dry film resist to obtain a sample for peelability evaluation. The pattern of the dry film resist applied to the sample for peelability evaluation was dots.

[0123] (Preparation of Sample for Evaluating Copper Corrosion Resistance)

[0124] The sample for evaluating copper corrosion resistance was prepared as follows. That is, electroplated copper (thickness: 35 μm) was performed on the surface of a copper-clad laminate (manufactured by Mitsubishi Gas Chemical Company, Inc., CCL-HL832NX) to obtain a sample for evaluating copper corrosion resistance.

[0125] (Peel Rate (L.P. (Peel Start Point)))

[0126] The aqueous compositions described in the examples and comparative examples were atomized by spraying at a spray pressure of 0.15 MPa at 50 °C and brought into contact with the above-mentioned sample for peelability evaluation.

[0127] Then, the time from the start of spraying of the aqueous composition until the dry film resist completely peeled off from the substrate of the sample for peelability evaluation was measured as L.P. (seconds). It should be noted that in the measurement of L.P., the dot pattern portion applied to the sample for peelability evaluation was visually observed as the time when the dry film resist was removed.

[0128] (Copper Corrosion Resistance (Cu E.R. (Etching Rate)))

[0129] The aqueous compositions described in the examples and comparative examples were atomized by spraying at a spray pressure of 0.15 MPa at 50 °C for 5 minutes and brought into contact with the above-mentioned sample for evaluating copper corrosion resistance cut into a square of 4 cm × 4 cm. Then, after washing with pure water, cleaning with 5 mass% sulfuric acid, and washing with pure water again, the sample for evaluating copper corrosion resistance was thoroughly dried.

[0130] The value of Cu E.R. (μm / min) was calculated as follows. That is, the mass of the sample for evaluating copper corrosion resistance before and after the spray treatment of the above-mentioned aqueous composition was measured, and from the mass difference, the density of copper (8.93 g / cm 3 ) and the sample size (treatment area [cm 2, It should be noted that the reverse side of the sample for evaluating the corrosion resistance of copper is protected with masking tape. Therefore, the treatment area is the area of the sample surface. Calculate the etched thickness and obtain the etching rate per minute through the following formula (I).

[0131]

[0132] (Peelability)

[0133] Spray the aqueous compositions described in the examples and comparative examples at a spray pressure of 0.15 MPa at 50 °C for 3 minutes to atomize and make them contact with the above-mentioned sample for peelability evaluation. Then, wash with pure water, clean with 5% by mass sulfuric acid, wash with pure water again, and dry thoroughly.

[0134] The peelability is evaluated as follows. That is, use an optical microscope (manufactured by Olympus Corporation, MX-61L, objective lens 50 times) to confirm the residue of the dry film resist on the sample for peelability evaluation after the spray treatment of the aqueous composition, and evaluate according to the following criteria.

[0135] Particularly good: The residues of the dry film resist are all 2 or less

[0136] Good: The residues of the dry film resist are all 110 or less

[0137] Poor: The residues of the dry film resist exceed 110

[0138] [Example 1]

[0139] Prepare an aqueous composition by adding the following substances to 323 g of pure water respectively: monoethanolamine (MEA) in an amount that finally becomes 6% by mass (32 g of 75% MEA aqueous solution), tetramethylammonium hydroxide (TMAH) in an amount that finally becomes 2% by mass (32 g of 25% TMAH aqueous solution), ammonium benzoate in an amount that finally becomes 1.0% by mass (4.0 g), and 4-methylimidazole in an amount that finally becomes 0.09% by mass (0.36 g). The L.P. of the obtained aqueous composition is 47 sec, the Cu E.R. is 0.03 μm / min, and the peelability is good.

[0140] The properties and evaluation results of the aqueous compositions are shown in Table 1 below.

[0141] [Examples 2 - 16 and Comparative Examples 1 - 7]

[0142] As shown in Table 1 below, any of the types and amounts of the respective components in the composition of Example 1 was changed, and further components were added in some of the examples and comparative examples. Other than that, an aqueous composition was prepared in the same manner as in Example 1, and an evaluation test was conducted. The properties and evaluation results of the aqueous compositions of the respective examples and comparative examples are shown in Table 1 below.

[0143] It should be noted that the tetramethylammonium hydrogencarbonate (TMBC) added to the aqueous composition of Example 12 or the like can be generated as a degradation product of tetramethylammonium hydroxide, which can reduce the stripping performance of the dry film resist caused by the aqueous composition. Therefore, in order to evaluate the stripping treatment caused by the aqueous composition in the case where the tetramethylammonium hydrogencarbonate is generated after long-term use, this hydrogencarbonate was added to the aqueous composition of this example.

[0144] [Table 1]

[0145]

[0146] As shown by the above results, for the aqueous composition of the example containing a specified ammonium ion source, it was confirmed that compared with the aqueous composition of the comparative example, the time represented by the value of L.P. (stripping start point) was shorter, the photoresist could be stripped rapidly, and the generation of resist residues could be suppressed. In addition, in the examples, compared with the comparative examples, the value of Cu E.R. (etching rate) tended to be lower, and a result with excellent corrosion resistance of copper was obtained.

[0147] It should be noted that when comparing Example 1 using ammonium benzoate as the ammonium ion source and Comparative Example 3 adding potassium benzoate, the time of L.P. (stripping start point) in Example 1 was shorter, and the stripping speed of the photoresist was excellent. In addition, even when comparing Example 7 using diammonium phthalate as the ammonium ion source and Comparative Example 4 adding phthalic acid, the same tendency was considered. From these results, it was confirmed that the stripping property of the photoresist, especially the stripping speed, was improved in the aqueous composition containing a specified ammonium ion source.

Claims

1. A composition for removing a photoresist used to form a pattern containing copper after the pattern is formed, the composition comprising: Alkaline agent, ammonium ion source and azole compound, The alkali agent includes one or more selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic bases.

2. The composition according to claim 1, wherein The etching rate of copper is less than 0.05 μm / min.

3. The composition according to claim 1, wherein, The ammonium ion source includes at least any one of ammonia and an ammonium salt of an organic acid.

4. The composition according to claim 3, wherein The ammonium ion source comprises an ammonium salt of an aromatic organic acid.

5. The composition according to claim 3, wherein The ammonium ion source includes at least any one of ammonium benzoate, diammonium phthalate, and ammonium formate.

6. The composition according to claim 1, wherein, The azole compound includes at least any one of an imidazole compound, a benzimidazole compound, and a pyrazole compound.

7. The composition according to claim 1, further comprising an organic solvent.

8. The composition according to claim 1, wherein The composition comprises, based on the total amount of the composition: 3.0 to 50% by mass of the alkali agent, 0.1 to 20% by mass of the ammonium ion source, and 0.001 to 1.0 mass % of the azole compound.

9. The composition according to claim 1, wherein The composition is water soluble.

10. The composition according to claim 1, wherein The composition does not contain chelating agents or sulfur-containing organic acids.

11. The composition according to claim 1, wherein, The pattern is a circuit pattern that is formed on an insulating layer having a copper wiring at least partially and serves as a connection terminal portion of the copper wiring.

12. A method for removing a photoresist, comprising: A photoresist removal step of bringing the composition according to any one of claims 1 to 11 into contact with a photoresist for forming a pattern containing copper.

13. The method for removing a photoresist according to claim 12, wherein, The pattern is a circuit pattern that is formed on an insulating layer having a copper wiring at least partially and serves as a connection terminal portion of the copper wiring.

14. A method for manufacturing a printed circuit board, a semiconductor component, or a semiconductor package, comprising: A photoresist removal step of bringing the composition according to any one of claims 1 to 11 into contact with a photoresist for forming a pattern containing copper.

15. The manufacturing method of a printed circuit board, semiconductor element, or semiconductor package according to claim 14, wherein, The pattern is a circuit pattern that is formed on an insulating layer having a copper wiring at least partially and serves as a connection terminal portion of the copper wiring.

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