Composition and kit, and resist removal method and method for manufacturing electronic substrate using same

Abstract

Provided are a composition and the like capable of suppressing oxidation of copper wiring after removal of a resist. A composition containing a basic compound and a copper surface protective agent, the copper surface protective agent containing at least one selected from the group consisting of an ammonium salt represented by formula (1), a heteroaryl salt having a substituted or unsubstituted alkyl group having 5-30 carbon atoms, and a substituted or unsubstituted thiol having 5-30 carbon atoms, the composition having a pH of 13 or more. In the formula (1), R1 is a substituted or unsubstituted alkyl group having 5-30 carbon atoms, a substituted or unsubstituted alkyl (poly) heteroalkylene group having 5-30 carbon atoms, or a substituted or unsubstituted aryl (poly) heteroalkylene group having 7-30 carbon atoms, R2 is each independently a substituted or unsubstituted alkyl group having 1-30 carbon atoms, or a substituted or unsubstituted aryl group having 6-30 carbon atoms, and R3 is each independently a substituted or unsubstituted alkyl group having 1-30 carbon atoms, or a substituted or unsubstituted aryl group having 6-30 carbon atoms. X is a halide ion, a hydroxide ion, an organic sulfonate ion, a tetrafluoroborate anion, or a hexafluorophosphate anion.

Description

Technical Field

[0001] This invention relates to compositions and kits, as well as methods for manufacturing electronic substrates using them and methods for removing resists. Background Technology

[0002] In recent years, electronic devices have been continuously miniaturized and made more functional. This has also led to requirements for miniaturization and increased functionality for electronic substrates with copper wiring used in these devices.

[0003] As a method for manufacturing an electronic substrate that meets such requirements, a method using a photoresist is known. Such a manufacturing method may include, for example, the following steps: a coating formation step, forming a coating of photosensitive resin on a substrate; a patterning step, patterning the obtained coating by exposure and development, thereby producing a substrate having a photoresist; a copper wiring formation step, forming copper wirings on the substrate exposed by development by plating or the like, thereby producing a substrate having copper wirings and photoresist disposed between the copper wirings; and a photoresist removal step, removing the photoresist using a cleaning agent.

[0004] As a method for manufacturing the electronic substrate, for example, Patent Document 1 describes a cleaning method that includes the following steps: using a cleaning agent composition containing an alkali (component A), an organic solvent (component B), and water (component C), wherein the coordinates of the Hansen solubility parameter of component B are within a specified range and the conductivity is 11 S / m or more, the resin mask is peeled off from the object to be cleaned to which the resin mask is attached.

[0005] According to Patent Document 1, a cleaning method is described that provides excellent removal of resin masks (resist).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2020 / 022491 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] However, it is known that copper can be oxidized by oxygen in the air to form copper oxide. For example, when the resist is removed using the cleaning agent composition described in Patent Document 1, the copper wiring is exposed, thereby increasing the contact area with oxygen in the air and making it easier for copper oxide to form. Therefore, in the manufacturing process of electronic substrates, it is sometimes difficult to store them for a long time after the resist is removed.

[0011] Therefore, the present invention provides a composition, etc., that can suppress oxidation of copper wiring after resist removal.

[0012] Solution for solving the problem

[0013] The present invention is described below, for example.

[0014] [1] A composition comprising an alkaline compound and a copper surface protectant,

[0015] The copper surface protectant comprises at least one selected from the group consisting of an ammonium salt of formula (1), a heteroaryl salt having substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms, and a substituted or unsubstituted thiol having 5 to 30 carbon atoms.

[0016]

[0017] In equation (1) above, R 1 It is a substituted or unsubstituted alkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl (poly)heteroalkylene group having 5 to 30 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 7 to 30 carbon atoms.

[0018] R 2 Each is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

[0019] X can be a halide ion, hydroxide ion, organic sulfonate ion, tetrafluoroborate anion, or hexafluorophosphate anion.

[0020] The pH of the composition is above 13.

[0021] [2] According to the composition described in [1] above, wherein the basic compound comprises a strongly basic compound.

[0022] [3] According to the composition described in [2] above, wherein the strong base compound comprises an inorganic strong base compound.

[0023] [4] According to the composition described in [2] or [3] above, wherein the content of the strong basic compound is 3 to 10 by mass relative to the total mass of the composition.

[0024] [5] The composition according to any one of [2] to [4] above, wherein the basic compound further comprises a weakly basic compound.

[0025] [6] The composition according to any one of [1] to [5] above, wherein the copper surface protectant comprises a heteroaryl salt having substituted or unsubstituted alkyl groups having 8 to 20 carbon atoms.

[0026] [7] According to the composition described in [6] above, the copper surface protectant comprises a pyridinium salt having substituted or unsubstituted alkyl groups having 14 to 20 carbon atoms.

[0027] [8] According to the composition described in [6] above, wherein the copper surface protectant comprises an imidazolium salt having substituted or unsubstituted alkyl groups having 8 to 14 carbon atoms.

[0028] [9] The composition according to any one of [1] to [8] above, wherein the copper surface protectant comprises substituted or unsubstituted thiols having 8 to 20 carbon atoms.

[0029]

[10] The composition according to any one of [1] to [9] above, wherein the content of the copper surface protectant is 0.07 to 0.5% by mass relative to the total mass of the composition.

[0030]

[11] The composition according to any one of [1] to

[10] above further comprises an organic solvent.

[0031]

[12] A method for manufacturing an electronic substrate includes the following steps: contacting the composition described in any one of [1] to

[11] above with a substrate having copper wiring and a resist disposed between the copper wiring to remove the resist, and forming a protective layer on the surface of the copper wiring.

[0032]

[13] A method for removing resist includes the following steps: contacting the composition described in any one of [1] to

[11] above with a substrate having copper wiring and resist disposed between the copper wiring to remove the resist, and forming a protective layer on the surface of the copper wiring.

[0033]

[14] A kit for use in the method for manufacturing an electronic substrate as described in

[12] above, wherein,

[0034] The solution comprises a first solution containing an alkaline compound and a second solution containing a copper surface protectant, in an immiscible state.

[0035] When using, mix the first solution with the second solution.

[0036]

[15] A kit for use in the resist removal method described in

[13] above, wherein,

[0037] The solution comprises a first solution containing an alkaline compound and a second solution containing a copper surface protectant, in an immiscible state.

[0038] When using, mix the first solution with the second solution.

[0039] The effects of the invention

[0040] According to the present invention, a composition or the like is provided that can suppress oxidation of copper wiring after resist removal. Detailed Implementation

[0041] The following is a detailed description of the methods for carrying out the present invention.

[0042] 1. Composition

[0043] The composition of the present invention comprises an alkaline compound and a copper surface protectant, said copper surface protectant comprising at least one selected from the group consisting of an ammonium salt of formula (1), a heteroaryl salt having substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms, and a substituted or unsubstituted thiol having 5 to 30 carbon atoms. In this case, the pH of the composition of the present invention is 13 or higher.

[0044] The compositions of the present invention, because they contain alkaline compounds, can remove resists. Furthermore, because the compositions of the present invention contain copper surface protectants, they can inhibit oxidation of copper wiring after resist removal.

[0045] [Basic compounds]

[0046] Alkaline compounds have the function of promoting the removal of photoresist. For example, by setting the pH of the composition of the present invention to 13 or higher, alkaline compounds dissolve or swell the resin constituting the photoresist, thereby reducing the adhesion between the substrate and the resin and removing the photoresist from the substrate.

[0047] Basic compounds include strongly basic compounds and weakly basic compounds. It should be noted that, in this specification, "strongly basic compounds" refers to compounds with a degree of ionization of 0.9 or higher in water at room temperature (23°C). Conversely, "weakly basic compounds" refers to compounds with a degree of ionization of less than 0.9 in water at room temperature (23°C).

[0048] (Strongly basic compound)

[0049] As a strong base compound, there are no particular limitations; both inorganic and organic strong base compounds can be listed.

[0050] As inorganic strong base compounds, there are no particular limitations; examples include strong base alkali metal compounds such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as strong base alkaline earth metal compounds such as calcium hydroxide.

[0051] As strong organic base compounds, there are no particular limitations, and quaternary ammonium compounds represented by the following formula (2) can be listed.

[0052]

[0053] In the above formula, R 4 Alkyl groups having 1 to 4 carbon atoms and hydroxyalkyl groups having 1 to 4 carbon atoms can be listed independently.

[0054] Here, alkyl groups having 1 to 4 carbon atoms can be listed as methyl, ethyl, propyl, isopropyl, butyl, etc.

[0055] Examples of hydroxyalkyl groups with 1 to 4 carbon atoms include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl.

[0056] Specific examples of the compounds shown in formula (2) include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide, tetra(2-hydroxypropyl)ammonium hydroxide, etc.

[0057] The above-mentioned strong alkaline compounds can be used alone or in combination of two or more.

[0058] (Weakly basic compound)

[0059] As a weakly basic compound, there are no particular limitations; both inorganic and organic weakly basic compounds can be listed.

[0060] As inorganic weakly basic compounds, there are no particular limitations, and examples include weakly basic alkali metal compounds such as sodium carbonate, potassium carbonate, sodium silicate, and potassium silicate; weakly basic alkaline earth metal compounds such as magnesium hydroxide, magnesium carbonate, calcium carbonate, calcium silicate, and magnesium silicate; transition metal compounds such as copper hydroxide and iron hydroxide; and ammonia.

[0061] As organic weak basic compounds, there are no particular limitations, and amine compounds represented by the following formulas (3) or (4) can be listed.

[0062]

[0063] In the above formula, R 5 It consists of hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and aminoalkyl groups having 1 to 4 carbon atoms. Additionally, R... 6 It consists of hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and hydroxyalkyl groups having 1 to 4 carbon atoms. Furthermore, R... 7 It is a hydroxyalkyl group with 1 to 4 carbon atoms or an aminoalkyl group with 1 to 6 carbon atoms.

[0064] R 8It is an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or an aminoalkyl group having 1 to 4 carbon atoms. In addition, p is an integer of 1 or more, preferably 1 to 6, and more preferably 2 or 3.

[0065] Here, alkyl groups having 1 to 4 carbon atoms can be listed as methyl, ethyl, propyl, isopropyl, butyl, etc.

[0066] Examples of hydroxyalkyl groups with 1 to 4 carbon atoms include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl.

[0067] Examples of aminoalkyl groups with 1 to 4 carbon atoms include aminomethyl, aminoethyl, aminopropyl, and aminobutyl.

[0068] Specific examples of amine compounds represented by formula (3) include monoethanolamine, monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, etc.

[0069] Specific examples of amine compounds represented by formula (4) include 1-methylpiperazine, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperazine, etc.

[0070] The aforementioned weakly basic compounds can be used alone or in combination of two or more.

[0071] In one embodiment, from the viewpoint of making the pH of the composition 13 or higher, the alkaline compound preferably includes a strong alkaline compound, and from the viewpoint of being able to further suppress the oxidation of copper wiring, it is more preferably to include an inorganic strong alkaline compound, and even more preferably to include a strong alkaline metal compound, especially preferably potassium hydroxide or sodium hydroxide.

[0072] In one embodiment, from the viewpoint of improving the peelability of the resist, the basic compound preferably contains both a strong basic compound and a weak basic compound, more preferably an organic weak basic compound, and particularly preferably an amine compound represented by formula (3). It is very preferably composed of at least one selected from the group consisting of monoethanolamine, monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-(β-aminoethyl)ethanolamine, and N-(β-aminoethyl)isopropanolamine. Most preferably, it contains at least one selected from the group consisting of monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, N-dimethylmonoethanolamine, N-diethylmonoethanolamine, and N-(β-aminoethyl)ethanolamine.

[0073] The content of the alkaline compound relative to the total mass of the composition is preferably 0.1 to 50% by mass, more preferably 1 to 20% by mass, even more preferably 3 to 20% by mass, and particularly preferably 3 to 10% by mass.

[0074] In one embodiment, the content of the strong alkaline compound relative to the total mass of the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, even more preferably 1 to 10% by mass, and from the viewpoint of further suppressing the oxidation of copper wiring, particularly preferably 3 to 10% by mass, and most preferably 3 to 6% by mass.

[0075] In one embodiment, the content of the weakly basic compound relative to the total mass of the composition is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass.

[0076] [Copper Surface Protectant]

[0077] Copper surface protectants have the function of adsorbing onto copper wiring to form a protective film, thereby inhibiting the oxidation of copper wiring. It can be considered that the oxidation inhibition effect on copper wiring is due to: for example, the pH of the composition being 13 or higher, the zeta (ζ) potential of the copper surface being negative, thus allowing cationic copper surface protectants to adsorb onto the copper surface; and the high affinity of sulfur for copper, thus allowing thiol-based copper surface protectants to adsorb onto the copper surface, etc. It should be noted that situations where the composition of the present invention exhibits the effects of the present invention for reasons other than those described above are also included within the scope of the present invention.

[0078] The copper surface protectant comprises at least one of the following groups: an ammonium salt selected from the formula (1), a heteroaryl salt having substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms, and a substituted or unsubstituted thiol having 5 to 30 carbon atoms.

[0079] (Ammonium salt shown in formula (1))

[0080] The ammonium salt of the present invention is represented by the following formula (1).

[0081]

[0082] In equation (1) above, R 1 It is a substituted or unsubstituted alkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl (poly)hexaalkylene group having 5 to 30 carbon atoms, or a substituted or unsubstituted aryl (poly)hexaalkylene group having 7 to 30 carbon atoms.

[0083] Alkyl groups having 5 to 30 carbon atoms are not particularly limited and can include pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tetradecyl, hexadecyl, octadecyl, triacontyl, etc.

[0084] When a substituted or unsubstituted alkyl group has 5 to 30 carbon atoms, the substituent is not particularly limited. Examples include halogen atoms such as fluorine, chlorine, bromine, and iodine; aryl groups with 6 to 20 carbon atoms such as phenyl and naphthyl; alkoxy groups with 1 to 6 carbon atoms such as methoxy, ethoxy, and propoxy; hydroxyl groups; cyano groups; and nitro groups. It should be noted that there can be one or more substituents. Furthermore, substituted alkyl groups with 5 to 30 carbon atoms refer to a total number of carbon atoms in both the substituent and the alkyl group that is 5 to 30.

[0085] Alkyl (poly)hexaalkylene compounds with 5 to 30 carbon atoms are composed of -(C n H 2n -Z-) m -R 3 In this case, n is independently 1 to 5, preferably 1 to 3, more preferably 1 to 2. m is 1 to 5, preferably 1 to 2. Z is independently oxygen atom (O), sulfur atom (S), and phosphorus atom (P), preferably oxygen atom (O). R 3 Alkyl groups having 1 to 30 carbon atoms can be listed as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, etc.

[0086] When a substituted or unsubstituted alkyl (poly)heteroalkylene group has 5 to 30 carbon atoms, and it has a substituent (substituted alkyl (poly)heteroalkylene group with 5 to 30 carbon atoms), there are no particular restrictions on the substituent. Examples include halogen atoms such as fluorine, chlorine, bromine, and iodine; aryl groups with 6 to 20 carbon atoms such as phenyl and naphthyl; alkoxy groups with 1 to 6 carbon atoms such as methoxy, ethoxy, and propoxy; hydroxyl groups; cyano groups; and nitro groups. It should be noted that this substituent usually replaces R. 3 The hydrogen atom. In addition, there can be one substituent or more than two. Furthermore, substituted alkyl (poly)hexaalkylene refers to a total number of carbon atoms of the substituent and the alkyl (poly)hexaalkylene when the number of carbon atoms is 5 to 30.

[0087] Aryl(poly)heteroalkylene groups with 7 to 30 carbon atoms are composed of -(C n H 2n -Z-) m -Ar represents the group. In this case, n is 1 to 5, preferably 1 to 3, and more preferably 1 to 2. m is 1 to 5, preferably 1 to 2. Z is an oxygen atom (O), a sulfur atom (S), or a phosphorus atom (P), preferably an oxygen atom (O). Ar is an aryl group with 6 to 18 carbon atoms, such as phenyl, naphthyl, anthracene, etc.

[0088] When a substituted or unsubstituted aryl(poly)heteroalkylene group has 7 to 30 carbon atoms, the substituent is not particularly limited, and examples include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, and 1,1,3,3-tetramethylbutyl; alkoxy groups with 1 to 6 carbon atoms such as methoxy, ethoxy, and propoxy; hydroxyl groups; cyano groups; and nitro groups. The substituent is usually replaced by a hydrogen atom of Ar. Furthermore, there can be one or more substituents. Specifically, substituted aryl(poly)heteroalkylene groups with 7 to 30 carbon atoms refer to a total number of carbon atoms in the substituent and the aryl(poly)heteroalkylene group that is 7 to 30.

[0089] In one implementation, R 1 Preferably, it is a substituted or unsubstituted alkyl group having 5 to 30 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, even more preferably an alkyl group having 10 to 20 carbon atoms, particularly preferably an alkyl group having 14 to 20 carbon atoms, and most preferably an alkyl group having 16 to 20 carbon atoms.

[0090] R 2 Each is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

[0091] Alkyl groups having 1 to 30 carbon atoms are not particularly limited and can include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, nonadecanyl, eicosyl, etc.

[0092] Substituents in substituted or unsubstituted alkyl groups (1-30 carbon atoms) include halogen atoms such as fluorine, chlorine, bromine, and iodine; aryl groups with 6-20 carbon atoms such as phenyl and naphthyl; alkoxy groups with 1-6 carbon atoms such as methoxy, ethoxy, and propoxy; hydroxyl groups; cyano groups; and nitro groups. It should be noted that there can be one or more substituents. Furthermore, substituted alkyl groups with 1-30 carbon atoms refer to alkyl groups with a total carbon number of 1-30, including both the substituent and the alkyl group.

[0093] There are no particular restrictions on aryl groups with 6 to 30 carbon atoms; examples include phenyl, naphthyl, and biphenyl.

[0094] When a substituted or unsubstituted aryl group has 6 to 30 carbon atoms, the substituents can include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, propyl, and isopropyl; alkoxy groups with 1 to 6 carbon atoms such as methoxy, ethoxy, and propoxy; hydroxyl groups; cyano groups; and nitro groups. It should be noted that there can be one or more substituents. Furthermore, substituted aryl groups with 6 to 30 carbon atoms refer to a total number of carbon atoms in the substituent and the alkyl group that is 6 to 30.

[0095] Among them, R 2 Preferably, it is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, more preferably methyl, ethyl, propyl, isopropyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, benzyl, hydroxymethyl, 2-hydroxyethyl, further preferably methyl, ethyl, benzyl, 2-hydroxyethyl, particularly preferably methyl or benzyl, and most preferably methyl. In another embodiment, R... 2 Preferably, it is an alkyl group with 1 to 10 carbons substituted by an aryl group having 6 to 20 carbons, more preferably an alkyl group with 1 to 5 carbons substituted by a phenyl group, further preferably benzyl or phenylethyl, and particularly preferably benzyl.

[0096] X can be a halide ion (fluoride ion, chloride ion, bromide ion, iodide ion, etc.), hydroxide ion, organic sulfonate ion (methanesulfonate ion, p-toluenesulfonate ion, etc.), tetrafluoroborate anion, or hexafluorophosphate anion. Preferably, X is a halide ion, and more preferably, a chloride ion or a bromide ion.

[0097] As R1 Specific examples of ammonium salts of formula (1) with substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms include: hexyltrimethylammonium bromide and other ammonium salts containing a hexyl group; heptyltrimethylammonium bromide and other ammonium salts containing a heptyl group; octyltrimethylammonium chloride, octyldimethylbenzylammonium chloride and other ammonium salts containing an octyl group; decyltrimethylammonium chloride, decyldimethylbenzylammonium chloride and other ammonium salts containing a decyl group; dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecylethyldimethylammonium chloride, dodecylethyldimethylammonium bromide, benzyldodecyldimethylammonium chloride, benzyldodecyldimethylammonium bromide, tris(dodecyl)methylammonium chloride ... Ammonium salts containing dodecyl groups, such as methylammonium bromide; ammonium salts containing tetradecyl groups, such as tetradecyltrimethylammonium bromide and benzyldimethyltetradecylammonium chloride; ammonium salts containing hexadecyl groups, such as hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, ethylhexadecyldimethylammonium chloride, ethylhexadecyldimethylammonium bromide, benzyldimethylhexadecylammonium chloride; and ammonium salts containing octadecyl groups, such as trimethyloctadecylammonium chloride, trimethyloctadecylammonium bromide, dimethylbisoctadecylammonium chloride, dimethylbisoctadecylammonium bromide, benzyldimethyloctadecylammonium chloride.

[0098] As R 1 Specific examples of ammonium salts of formula (1) that are substituted or unsubstituted alkyl (poly)heteroalkylene groups having 5 to 30 carbon atoms include trimethylpropyl di(oxoethylene)ammonium chloride, trimethylpropyl oxoethylene thioethylene ammonium chloride, etc.

[0099] As R 1 Specific examples of ammonium salts of formula (1) that are substituted or unsubstituted aryl (poly)heteroalkylene groups having 7 to 30 carbon atoms include benzyl dimethyl-2-{2-[4-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy}ethyl ammonium chloride (benzyl chloride), benzyl dimethylphenyl di(oxoethyl) ammonium chloride, etc.

[0100] (Heteroaryl salts with substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms)

[0101] There are no particular limitations on the heteroaryl salts having substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms. Examples include the salts of heteroaryl cations formed by bonding at least one nitrogen atom of a substituted or unsubstituted nitrogen-containing heteroaryl ring with a substituted or unsubstituted alkyl group having 5 to 30 carbon atoms.

[0102] There are no particular limitations on the heteroaryl ring containing the nitrogen atom, and examples include imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrazine, pyridazine, pyrimidine, quinoline, isoquinoline, etc.

[0103] At this point, the substituents that are substituents when the nitrogen-containing heteroaryl ring has substituents can be listed as follows: halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups with 1 to 4 carbons such as methyl, ethyl, propyl, and isopropyl; aryl groups with 6 to 20 carbons such as phenyl and naphthyl; alkoxy groups with 1 to 6 carbons such as methoxy, ethoxy, and propoxy; hydroxyl; cyano; nitro, etc.

[0104] There are no particular limitations on alkyl groups having 5 to 30 carbon atoms, and examples include pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tetradecyl, hexadecyl, octadecyl, triacontyl, etc.

[0105] Substituents in substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms (substituted alkyl groups having 5 to 30 carbon atoms) can include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and isopropyl; aryl groups having 6 to 20 carbon atoms such as phenyl and naphthyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and propoxy; hydroxyl groups; cyano groups; and nitro groups. It should be noted that there can be one or more substituents. Furthermore, substituted alkyl groups having 5 to 30 carbon atoms refer to a total number of carbon atoms in both the substituent and the alkyl group being 5 to 30.

[0106] The substituted or unsubstituted alkyl group having 5 to 30 carbon atoms is preferably a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, more preferably an alkyl group having 10 to 20 carbon atoms, and even more preferably decyl, dodecyl, tetradecyl, hexadecyl, or octadecyl.

[0107] The counter anion is a heteroaryl cation having substituted or unsubstituted alkyl groups with 5 to 30 carbon atoms. There are no particular limitations, and examples include halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions; hydroxide ions; organic sulfonate ions such as methanesulfonate ions and p-toluenesulfonate ions; tetrafluoroborate anions; and hexafluorophosphate anions. Preferably, the counter anion is a halide ion, more preferably a chloride ion or a bromide ion.

[0108] Specific examples of heteroaryl salts having substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms include 1-methyl-3-hexylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium bromide, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-dodecyl-3-methylimidazolium chloride, 1-dodecyl-3-methylimidazolium bromide. Imidazolium salts including 1-tetradecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium bromide, 1-hexadecyl-3-methylimidazolium chloride, 1-hexadecyl-3-methylimidazolium bromide, 1-octadecyl-3-methylimidazolium chloride, and 1-octadecyl-3-methylimidazolium bromide; oxazolium salts including 3-dodecyloxazolium chloride, 3-dodecyloxazolium chloride, 3-tetradecyloxazolium chloride, 3-hexadecyloxazolium chloride, and 3-octadecyloxazolium chloride; 3-decyl chloride... Thiazolium salts including thiazolyl chloride, 3-dodecylthiazolyl chloride, 3-tetradecylthiazolyl chloride, 3-hexadecylthiazolyl chloride, and 3-octadecylthiazolyl chloride; and pyridinium salts including 1-decylpyridinium bromide, 1-dodecylpyridinium bromide, 1-dodecylpyridinium chloride, 1-tetradecylpyridinium chloride, 1-tetradecylpyridinium bromide, 1-hexadecylpyridinium chloride, 1-hexadecylpyridinium bromide, 1-hexadecylpyridinium chloride, 1-octadecylpyridinium chloride, and 1-octadecylpyridinium bromide. Salts; pyrimidineonium salts such as 1-decylpyrimidineonium chloride, 1-dodecylpyrimidineonium chloride, 1-tetradecylpyrimidineonium chloride, 1-hexadecylpyrimidineonium chloride, and 1-octadecylpyrimidineonium chloride; quinolineonium salts such as decylquinolineonium chloride, dodecylquinolineonium chloride, tetradecylquinolineonium chloride, hexadecylquinolineonium chloride, and octadecylquinolineonium chloride; isoquinolineonium salts such as decylisoquinolineonium chloride, dodecylisoquinolineonium chloride, tetradecylisoquinolineonium chloride, hexadecylisoquinolineonium chloride, and octadecylisoquinolineonium chloride. Furthermore, they can also be used in hydrate form.

[0109] (substituted or unsubstituted thiols with 5 to 30 carbon atoms)

[0110] There are no particular restrictions on substituted or unsubstituted thiols with 5 to 30 carbon atoms, and examples include 1-pentanethiol, 2-pentanethiol, 3-pentanethiol, 1-hexanethiol, 1-heptanethiol, 1-octanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol, 1-dodecanethiol, 1-tetradecanethiol, 1-hexadecanethiol, and 1-octadecanethiol.

[0111] When substituted or unsubstituted thiols have substituents (5-30 carbon atoms), examples of substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine; aryl groups with 6-20 carbon atoms such as phenyl and naphthyl; alkoxy groups with 1-6 carbon atoms such as methoxy, ethoxy, and propoxy; hydroxyl groups; cyano groups; and nitro groups. It should be noted that there can be one or more substituents. Furthermore, substituted thiols with 5-30 carbon atoms refer to thiols where the total number of carbon atoms in the substituent and the thiolol is 5-30.

[0112] The above-mentioned copper surface protectants can be used alone or in combination of two or more.

[0113] In one embodiment, the copper surface protectant preferably comprises a heteroaryl salt having substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms, more preferably a heteroaryl salt having substituted or unsubstituted alkyl groups having 8 to 30 carbon atoms, and even more preferably at least one selected from the group consisting of pyridinium salts having substituted or unsubstituted alkyl groups having 8 to 30 carbon atoms and imidazolium salts having substituted or unsubstituted alkyl groups having 8 to 30 carbon atoms. From the viewpoint of further suppressing the oxidation of copper wiring, it is particularly preferred to include at least one selected from the group consisting of pyridinium salts having substituted or unsubstituted alkyl groups having 14 to 20 carbon atoms and imidazolium salts having substituted or unsubstituted alkyl groups having 8 to 14 carbon atoms.

[0114] That is, in a preferred embodiment, the copper surface protectant preferably contains a pyridinium salt having substituted or unsubstituted alkyl groups having 14 to 20 carbon atoms, more preferably a pyridinium salt having alkyl groups having 14 to 18 carbon atoms, a pyridinium salt having alkyl groups having 18 to 20 carbon atoms, even more preferably a pyridinium salt having alkyl groups having 14 to 16 carbon atoms, a pyridinium salt having alkyl groups having 16 to 18 carbon atoms, and particularly preferably a pyridinium salt having alkyl groups having 16 to 18 carbon atoms.

[0115] In addition, in a preferred embodiment, the copper surface protectant preferably comprises an imidazolium salt having substituted or unsubstituted alkyl groups having 8 to 14 carbon atoms, more preferably an imidazolium salt having alkyl groups having 10 to 14 carbon atoms, and even more preferably an imidazolium salt having alkyl groups having 12 to 14 carbon atoms.

[0116] In one embodiment, the copper surface protectant preferably contains substituted or unsubstituted thiols with 5 to 30 carbon atoms, more preferably substituted or unsubstituted thiols with 8 to 20 carbon atoms, even more preferably thiols with 8 to 16 carbon atoms, particularly preferably thiols with 10 to 16 carbon atoms, and most preferably thiols with 10 to 14 carbon atoms.

[0117] The content of the copper surface protectant relative to the total mass of the composition is preferably 0.0001 to 5% by mass, more preferably 0.001 to 1% by mass, and even more preferably 0.01 to 1% by mass. From the viewpoint that the oxidation of copper wiring can be further suppressed, it is particularly preferably 0.07 to 0.5% by mass, and most preferably 0.07 to 0.3% by mass.

[0118] [Organic solvents]

[0119] The compositions of the present invention preferably contain an organic solvent.

[0120] Organic solvents can facilitate the removal of photoresist. For example, due to their lipid solubility, organic solvents allow alkaline compounds and water to penetrate into the photoresist. In addition, they reduce the adhesion between the substrate and the resin, thus effectively removing the photoresist.

[0121] As organic solvents, there are no particular limitations, and examples include monools such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, tert-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, and 1-decanol; diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,2-hexanediol, 1,6-hexanediol, and 2-ethylhexane-1,3-diol; polyols such as glycerol; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and 1,4-dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol n-butyl ether (2-butoxyethanol), and ethylene glycol monophenyl ether (…). Diol ethers include phenoxyethanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, propylene glycol phenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, dipropylene glycol dimethyl ether, etc.; amides such as dimethylformamide, diethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.; and heterocyclic compounds such as pyrrole, pyridine, and triazole. The organic solvent preferably includes glycol ethers, and more preferably includes at least one selected from the group consisting of ethylene glycol monoethyl ether, 2-butoxyethanol, phenoxyethanol, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and diethylene glycol monophenyl ether. It should be noted that the above-mentioned organic solvents can be used alone or in combination of two or more.

[0122] The content of organic solvent relative to the total mass of the composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 1 to 10% by mass.

[0123] [water]

[0124] Water can sometimes facilitate the removal of photoresist. For example, by combining water with alkaline compounds to dissolve alkaline-soluble resins, the structure of the photoresist changes, reducing the adhesion between the substrate and the resin, thus enabling the photoresist to be properly removed from the substrate.

[0125] The water content relative to the total mass of the composition is preferably 60-99% by mass, more preferably 60-80% by mass, 70-99% by mass, 80-99% by mass, or 90-99% by mass.

[0126] [Physical properties of the composition]

[0127] The composition of the present invention has a pH of 13 or higher, preferably 13 to 14.5, and more preferably 13 to 14. By setting the pH to 13 or higher, the resist can be removed, and the oxidation of the copper wiring can be suppressed.

[0128] 2. Manufacturing method of electronic substrate

[0129] According to one aspect of the present invention, a method for manufacturing an electronic substrate is provided. The method for manufacturing an electronic substrate includes the steps of: contacting the above-described composition with a substrate having copper wiring and a photoresist disposed between the copper wiring to remove the photoresist, and forming a protective layer on the surface of the copper wiring.

[0130] [Substrate]

[0131] The substrate has copper wiring and a resist disposed between the copper wiring.

[0132] There are no particular limitations on the substrate, and examples include resin substrates (substrates made by impregnating paper, glass, etc. with resins such as phenolic resin, epoxy resin, fluororesin, and bismaleimide-triazine resin; specifically, paper-phenol substrates, paper-epoxy boards, Teflon substrates, glass-epoxy boards, etc.), silicon substrates, silicon carbide substrates, sapphire substrates, gallium phosphide (GaP) substrates, gallium arsenide (GaAs) substrates, indium phosphide (InP) substrates, gallium nitride (GaN) substrates, and glass substrates. Among these, resin substrates or silicon substrates are preferred.

[0133] In one embodiment, the substrate is a single-layer substrate such as a resin substrate.

[0134] In another embodiment, the substrate can be a laminated structure having a seed layer (conductive layer). In one embodiment, the substrate is a laminated substrate of a resin substrate or the like with a seed layer. In this case, the seed layer can be a copper plating layer or sputtered copper layer used in the SAP process or the like, or a copper foil layer used in the MASP process or the like.

[0135] In another embodiment, the substrate may have a patterned metal circuit. In one embodiment, the substrate is a circuit board having a resin substrate or the like and a metal circuit. In this case, the metal constituting the metal circuit is not particularly limited, but is preferably copper, aluminum, cobalt, or a combination thereof, and more preferably copper.

[0136] The substrate has copper wiring and a resist disposed between the copper wiring.

[0137] For example, when the substrate is a single-layer substrate such as a resin substrate or a silicon substrate, copper wiring (circuit) and photoresist are formed on the surface of the single-layer substrate (resin substrate, silicon substrate, etc.).

[0138] In addition, when the substrate is a laminated substrate of resin substrate or the seed layer, copper wiring (circuit) and resist are formed on the surface of the seed layer.

[0139] Furthermore, when the substrate is a circuit board having a resin substrate or the like and a metal circuit, copper wiring (connection terminals such as pillars and bumps) is formed on the metal circuit, and a photoresist is formed on the resin substrate or the like.

[0140] It should be noted that the patterns that can be formed on the substrate are usually formed based on pattern designs made according to the application, desired performance, etc.

[0141] For example, when the substrate is a single-layer substrate or a multilayer substrate, the pattern that can be formed on the substrate can be a circuit. Examples of such circuit patterns include comb patterns (also known as "line and spacing patterns", which are patterns with metal wiring formed in parallel lines).

[0142] Furthermore, when the substrate is a circuit board, the pattern formed on the substrate can be a pattern of connecting terminals such as pillars or bumps. Examples of such connecting terminal patterns include dot patterns (also known as "pillar patterns") and patterns in which metal wiring is formed in the shape of water droplets.

[0143] It should be noted that known methods can be appropriately used for patterning.

[0144] (copper cabling)

[0145] Copper wiring is wiring primarily composed of copper. In this case, copper wiring may further contain copper oxide, unavoidable impurities, etc. It should be noted that there are no particular restrictions on the shape of copper wiring.

[0146] The copper wiring width is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, and particularly preferably less than 15 μm. There is no particular limitation on the lower limit of the copper wiring width, but it is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more. A copper wiring width of 50 μm or less is preferred because it enables the manufacture of miniaturized electronic substrates. It should be noted that, in this specification, "copper wiring width" refers to the minimum length of the copper wiring width when it is formed into a straight line by patterning with a comb-like pattern or the like. In this case, the copper wiring width is the average of any 30 copper wiring widths. Furthermore, the copper wiring width is also referred to as a line.

[0147] There are no particular limitations on the dot diameter of the copper wiring, but it is preferably 800 μm or less, more preferably 10 to 600 μm, even more preferably 50 to 500 μm, and particularly preferably 100 to 300 μm. A dot diameter of 800 μm or less allows for the manufacture of miniaturized electronic substrates, and is therefore preferred. It should be noted that, in this specification, "dot diameter of the copper wiring" refers to the diameter of the outermost surface (the opposite surface of the substrate contact surface) of the copper wiring (cylindrical) when it is formed into a cylindrical shape through patterning into a dot pattern, etc. In this case, "diameter" refers to the maximum distance between two points on the outer edge of the circle. Furthermore, the dot diameter of the copper wiring is the average of the dot diameters of any 30 copper wirings.

[0148] There are no particular limitations on the thickness of the copper wiring, but 1 μm or more is preferred, 5 to 50 μm is more preferred, and 10 to 30 μm is even more preferred. When the thickness of the copper wiring is 1 μm or more, the resistance of the printed circuit board can be reduced, which is therefore preferable. Furthermore, in this specification, "thickness of the copper wiring" refers to the longest distance between the substrate contact surface of the copper wiring and the outermost surface of the copper wiring (the surface opposite the substrate contact surface). In this case, the thickness of the copper wiring is the average of the thicknesses of any 30 copper wirings.

[0149] (Anticorrosion agent applied between metal wiring)

[0150] Examples of photoresists include dry film photoresists and liquid photoresists. Dry film photoresists are preferred.

[0151] There are no particular limitations on the dry film resist, but it is preferably formed from a photosensitive resin. Examples of photosensitive resins include negative photosensitive resins and positive photosensitive resins.

[0152] There are no particular limitations on negative photosensitive resins, and examples include azide-based photosensitive resins, diazo-based photosensitive resins, low-molecular-weight alkyne photosensitive resins, low-molecular-weight olefin photosensitive resins, insoluble high-molecular-weight photosensitive resins, and chromic acid-based photosensitive resins. These negative photosensitive resins can be used alone or in combination of two or more.

[0153] There are no particular limitations on positive photosensitive resins; examples include quinone diazide-based photosensitive resins and soluble polymer-based photosensitive resins. These positive photosensitive resins can be used alone or in combination of two or more.

[0154] The dry film resist is preferably formed from a negative photosensitive resin.

[0155] The resist width is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, and particularly preferably 15 μm or less. There is no particular limitation on the lower limit of the resist width, but it is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more. A resist width of 50 μm or less is preferred because it enables the manufacture of miniaturized electronic substrates. It should be noted that, in this specification, "resist width" refers to the minimum length of the resist width when it is patterned into a straight line using a comb-shaped pattern or similar method. In this case, the resist width is the average of any 30 resist widths.

[0156] The copper wiring width / resist width of the substrate is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, and particularly preferably 3 to 15 μm. When the copper wiring width / resist width of the substrate is 50 μm or less, miniaturized electronic substrates can be manufactured, and therefore this is preferred.

[0157] (touch)

[0158] In the resist removal process, the substrate is brought into contact with the composition of the present invention to remove the resist, and a protective layer is formed on the surface of the copper wiring. This allows for the removal of the resist, resulting in an electronic substrate with patterns formed on the copper wiring. Furthermore, because a protective layer is formed on the surface of the copper wiring, the substrate can be stored for a long period even after the resist has been removed.

[0159] There are no particular limitations on the contact method; any known technique may be appropriately employed. Specifically, the substrate may be immersed in the composition of the present invention, sprayed with the composition of the present invention onto the substrate, or dripped onto the substrate (e.g., single-piece spin processing). In this case, the immersion may be repeated more than twice, the spraying may be repeated more than twice, the dripping may be repeated more than twice, or a combination of immersion, spraying, and dripping may be used.

[0160] There are no particular limitations on the contact temperature, but it is preferably 0~90℃, more preferably 15~70℃, and even more preferably 20~60℃.

[0161] The contact time is not particularly limited, but is preferably 1 second to 30 minutes, more preferably 30 seconds to 20 minutes, even more preferably 1 to 20 minutes, and particularly preferably 2 to 20 minutes. If the contact time is more than 1 second, the resist can be removed with a high peeling rate, which is therefore preferred. On the other hand, when the contact time is less than 30 minutes, production costs are reduced, which is also preferred.

[0162] The resist removal process is preferably carried out within 10 minutes, more preferably within 7 minutes, further preferably within 5 minutes, particularly preferably within 3 minutes, and most preferably within 50 seconds. Furthermore, in this specification, "lifting time" refers to the time from immersing the substrate in the composition of the present invention until the peeling is completed.

[0163] The protective layer formed on the surface of the copper wiring is preferably removed after storage. For example, the protective layer can be removed by cleaning the surface of the electronic substrate with acidic aqueous solution, alkaline aqueous solution, warm water (40~80°C, preferably 40~60°C), or by heat treatment of the electronic substrate with annealing (90~150°C, preferably 100~140°C).

[0164] Furthermore, when the electronic substrate is a laminated substrate such as a resin substrate and a seed layer, the protective layer can be removed simultaneously by performing rapid etching of the seed layer after the resist is removed.

[0165] [Electronic substrate]

[0166] An electronic substrate includes a substrate and metal wiring disposed on the substrate.

[0167] At this point, the metal wiring can reflect the shape of the metal wiring formed on the substrate before the pre-processing step.

[0168] The substrate, type of metal wiring, width (line) of metal wiring, dot diameter of metal wiring, and thickness of metal wiring are as described above.

[0169] By removing the resist, the substrate surface of an electronic substrate can be exposed. For example, in a comb pattern (line and spacer pattern), the exposed portion of the substrate (the portion where the resist has been removed) is called a spacer.

[0170] The spacing width reflects the width of the resist. Specifically, the spacing width is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, and particularly preferably less than 15 μm. There are no particular limitations on the lower limit of the spacing width, but it is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more. Furthermore, in this specification, "spacing width" refers to the minimum length of the spacing width when the spacing is formed into a straight line through patterning processing such as a comb pattern. In this case, the spacing width is the average of any 30 spacing widths.

[0171] The line spacing of the electronic substrate is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, and particularly preferably 3 to 15 μm. When the line spacing of the electronic substrate is 50 μm or less, miniaturization and high functionality of electronic devices can be achieved, and therefore it is preferred.

[0172] 3. Resist Removal Methods

[0173] According to one aspect of the present invention, a method for removing resist is provided. The method includes the steps of: contacting the composition with a substrate having copper wiring and resist disposed between the copper wiring to remove the resist, and forming a protective layer on the surface of the copper wiring.

[0174] According to the removal method, the resist can be removed. Furthermore, according to the removal method, a copper surface protectant is used to protect the copper wiring, thus inhibiting the oxidation of the copper wiring.

[0175] The resist removal process, etc., are as described above.

[0176] 4. Reagent kit

[0177] According to one aspect of the present invention, a kit is provided. The kit is used in the above-described method for manufacturing an electronic substrate or the above-described method for removing resist. The kit comprises, in an immiscible state, a first solution containing an alkaline compound and a second solution containing a copper surface protectant, wherein the first solution and the second solution are mixed during use.

[0178] [First Solution]

[0179] The first solution contains an alkaline compound, preferably a strongly alkaline compound. Additionally, it may contain water, organic solvents, etc., as needed.

[0180] The above-mentioned substances are used in the production of alkaline compounds, water, and organic solvents.

[0181] In a preferred embodiment, the first solution comprises a strongly alkaline compound and water.

[0182] [Second solution]

[0183] The second solution contains a copper surface protectant. Additionally, it may contain a weakly alkaline compound, water, organic solvents, etc., depending on the requirements.

[0184] Copper surface protectant, weak alkaline compound, water, and organic solvents are used.

[0185] In a preferred embodiment, the second solution comprises a copper surface protectant (preferably a heteroaryl salt having substituted or unsubstituted alkyl groups with 5 to 30 carbon atoms, more preferably an imidazolium salt having substituted or unsubstituted alkyl groups with 5 to 30 carbon atoms) and water.

[0186] In another preferred embodiment, the second solution comprises a copper surface protectant (preferably a heteroaryl salt having substituted or unsubstituted alkyl groups with 5 to 30 carbon atoms, more preferably an imidazolium salt having substituted or unsubstituted alkyl groups with 5 to 30 carbon atoms), a weakly basic compound, and water.

[0187] In another preferred embodiment, the second solution comprises a copper surface protectant (preferably a heteroaryl salt having substituted or unsubstituted alkyl groups with 5 to 30 carbon atoms, more preferably an imidazolium salt having substituted or unsubstituted alkyl groups with 5 to 30 carbon atoms), an organic solvent, and water.

[0188] In another preferred embodiment, the second solution comprises a copper surface protectant (preferably a heteroaryl salt having substituted or unsubstituted alkyl groups with 5 to 30 carbon atoms, more preferably an imidazolium salt having substituted or unsubstituted alkyl groups with 5 to 30 carbon atoms), a weakly basic compound, an organic solvent, and water.

[0189] It should be noted that when the copper surface protectant is a heteroaryl salt with substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms (preferably an imidazolium salt with substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms), by making the second solution containing the heteroaryl salt immiscible with the first solution containing the strong basic compound, the decomposition reaction (nucleophilic substitution reaction, β-elimination reaction, hydrolysis reaction, etc.) of the heteroaryl salt can be prevented.

[0190] In use, the first solution and the second solution can be mixed to prepare a composition, thereby allowing the kit to be used in the aforementioned electronic substrate manufacturing method or the aforementioned resist removal method, etc. At this time, to adjust the composition of the final composition, at least one selected from the group consisting of an alkaline compound, a copper surface protectant, water, and an organic solvent, preferably water, can be added together with the first and second solutions.

[0191] Example

[0192] The present invention will be specifically described below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0193] [Example 1]

[0194] A composition is prepared by mixing 2 parts by mass of tetramethylammonium hydroxide (TMAH) as an alkaline compound (strong alkaline compound), 0.05 parts by mass of 1-hexadecylpyridinium chloride monohydrate (1-HexDPC) as a copper surface protectant, and 97.95 parts by mass of water.

[0195] The pH of the manufactured composition was measured and the result was 13.5. It should be noted that the pH was measured at 20°C using a benchtop pH meter (F-71) (manufactured by Horiba Corporation) and a pH electrode (9615S-10D) (manufactured by Horiba Corporation).

[0196] [Examples 2-15 and Comparative Examples 1-6]

[0197] The composition was changed to the composition described in Table 1, except that it was manufactured by the same method as in Example 1.

[0198] [Table 1]

[0199]

[0200] It should be noted that the structural formulas of the copper surface protectants, etc., used in the embodiments and comparative examples are shown below.

[0201]

[0202] [evaluate]

[0203] Various evaluations were performed on the compositions prepared in Examples 1-15 and Comparative Examples 1-6.

[0204] (Copper oxidation rate)

[0205] (1) Preprocessing

[0206] Electrolytically plated copper substrates (copper film thickness: 15000 Å) were cut into 2cm × 2cm pieces. The substrates were immersed in a mixed solution of 1% hydrogen peroxide (H₂O₂), 1% sulfuric acid (H₂SO₄), and 98% water for 20 seconds at room temperature (23°C), then rinsed with water and dried. Next, the dried substrates were immersed in a 1% sulfuric acid (H₂SO₄) aqueous solution at room temperature (23°C) for 5 minutes, then rinsed with water and dried. X-ray photoelectron spectroscopy (XPS; PHI Quantera II, manufactured by ULVAC-PHI Corporation) was used to analyze the surface of the freshly treated electrolytically plated copper substrates, confirming the absence of copper oxide (CuO) on the surface.

[0207] (2) Formation of copper surface protective layer

[0208] The electroplated copper substrate, after removing copper oxide (CuO), is immersed in the composition with stirring at 50°C. Then, it is rinsed with water at 23°C for 10 seconds and purged with nitrogen to remove water from the surface, forming a copper surface protective layer on the copper layer of the electroplated copper substrate.

[0209] It should be noted that the stirring and impregnation time of the electrolytically plated copper substrate in the composition is the same as the stirring and impregnation time of the substrate in the composition (processing time in Table 2) in the evaluation of the peelability of the dry film resist described later.

[0210] (3) Evaluation of copper oxidation rate

[0211] The electrolytically plated copper substrate with a copper surface protective layer was stored in the atmosphere at 20°C for 24 hours.

[0212] The copper oxidation rate of an electrolytically plated copper substrate with a copper surface protective layer was measured after storage.

[0213] Specifically, X-ray photoelectron spectroscopy (XPS; PHI Quantera II manufactured by ULVAC-PHI Corporation) was used to analyze the stored electrolytically plated copper substrate with a copper surface protective layer to obtain the narrow-scan spectrum of Cu2p. The obtained narrow-scan spectrum of Cu2p was analyzed by curve fitting to calculate the Cu... 2+ The peak areas of copper(II) oxide (CuO) and copper(II) hydroxide (Cu(OH)2) respectively are related to Cu + The sum of the peak areas of Cu and Cu. Using the obtained peak areas, the copper oxidation rate (Cu) can be calculated. 2+ The peak area of ​​copper(II) oxide (CuO) divided by Cu + (The value is obtained by summing the peak areas of Cu and Cu). It should be noted that the higher the copper oxidation rate, the greater the sum of the peak areas of Cu and Cu. + Compared to Cu, Cu 2+The higher the copper oxide (II)(CuO) content, the more the Cu layer surface of the Cu sample is oxidized during the storage of the electroplated copper substrate. The results are shown in Table 2 below. It should be noted that Table 2 also shows the results of a reference example in which "(2) formation of copper surface protective layer" (without using composition, etc.) was not performed.

[0214] (Lifting Time and Peelability of Dry Film Resist)

[0215] (1) Substrate preparation

[0216] RD-1225 (manufactured by Showa Denko Materials Co., Ltd., thickness: 25 μm) as a negative dry film resist is laminated onto a copper-clad laminate (manufactured by Mitsubishi Gas Chemical Co., Ltd., "CCL-HL832NS(MT-FL)") serving as the substrate, and the exposed areas are cured by exposure treatment. Next, the unexposed areas are removed with a developer (1 wt% sodium carbonate aqueous solution), resulting in a substrate with a resist pattern. The formed resist pattern is a comb-shaped pattern with a line / space ratio of 20 μm / 20 μm (exposed with parallel lines). Then, copper plating is performed on the substrate exposed by development to construct copper wiring with a thickness of 10 μm. Thus, a substrate having copper wiring (thickness: 10 μm) and resist (thickness: 25 μm) disposed between the copper wiring is manufactured.

[0217] (2) Evaluation of Lifting Time (LT)

[0218] The substrate was cut into 2cm × 2cm pieces and immersed in the composition while stirring at 50°C. The time from the start of immersion to the end of peeling was measured as the lift-off time. It should be noted that "end of peeling" means that the entire surface of the substrate contact area with the resist has been peeled off from the substrate. At this point, the end of peeling is determined visually.

[0219] (3) Evaluation of peelability

[0220] The substrate is stirred and impregnated until the impregnation time in the composition reaches the specified time, and then washed and dried to manufacture the electronic substrate.

[0221] Peelability was evaluated using an optical microscope MX-63L (manufactured by Olympus Corporation) according to the following criteria.

[0222] A: It can be peeled off, and there are no peeling residues.

[0223] B: There are some peeling residues, but it is generally possible to peel them off.

[0224] C: Excessive peeling residue, or inability to peel.

[0225] [Table 2]

[0226]

[0227] As can be seen from the results in Table 2, the compositions of Examples 1 to 15 can appropriately inhibit the oxidation of the copper surface and appropriately remove the resist by protecting the copper surface.

Claims

1. A composition comprising an alkaline compound and a copper surface protectant, The copper surface protectant comprises at least one selected from the group consisting of an ammonium salt of formula (1), a heteroaryl salt having substituted or unsubstituted alkyl groups having 5 to 30 carbon atoms, and a substituted or unsubstituted thiol having 5 to 30 carbon atoms. In equation (1) above, R 1 It is a substituted or unsubstituted alkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl (poly)heteroalkylene group having 5 to 30 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 7 to 30 carbon atoms. R 2 Each is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. X can be a halide ion, hydroxide ion, organic sulfonate ion, tetrafluoroborate anion, or hexafluorophosphate anion. The pH of the composition is above 13.

2. The composition according to claim 1, wherein, The basic compound includes strongly basic compounds.

3. The composition according to claim 2, wherein, The strong base compound includes inorganic strong base compounds.

4. The composition according to claim 2, wherein, The content of the strong basic compound is 3 to 10% of the total mass of the composition.

5. The composition according to claim 2, wherein, The basic compounds also include weakly basic compounds.

6. The composition according to claim 1, wherein, The copper surface protectant comprises heteroaryl salts with substituted or unsubstituted alkyl groups having 8 to 20 carbon atoms.

7. The composition according to claim 6, wherein, The copper surface protectant comprises a pyridinium salt having substituted or unsubstituted alkyl groups having 14 to 20 carbon atoms.

8. The composition according to claim 6, wherein, The copper surface protectant comprises an imidazolium salt having substituted or unsubstituted alkyl groups having 8 to 14 carbon atoms.

9. The composition according to claim 1, wherein, The copper surface protectant contains substituted or unsubstituted thiols with 8 to 20 carbon atoms.

10. The composition according to claim 1, wherein, The content of the copper surface protectant is 0.07 to 0.5% of the total mass of the composition.

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

12. A method for manufacturing an electronic substrate, comprising the steps of: contacting the composition of any one of claims 1 to 11 with a substrate having copper wiring and a resist disposed between the copper wiring to remove the resist, and forming a protective layer on the surface of the copper wiring.

13. A method for removing resist, comprising the steps of: contacting the composition of any one of claims 1 to 11 with a substrate having copper wiring and resist disposed between the copper wiring to remove the resist, and forming a protective layer on the surface of the copper wiring.

14. A kit for use in the method of manufacturing an electronic substrate according to claim 12, wherein, The solution comprises a first solution containing an alkaline compound and a second solution containing a copper surface protectant, in an immiscible state. When using, mix the first solution with the second solution.

15. A kit for use in the resist removal method of claim 13, wherein, The solution comprises a first solution containing an alkaline compound and a second solution containing a copper surface protectant, in an immiscible state. When using, mix the first solution with the second solution.

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