TW202328424A - Method for manufacturing printed wiring board, method for peeling resist, and resist peeling pretreatment liquid used in said methods - Google Patents

Abstract

Provided is a method which is for manufacturing a printed wiring board and by which a resist can be quickly removed. This method for manufacturing a printed wiring board comprises: a pretreatment step for bringing a board, which has metal wirings and a resist disposed between the metal wirings, into contact with a resist peeling pretreatment liquid (A), which contains an oxidizing agent (a), a nitrogen atom-containing chelating agent (b), and water and has a pH of 3-10; and a resist removal step for removing the resist by bringing the board obtained in the pretreatment step into contact with a resist peeling liquid (B), which contains a basic compound ([alpha]), an organic solvent ([beta]), and water.

Description

Manufacturing method of printed wiring board, resist stripping method, and resist stripping pretreatment solution used in these methods

The present invention relates to a method for manufacturing a printed wiring board, a method for stripping a resist, and a pretreatment solution for stripping a resist used in these methods.

In recent years, miniaturization and high functionality of electronic devices have progressed, and miniaturization and high functionality have also been demanded for printed wiring boards used in such electronic devices.

A method using a resist is known as a method of manufacturing a printed wiring board satisfying such a desire. The aforementioned manufacturing method includes, for example, a method comprising the following steps: a coating film forming step of forming a coating film of a photosensitive resin on a substrate; and a process of producing a substrate having a resist by exposing and developing the obtained coating film to pattern it. A patterning step; a metal wiring forming step of forming a metal wiring on the substrate exposed by development by plating or the like to produce a substrate having a resist disposed between the metal wiring and the aforementioned metal wiring; using a stripping liquid to remove the resist Resist removal step for removal.

Regarding the stripping liquid used in the above-mentioned method of manufacturing a printed wiring board, for example, Patent Document 1 describes an invention of a cleaning method comprising the steps of using an alkaline agent (component A), an organic solvent (component B), And water (component C), and the coordinate system of the Hansen solubility parameter of component B falls within the predetermined range, and the electrical conductivity is 11S/m or more, the object to be cleaned from the resin mask The step of peeling off the resin mask.

According to Patent Document 1, it is described to provide a cleaning method excellent in resin mask (resist) removability. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2020/022491

[Problem to be Solved by the Invention]

When removing a resist using a stripping liquid, if a resist can be removed rapidly, the productivity of a printed wiring board will improve. Therefore, a means for rapidly removing the resist is sought. [Means to solve the problem]

The present invention includes, for example, the following aspects.

[1] A method of manufacturing a printed wiring board, comprising the following steps: In the pretreatment step, the substrate having the metal wiring and the resist arranged between the metal wiring is exposed to the resist containing the oxidizing agent (a), the chelating agent (b) containing nitrogen atoms, and water and the pH is 3-10. Pretreatment solution (A); In the resist removal step, the substrate obtained in the pretreatment step is brought into contact with a resist stripping solution (B) containing a basic compound (α), an organic solvent (β), and water to remove the resist. [2] The method for producing a printed wiring board according to [1], wherein the oxidizing agent (a) is selected from the group consisting of hydrogen peroxide, persulfuric acid, permanganic acid, percarbonic acid, perboric acid, percarboxylic acid, and halogenated oxyacids. , their salts, and at least one member of the group consisting of organic peroxides, but the organic peroxides do not include percarboxylic acids and their salts. . [3] The method for producing a printed wiring board according to [1] or [2], wherein the content of the oxidizing agent (a) is 5 to 30% by mass relative to the entire mass of the resist stripping pretreatment liquid (A). [4] The method for producing a printed wiring board according to any one of [1] to [3], wherein the nitrogen-atom-containing chelating agent (b) contains a phosphonic acid-based chelating agent. [5] The method for producing a printed wiring board according to [4], wherein the phosphonic acid-based chelating agent contains diethylenetriaminepentamethylenephosphonic acid and/or 1,2-propylenediaminetetramethylene Phosphonic acid. [6] The method for producing a printed wiring board according to any one of [1] to [5], wherein the content of the nitrogen atom-containing chelating agent (b) is relative to the entire amount of the resist stripping pretreatment liquid (A) The mass is 0.0001 to 0.1 mass%. [7] The method for producing a printed wiring board according to any one of [1] to [6], wherein the resist stripping pretreatment liquid (A) further contains a basic compound (c). [8] The method for producing a printed wiring board according to [7], wherein the basic compound (c) includes an inorganic basic compound. [9] The method for producing a printed wiring board according to any one of [1] to [8], wherein the basic compound (α) contains potassium hydroxide and/or sodium hydroxide. [10] The method for producing a printed wiring board according to any one of [1] to [9], wherein the organic solvent (β) contains glycol ethers. [11] The method for producing a printed wiring board according to any one of [1] to [10], wherein the organic solvent (β) contains a solvent selected from ethylene glycol monoethyl ether, 2-butoxyethanol, and phenylethylene glycol. At least one member selected from the group consisting of (phenyl glycol), propylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and diethylene glycol monophenyl ether. [12] The method for producing a printed wiring board according to any one of [1] to [11], wherein the line/space of the printed wiring board is 50 μm or less/50 μm or less. [13] The method for producing a printed wiring board according to any one of [1] to [12], wherein the resist is a dry thin film resist. [14] The method for producing a printed wiring board according to any one of [1] to [13], wherein the metal wiring contains Cu and/or Co. [15] A resist stripping method, comprising the following steps: In the pretreatment step, the substrate having the metal wiring and the resist arranged between the metal wiring is exposed to the resist containing the oxidizing agent (a), the chelating agent (b) containing nitrogen atoms, and water and the pH is 3-10. Pretreatment solution (A); In the resist removal step, the substrate obtained in the pretreatment step is brought into contact with a resist stripping solution (B) containing a first basic compound (α), an organic solvent (β), and water to remove the resist. [16] A pretreatment solution for resist stripping, which is a pretreatment solution for resist stripping used before stripping the resist from a substrate having metal wiring and a resist disposed between the metal wirings using a resist stripping solution (A ), which is characterized by: comprising an oxidizing agent (a), a nitrogen-containing chelating agent (b), and water, and The pH is 3~10. [17] The pretreatment solution for resist stripping as described in [16], wherein the oxidizing agent (a) contains a compound selected from the group consisting of hydrogen peroxide, persulfuric acid, permanganic acid, percarbonic acid, perboric acid, percarboxylic acid, and halogen oxyacids. , their salts, and at least one member of the group consisting of organic peroxides. [18] The resist stripping pretreatment liquid according to [16] or [17], wherein the content of the oxidizing agent (a) is 5 to 30% by mass relative to the total mass of the resist stripping pretreatment liquid (A). [19] The resist stripping pretreatment solution according to any one of [16] to [18], wherein the nitrogen-atom-containing chelating agent (b) includes a phosphonic acid-based chelating agent. [20] The resist stripping pretreatment solution according to [19], wherein the phosphonic acid-based chelating agent contains diethylenetriaminepentamethylenephosphonic acid and/or 1,2-propylenediaminetetramethylene Phosphonic acid. [21] The resist stripping pretreatment solution according to any one of [16] to [20], wherein the content of the nitrogen atom-containing chelating agent (b) is relative to the entire resist stripping pretreatment solution (A) The mass is 0.0001 to 0.1 mass%. [22] The resist stripping pretreatment solution according to any one of [16] to [21], further comprising a basic compound (c). [23] The resist stripping pretreatment solution according to [22], wherein the basic compound (c) contains an inorganic basic compound. [24] The resist stripping pretreatment solution according to any one of [16] to [23], wherein the metal wiring width/resist width of the substrate is 50 μm or less/50 μm or less. [25] The resist stripping pretreatment solution according to any one of [16] to [24], wherein the resist is a dry thin film resist. [26] The resist stripping pretreatment solution according to any one of [16] to [25], wherein the metal wiring contains Cu and/or Co. [Effect of Invention]

According to this invention, the manufacturing method of the printed wiring board which can remove a resist rapidly, etc. are provided.

Hereinafter, the form for carrying out this invention is demonstrated in detail.

＜Manufacturing method of printed wiring board＞ The manufacturing method of the printed wiring board of the present invention includes the following steps: a pretreatment step, making the substrate with metal wiring and the resist disposed between the aforementioned metal wirings contact the chelating agent (b) containing oxidant (a) and nitrogen atoms , and water and a resist stripping pretreatment solution (A) with a pH of 3 to 10; the resist removal step is to make the substrate obtained in the aforementioned pretreatment step contact with a basic compound (α), an organic solvent (β), and Water resist stripping solution (B) to remove the aforementioned resist.

When removing the resist using a resist stripping solution, it may be difficult for the resist stripping solution to penetrate into the resist, and the resist removal ability of the resist stripping solution may be insufficient, and the removal of the resist may take time. As a result, the productivity of a printed wiring board may fall. In contrast, if the pretreatment step of making the resist stripping pretreatment solution (A) contact the resist is performed, the properties of the resist, especially the surface portion of the resist, can be changed. In terms of the change in the aforementioned properties, examples include cutting off the cross-linkage of the inhibitor, and changing the hydrophobic group to a hydrophilic group. Also, if the resist removal step of bringing the resist stripping solution (B) into contact with the resist is performed after the pretreatment step, the stripping solution easily penetrates into the resist because the state of the resist changes in the pretreatment step. , and/or the resist stripping ability of the stripping solution can still remove the resist even if it is not sufficient. As a result, if the resist stripping solution (B) is brought into contact with the resist, the resist can be quickly removed.

[Preprocessing steps] The pretreatment step is to make the substrate with the metal wiring and the resist arranged between the metal wirings contact the resist containing the oxidizing agent (a), the chelating agent (b) containing nitrogen atoms, and water with a pH of 3-10 The step of stripping the pretreatment solution (A).

(substrate) The substrate has metal wiring and a resist disposed between the metal wiring.

There are no particular limitations on the substrate, and examples include resin substrates (substrates formed by impregnating paper, glass, etc. ; Specifically, paper phenol substrate, paper epoxy substrate, Teflon substrate, glass epoxy resin substrate, etc.), silicon substrate, silicon carbide substrate, sapphire substrate, gallium phosphide (GaP) substrate, gallium arsenide (GaAs ) substrates, indium phosphide (InP) substrates, gallium nitride (GaN) substrates, etc. Among these, the substrate is preferably a resin substrate or a silicon substrate.

In addition, the pattern that can be formed on the substrate is generally formed based on the pattern design made according to the application, required performance, and the like. In addition, the patterns that can be formed on the substrate can also be comb-shaped patterns (also known as "straight and space patterns" that form metal wiring in parallel lines), dot-shaped patterns (also known as "columnar patterns") A pattern in which metal wiring is formed in a bead shape) and the like. In addition, the method of patterning process uses a well-known method suitably.

Metal wiring The metal wiring is not particularly limited, and examples thereof include aluminum (Al), copper (Cu), cobalt (Co), and combinations thereof. Among these, the metal wiring is preferably Cu, Al, Co, and combinations thereof, and is more preferably Cu and/or Co. That is, in a more desirable embodiment, the metal wiring contains Cu and/or Co.

The metal wiring width is preferably 50 μm or less, more preferably 30 μm or less, more preferably 20 μm or less, and particularly preferably less than 15 μm. There is no particular limitation on the lower limit of the metal wiring width, but it is preferably at least 1 μm, more preferably at least 3 μm, and even more preferably at least 5 μm. If the metal wiring width is 50 μm or less, it is preferable because a miniaturized printed wiring board can be produced. In addition, in this specification, the "metal wiring width" refers to the minimum length among the widths of the metal wiring when the metal wiring is formed into a straight line by patterning with a comb-shaped pattern or the like. In this case, the metal wiring width is an average value of any 30 metal wiring widths. In addition, the metal wiring width is also called a line (line).

The dot diameter of the metal wiring is not particularly limited, but is preferably 800 μm or less, more preferably 10-600 μm, more preferably 50-500 μm, and particularly preferably 100-300 μm. If the dot diameter of the metal wiring is 800 μm or less, it is preferable because a miniaturized printed wiring board can be produced. In addition, in this specification, the "dot diameter of the metal wiring" refers to the outermost surface (substrate contact surface) of the metal wiring (cylindrical shape) when the metal wiring is formed into a cylindrical shape by patterning into a dot pattern or the like. The diameter of the opposite face of the face). In this case, the so-called "diameter" refers to the largest distance between two points on the outer edge of the circle. In addition, the dot diameter of the metal wiring is an average value of the dot diameters of arbitrary 30 metal wirings.

The thickness of the metal wiring is not particularly limited, but it is more preferably 1 μm or more, more preferably 5-50 μm, and more preferably 10-30 μm. If the thickness of the metal wiring is 1 μm or more, it is preferable because the resistance of the printed wiring board can be reduced. In addition, in this specification, the "thickness of the metal wiring" refers to the longest distance between the substrate contact surface of the metal wiring and the outermost surface of the metal wiring (the surface opposite to the substrate contact surface). At this time, the thickness of the metal wiring is an average value of the thicknesses of 30 arbitrary metal wirings.

Resist placed between metal wiring Examples of the aforementioned resist include dry film resists, liquid resists, and the like. Among these, the resist is preferably a dry film resist.

The dry film resist is not particularly limited, but it is preferably formed of a photosensitive resin. As said photosensitive resin, a negative photosensitive resin and a positive photosensitive resin are mentioned, for example.

The negative photosensitive resin is not particularly limited, but examples thereof include azide-based photosensitive resins, disazo-based photosensitive resins, acetylene-based low-molecular-weight photosensitive resins, and ethylene-based low-molecular-weight photosensitive resins. , Insoluble polymer photosensitive resin, chromic acid photosensitive resin. These negative photosensitive resins may be used alone or in combination of two or more.

The positive-type photosensitive resin is not particularly limited, and examples thereof include quinonediazide-based photosensitive resins, solubilized polymer-based photosensitive resins, and the like. These positive photosensitive resins may be used alone or in combination of two or more.

Among these, dry film resists are preferably formed of negative photosensitive resins. Thereby, the effects of the present invention can be more effectively exerted. Specifically, since the negative photosensitive resin is hardened by the exposure treatment during pattern formation and becomes insoluble in the developer solution, the exposed part (the part where the negative photosensitive resin is hardened) will be treated as a dry film resist. form remains. Here, during exposure, the hardening of the negative photosensitive resin, especially the surface portion exposed to exposure, is easy to proceed, and the surface portion of the obtained dry film resist will have a particularly dense structure. Therefore, even if the dry film resist is intended to be removed with a stripping liquid, it may be difficult for the stripping liquid to penetrate into the dry film resist. Moreover, since the resist removal ability by the stripping liquid is not sufficient, it may not be possible to remove the dry thin film resist. As a result, the removal of dry film resists can be time-consuming. On the other hand, in this embodiment, by performing the pretreatment step, the properties of the surface of the dry film resist are changed. As a result, the stripping liquid easily penetrates into the dry film resist, and the dry film resist is quickly removed, so that the dry film resist can be quickly removed.

The resist width is preferably 50 μm or less, more preferably 30 μm or less, more preferably 20 μm or less, and particularly preferably less than 15 μm. The lower limit of the resist width is not particularly limited, but it is more preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more. If the resist width is 50 μm or less, it is preferable because a miniaturized printed wiring board can be produced. In addition, in this specification, the "resist width" means the minimum length among the widths of the resist when the resist is formed in a linear shape by patterning with a comb-shaped pattern or the like. In this case, the resist width is an average value of any 30 resist widths.

The metal wiring width/resist width of the substrate is preferably 50 μm or less/50 μm or less, more preferably 30 μm or less/30 μm or less, more preferably 20 μm or less/20 μm or less, and 3~15 μm/3~15 μm is particularly ideal. If the metal wiring width/resist width of the substrate is 50 μm or less/50 μm or less, it is preferable because a miniaturized printed wiring board can be produced.

(Resist stripping pre-treatment solution (A)) The resist stripping pretreatment solution (A) includes an oxidizing agent (a), a nitrogen atom-containing chelating agent (b), and water. The resist stripping pretreatment solution (A) may further include other chelating agents, basic compounds (c), and organic solvents.

The pH of the resist stripping pre-treatment solution (A) is 3-10, considering that the resist can be removed quickly, it is more ideally 5-10, and more preferably 8-10. In addition, in one embodiment, the pH of the resist stripping pretreatment solution (A) is preferably 3-7, more preferably 3-5, in consideration of increasing the stability of the oxidizing agent (a).

Oxidant (a) The oxidizing agent (a) has the function of changing the properties of the resist (preferably, the surface portion of the resist), and the like. At this time, the change of the above-mentioned properties includes, for example, the cleavage of the cross-linkage bond of the inhibitor, and the conversion of the hydrophobic group to the hydrophilic group.

The oxidizing agent (a) is not particularly limited, but includes those selected from hydrogen peroxide, persulfuric acid, permanganic acid, percarbonic acid, perboric acid, percarboxylic acid, halogen oxyacids, and their salts, and organic At least one member of the group consisting of peroxides (excluding percarboxylic acids and their salts) is preferred.

The aforementioned percarboxylic acid is not particularly limited, but examples thereof include peracetic acid, perbenzoic acid, m-chloroperoxybenzoic acid, and the like.

The aforementioned halogen oxyacids are not particularly limited, but examples include chlorine oxyacids such as hypochlorous acid, chlorous acid, chloric acid, and perchloric acid; hypobromous acid, bromic acid, bromic acid, etc. , perbromic acid and other bromine oxyacids;

As far as the salt of the aforementioned oxidant (a) is concerned, there is no particular limitation, but examples include alkali metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, and cesium salts of the aforementioned oxidant (a); beryllium salts of the aforementioned oxidant , magnesium salt, calcium salt, strontium salt, barium salt and other alkaline earth metal salts; aluminum salts, copper salts, zinc salts, silver salts and other metal salts of the aforementioned oxidizing agents; ammonium salts of the aforementioned oxidizing agents, etc.

The aforementioned organic peroxides are not particularly limited as long as they are percarboxylic acids and their salts, but examples include benzoyl peroxide, lauryl peroxide, butyl peroxide, and amyl peroxide. Such as alkyl peroxyesters, peroxycarbonates, alkyl hydroperoxides, diacyl peroxides, etc.

Among these, the oxidizing agent (a) includes those selected from the group consisting of hydrogen peroxide, persulfuric acid, permanganic acid, percarbonic acid, perboric acid, percarboxylic acid, halogen oxyacids, and salts thereof It is preferably at least one, more preferably at least one selected from hydrogen peroxide, halogen oxyacids, and salts thereof, more preferably hydrogen peroxide. Moreover, the said oxidizing agent (a) may be used individually, and may use it in combination of 2 or more types.

The content of the oxidizing agent is preferably 5 to 30% by mass, more preferably 10 to 20% by mass, based on the total mass of the resist stripping pretreatment solution (A). When the content of the oxidizing agent falls within the above range, it is preferable because the resist can be stripped quickly.

Nitrogen-containing chelating agent (b) The nitrogen atom-containing chelating agent (b) has the function of maintaining the stability of the oxidizing agent (a), etc.

There are no particular limitations on the aforementioned nitrogen-containing chelating agent (b), but examples include aminocarboxylic acid-based chelating agents, phosphonic acid-based chelating agents, and their ammonium salts, metal salts, organic alkali salts, etc. .

There are no particular limitations on the aforementioned aminocarboxylic acid-based chelating agents, but examples include ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), dihydroxyethylethylenediaminetetra Acetic acid (DHEDDA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraaminehexaacetic acid (TTNA), nitrogen triacetic acid (NTA), hydroxyethyliminodiacetic acid (HIMDA), etc.

There are no particular limitations on the aforementioned phosphonic acid-based chelating agents, but examples include amino trimethylene phosphonic acid, ethyl amino dimethylene phosphonic acid, dodecyl amino dimethylene phosphonic acid, , ethylenediaminedimethylphosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid (DTPP), 1,2 - propane diamine tetramethylene phosphonic acid (PDTP) and the like.

For the ammonium salt, metal salt, and organic alkali salt of the aforementioned chelating agent (b) containing nitrogen atoms, ammonium salts, sodium salts, potassium salts, calcium salts, Triethylamine salt, etc.

Among these, the nitrogen atom-containing chelating agent (b) considers the viewpoint of making the stability of the oxidizing agent (a) higher, and it is more desirable to include a phosphonic acid-based chelating agent, including diethylenetriaminepentamethylenephosphonic acid ( DTPP) and/or 1,2-propanediaminetetramethylenephosphonic acid (PDTP) are more desirable. Moreover, the said nitrogen atom containing chelating agent (b) may be used individually, and may use it in combination of 2 or more types.

The content of the nitrogen atom-containing chelating agent (b) is preferably 0.0001-0.1% by mass, more preferably 0.0001-0.03% by mass, and 0.0003-0.01% by mass relative to the total mass of the resist stripping pretreatment solution (A) Even more ideal. If the content of the nitrogen atom-containing chelating agent (b) falls within the above range, the corrosion rate to the metal wiring can be reduced, and the corrosion of the metal wiring in the pretreatment step can be prevented or suppressed, so it is ideal.

other chelating agents The pretreatment solution (A) for resist stripping may further contain other chelating agents. In this case, other chelating agents refer to chelating agents other than the nitrogen atom-containing chelating agent (b). Other chelating agents are not particularly limited, but examples include phosphonic acid-based chelating agents not containing nitrogen atoms, inorganic chelating agents, their ammonium salts, metal salts, and organic alkali salts.

There are no particular limitations on the aforementioned phosphonic acid chelating agents that do not contain nitrogen atoms, but examples include methyl diphosphonic acid, ethylene diphosphonic acid, hydroxyethylene diphosphonic acid, 1-hydroxypropylene diphosphonic acid, Base-1,1-diphosphonic acid, nitrilo trimethylene phosphonic acid, etc.

The inorganic chelating agent is not particularly limited, but examples thereof include metaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, and tripolyphosphoric acid.

Ammonium salts, metal salts, and organic bases of other chelating agents include, for example, ammonium salts, sodium salts, potassium salts, calcium salts, and triethylamine salts of other chelating agents.

The above-mentioned other chelating agents may be used alone or in combination of two or more.

The content of other chelating agents is preferably 0.1% by mass or less, more preferably 0.03% by mass or less, and even more preferably 0.0001 to 0.01% by mass relative to the total mass of the resist stripping pretreatment solution (A).

Basic compound (c) The resist stripping pretreatment solution (A) may further contain a basic compound (c). The basic compound (c) has the function of adjusting the pH of the resist stripping pretreatment liquid (A). The resist stripping pretreatment solution (A) contains the oxidizing agent (a) and the chelating agent (b) containing nitrogen atoms, so the liquid acidity and alkalinity of the resist stripping pretreatment solution (A) becomes acidic (pH less than 7) tendency. The pH can be adjusted by adding the basic compound (c) to the resist stripping pretreatment liquid (A). In addition, at the pH of the pre-resist stripping treatment solution (A), the removal of the resist by the basic compound (c) does not occur or hardly occurs.

The basic compound (c) is not particularly limited, and examples thereof include inorganic base compounds and organic base compounds.

As far as the inorganic alkali compound is concerned, there is no particular limitation, but examples include alkali metal compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and potassium silicate; magnesium hydroxide, Calcium hydroxide, magnesium carbonate, calcium carbonate, calcium silicate, magnesium silicate and other alkaline earth metal compounds; copper hydroxide, iron hydroxide and other transition metal compounds; ammonia, etc.

The organic base compound is not particularly limited, but examples include compounds containing nitrogen atoms such as triethylamine, diazabicycloundecene (DBU), and diazabicyclononene (DBN).

Among these, the basic compound (c) preferably includes an inorganic basic compound, more preferably an alkali metal compound, and more preferably includes sodium hydroxide and/or potassium hydroxide. Moreover, the said basic compound (c) may be used individually, and may use it in combination of 2 or more types.

The content of the basic compound (c) is not particularly limited, and it is desirable to add it in an amount to obtain a desired pH.

In addition, from the viewpoint of pH control, acidic compounds (hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid, etc.) can also be used.

water Water functions as a medium for the oxidizing agent (a) and the nitrogen atom-containing chelating agent (b).

The content of water is preferably 70 to 95% by mass, more preferably 80 to 95% by mass, based on the total mass of the resist stripping pretreatment liquid (A).

Organic solvents The pretreatment solution (A) for resist stripping may further contain an organic solvent. The organic solvent has a function of improving wettability with respect to the resist, and the like.

The organic solvent is not particularly limited, but examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, tert-butanol, 1-pentanol, 1-hexanol, 1- Heptanol, 1-octanol, 1-nonanol, 1-decanol and other unit alcohols; ethylene glycol, propylene glycol, neopentyl glycol, 1,2-hexanediol, 1,6-hexanediol, 2 -Ethylhexane-1,3-diol and other diols; glycerin and other polyols; dimethyl ether, diethyl ether, tetrahydrofuran, 1,4-dioxane and other ethers; ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol n-butyl ether (2-butoxyethanol), ethylene glycol monophenyl ether (phenyl glycol), propylene glycol monomethyl ether, propylene glycol mono Diethyl 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 mono Methyl 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 and other glycol ethers; two Amides such as methylformamide, diethylformamide, dimethylacetamide, and N-methylpyrrolidone; heterocyclic compounds such as pyrrole, pyridine, and triazole, etc. Among these, it is desirable that the organic solvent contains glycol ethers selected from the group consisting of ethylene glycol monoethyl ether, 2-butoxyethanol, phenyl glycol, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, At least one selected from the group consisting of ethylene glycol monobutyl ether and diethylene glycol monophenyl ether is more preferable. Moreover, the said organic solvent may be used individually, and may use it in combination of 2 or more types.

The content of the organic solvent is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less, based on the total mass of the resist stripping pretreatment solution (A). The lower limit of the content of the organic solvent is not particularly limited, but, for example, is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the entire mass of the resist stripping pretreatment liquid (A).

(touch) In a pretreatment process, the said board|substrate which has the resist arrange|positioned between metal wiring and the said metal wiring is brought into contact with resist stripping pretreatment liquid (A). Thereby, the properties of the resist on the substrate, especially the surface portion of the resist, can be changed. As a result, the resist can be quickly removed in the resist removal step described later.

The contact method is not particularly limited, and known techniques can be appropriately used. Specifically, the substrate may be immersed in the resist peeling pretreatment liquid (A), or the resist peeling pretreatment liquid (A) may be sprayed or dripped (single-wafer spin treatment, etc.) on the substrate. At this time, the aforementioned immersion may be repeated two or more times, the spraying may be repeated two or more times, the dripping may be repeated two or more times, and dipping, spraying, and dripping may be combined.

The contact temperature is not particularly limited, but is preferably 0 to 90°C, more preferably 15 to 70°C, and more preferably 20 to 60°C.

The contact time is not particularly limited, but is preferably 10 seconds to 1 hour, more preferably 15 seconds to 30 minutes, even more preferably 30 seconds to 15 minutes, and particularly preferably 1 minute 30 seconds to 10 minutes. If the contact time is 10 seconds or more, it is preferable from the viewpoints that the resist removal in the resist removal step can be rapidly performed and the resist removal ability becomes higher. On the other hand, when the contact time is 1 hour or less, it is preferable because the production cost will be reduced.

[Resist removal procedure] The resist removal step is a step of removing the resist by bringing the substrate obtained in the pretreatment step into contact with a resist stripping solution (B) containing a basic compound (α), an organic solvent (β), and water. By performing the resist removal step after the pretreatment step, the resist can be quickly removed in the resist removal step.

(substrate) The substrate is the substrate obtained in the pretreatment step. The specific constitution is the same as that described in the preprocessing step. However, in the substrate, at least a part of the surface of the resist included in the substrate has a property change. In addition, sometimes a portion of the resist has been removed from the substrate.

(Resist stripper (B)) The resist stripping solution (B) contains a basic compound (α), an organic solvent (β), and water. Others may further include a corrosion inhibitor and the like.

The pH of the resist stripping solution (B) is preferably 12 or higher, more preferably 13 or higher.

Basic compound (α) The basic compound (α) has a function of promoting the removal of the resist. For example, the basic compound (α) will change the liquid acidity and alkalinity of the resist stripping solution (B) into alkaline, and dissolve the alkaline soluble resin constituting the resist in the resist stripping solution (B), thereby making the substrate- The adhesive force between resins falls, and a resist is removed from a board|substrate.

The basic compound (α) is not particularly limited, and examples thereof include inorganic basic compounds and organic basic compounds.

As far as the aforementioned inorganic alkaline compounds are concerned, there are no particular limitations, but examples 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, calcium hydroxide, magnesium carbonate, calcium carbonate, calcium silicate, and magnesium silicate; transition metal compounds such as copper hydroxide and iron hydroxide; ammonia, etc.

There are no particular limitations on the aforementioned organic basic compounds, but examples include quaternary ammonium compounds represented by the following formula (1), and tertiary amine compounds represented by the following formula (2) or (3).

[chemical 1]

In the above formula, R ¹ are each independently, for example, an alkyl group having 1 to 6 carbons, and a hydroxyalkyl group having 1 to 6 carbons.

R ² is a hydrogen atom, an alkyl group with 1 to 6 carbons, or an aminoalkyl group with 1 to 6 carbons. Also, R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbons, or a hydroxyalkyl group having 1 to 6 carbons. Also, R ⁴ is a hydroxyalkyl group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms.

R ⁵ is an alkyl group with 1 to 6 carbons, a hydroxyalkyl group with 1 to 6 carbons, or an aminoalkyl group with 1 to 6 carbons. Also, p is an integer of 1 or more, preferably 1 to 6, more preferably 2 or 3.

Here, examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.

Examples of hydroxyalkyl groups having 1 to 6 carbon atoms include hydroxymethyl groups, hydroxyethyl groups, and hydroxypropyl groups.

Examples of aminoalkyl groups having 1 to 6 carbon atoms include aminomethyl groups, aminoethyl groups, aminopropyl groups, and aminobutyl groups.

Specific examples of the compound represented by the formula (1) include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylhydroxide Ammonium Hydroxide (Choline), 2-Hydroxyethyltriethylammonium Hydroxide, 2-Hydroxyethyltripropylammonium Hydroxide, 2-Hydroxypropyltrimethylammonium Hydroxide, 2-Hydroxypropyltriethylammonium Hydroxide Ammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropyl Bis(2-hydroxyethyl)ammonium hydroxide, ginseng(2-hydroxyethyl)methylammonium hydroxide, ginseng(2-hydroxyethyl)ethylammonium hydroxide, ginseng(2-hydroxyethyl)propyl Ammonium hydroxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, tetrakis(2-hydroxypropyl)ammonium hydroxide and the like.

Specific examples of the compound represented by formula (2) include monoethanolamine, monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N -Ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine Alcoholamine, 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.

Specific examples of the compound represented by the formula (3) include, for example, 1-methylpiperone, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperone, and the like.

Among these, the basic compound (α) preferably includes an inorganic basic compound and/or a compound represented by the formula (1), and it is more preferable to include an inorganic basic compound from the viewpoint of reducing the environmental load of the waste liquid. Potassium and/or sodium hydroxide are more desirable. In addition, inorganic basic compounds have relatively low affinity for resists compared with organic basic compounds, and there may be cases where the ability to remove resists is insufficient. However, inorganic basic compounds can be ideally used by performing a pretreatment step. basic compound. Moreover, the said basic compound (α) may be used individually, and may use it in combination of 2 or more types.

The content of the basic compound (α) is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the entire mass of the resist stripping solution (B).

Organic solvent (β) The organic solvent (β) has a function of promoting the removal of the resist. For example, the organic solvent (β) allows the basic compound (α) and water to penetrate into the inside of the resist due to its fat solubility, and also reduces the adhesion between the substrate and the resin to remove the resist.

The organic solvent (β) is not particularly limited, but examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, tert-butanol, 1-pentanol, 1-hexane Alcohol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol and other monoalcohols; ethylene glycol, propylene glycol, neopentyl glycol, 1,2-hexanediol, 1,6-hexane Glycol, 2-ethylhexane-1,3-diol and other diols; glycerin and other polyols; dimethyl ether, diethyl ether, tetrahydrofuran, 1,4-dioxane and other ethers; ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol n-butyl ether (2-butoxyethanol), ethylene glycol monophenyl ether (phenyl glycol), propylene glycol monomethyl ether 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 and other diols Ethers; amides such as dimethylformamide, diethylformamide, dimethylacetamide, and N-methylpyrrolidone; heterocyclic compounds such as pyrrole, pyridine, and triazole, etc. Among these, the organic solvent (β) preferably contains glycol ethers selected from the group consisting of ethylene glycol monoethyl ether, 2-butoxyethanol, phenylglycol, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, More preferably, at least one selected from the group consisting of diethyl ether, diethylene glycol monobutyl ether, and diethylene glycol monophenyl ether. Moreover, the said organic solvent ((beta)) may be used individually or in combination of 2 or more types.

The content of the organic solvent (β) is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, more preferably 1 to 10% by mass based on the total mass of the resist stripping solution (B).

water Water has the function of promoting the removal of resist. For example, water will change the structure of the resist by dissolving the alkali-soluble resin, and reduce the adhesion between the substrate and the resin, so that the resist can be removed from the substrate.

The content of water is preferably 70 to 95% by mass, more preferably 80 to 95% by mass, based on the total mass of the resist stripping solution (B).

(touch) In the resist removal step, the resist is removed by contacting the substrate obtained in the pretreatment step with a resist stripping solution (B). Thereby, a resist can be removed, and the printed wiring board patterned by metal wiring can be obtained. In this case, by performing the pretreatment step, the resist can be quickly removed in the resist removal step.

The contact method is not particularly limited, and known techniques can be appropriately used. Specifically, the substrate may be immersed in the resist stripping solution (B), the resist stripping solution (B) may be sprayed on the substrate, or may be dripped (single-wafer spin processing, etc.) on the substrate. At this time, the aforementioned immersion may be repeated two or more times, the spraying may be repeated two or more times, the dripping may be repeated two or more times, and dipping, spraying, and dripping may be combined.

The contact temperature is not particularly limited, but is preferably 0 to 90°C, more preferably 15 to 70°C, and more preferably 20 to 60°C.

The contact time is not particularly limited, but is preferably 1 second to 30 minutes, more preferably 15 seconds to 10 minutes, more preferably 20 seconds to 8 minutes, particularly preferably 25 seconds to 7 minutes, and 45 seconds to 45 seconds. 6 minutes is extremely ideal, and 1 to 5 minutes is the most ideal. If the contact time is 1 second or more, it is preferable because the resist can be removed with a high peeling rate. On the other hand, if the contact time is 30 minutes or less, the production cost will be lowered, so it is preferable.

The resist stripping time in the resist removal step is preferably 60 seconds or less, more preferably 40 seconds or less, more preferably 30 seconds or less, particularly preferably 20 seconds or less. By performing the pretreatment step, the resist stripping solution (B) can quickly penetrate into the inside of the resist, so the stripping of the resist will occur faster. In addition, in this specification, a "lifting time (lifting time)" means the time from immersing a board|substrate in resist stripping liquid (B) to the time from the end of peeling.

[Printed Wiring Board] The printed wiring board includes a substrate and metal wiring arranged on the substrate.

At this time, the metal wiring reflects the shape of the metal wiring formed on the substrate before the preprocessing step.

The substrate, the type of metal wiring, the width (line) of metal wiring, the dot diameter of metal wiring, and the thickness of metal wiring are as above.

In the printed wiring board, the surface of the substrate can be exposed by removing the resist. For example, in a comb pattern (line and space pattern), the exposed portion (resist removed portion) of the substrate is called a space.

A wider spacer will reflect a wider resist. That is, the interval 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. The lower limit of the space width is not particularly limited, but it is preferably 1 μm or more, more preferably 3 μm or more, and more preferably 5 μm or more. In addition, in this specification, the "space width" refers to the minimum length among the widths of the spaces when the spaces are formed linearly by patterning into a comb-tooth pattern or the like. In this case, the interval width is an average value of 30 arbitrary interval widths.

The line/interval of the printed wiring board is preferably 50 μm or less/50 μm or less, more preferably 30 μm or less/30 μm or less, more preferably 20 μm or less/20 μm or less, and 3~15 μm/3~15 μm is particularly ideal. If the line/space of a printed wiring board is 50 micrometers or less/50 micrometers or less, since miniaturization and high functionality of an electronic device can be achieved, it is preferable.

＜Resist stripping method＞ According to one aspect of this invention, the peeling method of a resist is provided. The stripping method of the aforementioned resist includes the following steps: making the substrate having the metal wiring and the resist arranged between the aforementioned metal wiring contact the oxidizing agent (a), the chelating agent (b) containing nitrogen atoms, and water with a pH of 3 ~10 Pretreatment step of the resist stripping pretreatment solution (A); make the substrate obtained in the above pretreatment step contact the resist stripping solution containing the first basic compound (α), organic solvent (β), and water (B) A resist removal step for removing the aforementioned resist.

By the aforementioned stripping method, the resist can be quickly removed. Moreover, by the above-mentioned stripping method, there is an effect that the resist can be removed at a high stripping rate.

The pretreatment step, the resist removal step, and the like are as described above.

＜Pretreatment solution for resist stripping＞ According to an aspect of the present invention, there is provided a resist stripping pretreatment liquid used before stripping a resist from a substrate having a metal wiring and a resist arranged between the metal wirings using a resist stripping liquid. The aforementioned resist stripping pretreatment solution includes an oxidizing agent (a), a nitrogen atom-containing chelating agent (b), and water. Also, the pH of the aforementioned resist stripping pretreatment solution is 3-10.

The resist stripping pre-treatment liquid, in terms of the pre-treatment steps before the resist removal, acts on the substrate having the metal wiring and the resist disposed between the metal wirings, and the resist stripping liquid can be used to remove the resist. Remove the resist quickly when removing it. In addition, the resist can be removed at a high stripping rate; the oxidizing agent (a) does not decompose, or hardly decomposes, but has high storage stability; does not corrode metal wiring, or hardly corrodes, but has high stability Wait for at least 1 effect.

The composition and the like of the pre-treatment solution for resist stripping are as above. [Example]

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples.

＜Pretreatment solution (A)＞ [Example 1-1] Prepare the pre-treatment solution for resist stripping. Specifically, hydrogen peroxide, which is an oxidizing agent (a), diethylenetriaminepentamethylenephosphonic acid (DTPP), which is a chelating agent containing nitrogen atoms (b), and water are mixed to prepare a resist stripping agent. Pretreatment solution. At this time, the contents of hydrogen peroxide and DTPP were 20% by mass and 0.005% by mass, respectively, with respect to the entire mass of the resist stripping pretreatment liquid. Also, the pH of the resist stripping pretreatment liquid was measured and found to be 4.

[Example 1-2] Prepare the pre-treatment solution for resist stripping. Specifically, the content of DTPP was prepared in the same manner as in Example 1-1 except that DTPP was used in an amount of 0.0005% by mass relative to the total mass of the resist stripping pretreatment liquid. Pretreatment solution for resist stripping. In addition, the pH of the pretreatment solution for resist stripping was 4.

[Example 1-3] Prepare the pre-treatment solution for resist stripping. Specifically, the content of DTPP was prepared in the same manner as in Example 1-1 except that DTPP was used in an amount of 0.05% by mass relative to the total mass of the resist stripping pretreatment liquid. Pretreatment solution for resist stripping. In addition, the pH of the pretreatment solution for resist stripping was 4.

[Example 1-4] Prepare the pre-treatment solution for resist stripping. Specifically, the resist stripping pretreatment liquid was prepared in the same manner as in Example 1-1 except that sodium hydroxide was added so that the pH of the resist stripping pretreatment liquid became 7. In addition, the pH of the resist stripping pretreatment liquid was 7.

[Example 1-5] Prepare the pre-treatment solution for resist stripping. Specifically, the content of hydrogen peroxide was used in an amount of 15% by mass with respect to the total mass of the resist stripping pretreatment liquid, and the content of hydrogen peroxide was the same as in Examples 1-4 except that. Prepare the pre-treatment solution for resist stripping in the same way. In addition, the pH of the resist stripping pretreatment liquid was 7.

[Example 1-6] Prepare the pre-treatment solution for resist stripping. Specifically, the content of hydrogen peroxide was used in an amount of 10% by mass relative to the total mass of the resist stripping pretreatment liquid, and the same method as in Examples 1-4 was used except that Prepare the pre-treatment solution for resist stripping in the same way. In addition, the pH of the resist stripping pretreatment liquid was 7.

[Example 1-7] Prepare the pre-treatment solution for resist stripping. Specifically, the content of DTPP was prepared in the same manner as in Example 1-4 except that DTPP was used in an amount of 0.0005% by mass relative to the total mass of the resist stripping pretreatment liquid. Pretreatment solution for resist stripping. In addition, the pH of the resist stripping pretreatment liquid was 7.

[Example 1-8] Prepare the pre-treatment solution for resist stripping. Specifically, the content of DTPP was prepared in the same manner as in Example 1-4 except that DTPP was used in an amount of 0.05% by mass relative to the total mass of the resist stripping pretreatment liquid. Pretreatment solution for resist stripping. In addition, the pH of the resist stripping pretreatment liquid was 7.

[Example 1-9] Prepare the pre-treatment solution for resist stripping. Specifically, except that 1,2-propanediaminetetramethylenephosphonic acid (PDTP) was used instead of DTPP, the resist stripping pretreatment liquid was prepared in the same manner as in Examples 1-4. In addition, the pH of the resist stripping pretreatment liquid was 7.

[Example 1-10] Prepare the pre-treatment solution for resist stripping. Specifically, except that ethylenediaminetetraacetic acid (EDTA) was used instead of DTPP, the resist stripping pretreatment liquid was prepared in the same manner as in Examples 1-4. In addition, the pH of the resist stripping pretreatment liquid was 7.

[Example 1-11] Prepare the pre-treatment solution for resist stripping. Specifically, except that diethylenetriaminepentaacetic acid (DTPA) was used instead of DTPP, the resist stripping pretreatment liquid was prepared in the same manner as in Examples 1-4. In addition, the pH of the resist stripping pretreatment liquid was 7.

[Example 1-12] Prepare the pre-treatment solution for resist stripping. Specifically, the resist stripping pretreatment liquid was prepared in the same manner as in Example 1-1 except that sodium hydroxide was added so that the pH of the resist stripping pretreatment liquid became 9. In addition, the pH of the pretreatment solution for resist stripping was 9.

[Comparative Example 1-1] Prepare the pre-treatment solution for resist stripping. Specifically, except that DTPP was not added, a resist stripping pretreatment liquid was prepared in the same manner as in Examples 1-4. In addition, the pH of the resist stripping pretreatment liquid was 7.

[Comparative example 1-2] Prepare the pre-treatment solution for resist stripping. Specifically, except that 1-hydroxyethane-1,1-diphosphonic acid (HEDP) was used instead of DTPP, the resist stripping pretreatment liquid was prepared in the same manner as in Examples 1-4. In addition, the pH of the resist stripping pretreatment liquid was 7.

The resist stripping pretreatment solutions prepared in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-2 are shown in Table 1 below.

[Table 1] Oxidant (a) Chelating agent (b) Pretreatment solution Content of hydrogen peroxide (mass%) type Content (mass%) pH Example 1-1 20 DTPP 0.005 4 Example 1-2 20 DTPP 0.0005 4 Example 1-3 20 DTPP 0.05 4 Example 1-4 20 DTPP 0.005 7 Example 1-5 15 DTPP 0.005 7 Examples 1-6 10 DTPP 0.005 7 Example 1-7 20 DTPP 0.0005 7 Examples 1-8 20 DTPP 0.05 7 Examples 1-9 20 PDTP 0.005 7 Examples 1-10 20 EDTA 0.005 7 Examples 1-11 20 DTPA 0.005 7 Examples 1-12 20 DTPP 0.005 9 Comparative example 1-1 20 DTPP 0 7 Comparative example 1-2 20 HEDP 0.005 7

[Chem 2]

[Hydrogen peroxide stability] Regarding Examples 1-1, 1-4, 1-7 to 1-12, and Comparative Examples 1-1 to 1-2, the stability of hydrogen peroxide contained in the resist stripping pretreatment liquid was evaluated.

Specifically, the resist stripping pretreatment liquid was left to stand at 50° C. for 24 hours. After that, the content rate of hydrogen peroxide in the resist stripping pretreatment liquid was measured, and the decomposition rate of hydrogen peroxide was calculated. The results obtained are shown in Table 2 below.

[Table 2] Hydrogen peroxide decomposition rate (%) Example 1-1 <1 Example 1-4 <1 Example 1-7 <1 Examples 1-8 <1 Examples 1-9 3 Examples 1-10 11 Examples 1-11 5 Examples 1-12 11 Comparative example 1-1 27 Comparative example 1-2 100

According to the results in Table 2, it can be understood that if the pH of the resist stripping pretreatment solution is below 7, the stability of hydrogen peroxide is high (Example 1-1, 1-4, and 1-12).

Again, it can be understood that if the nitrogen-containing chelating agent is a nitrogen-containing phosphonic acid chelating agent, then the stability of hydrogen peroxide is very high (Examples 1-1 and 1-9), and secondly, if the nitrogen-containing The chelating agent is amino carboxylic acid chelating agent, then the stability of hydrogen peroxide is high (embodiment 1-10 and 1-11). On the other hand, it can be understood that if the chelating agent does not contain nitrogen atoms, the stability of hydrogen peroxide is low (Comparative Example 1-2).

[etching speed] With respect to Examples 1-1 to 1-3, the corrosion rate of copper in the resist stripping pretreatment solution was evaluated.

Specifically, a copper-plated plate was produced on a resin substrate by electrolytic plating. The temperature of the pre-treatment solution for resist stripping was raised to 50°C, and the copper-plated board was sprayed for 5 minutes. The corrosion rate to copper was calculated from the amount of weight loss caused by immersion of the copper-plated sheet. The results obtained are shown in Table 3 below.

[table 3] Etching speed (μm/min) Example 1-1 <0.01 Example 1-2 <0.01 Example 1-3 0.04

From the results in Table 3, it can be understood that the lower the concentration of the chelate, the lower the corrosion rate of the copper plating.

＜Resist Stripping Solution (B)＞ [Preparation Example 1] Prepare resist stripping solution. Specifically, potassium hydroxide which is a basic compound (α), 2-butoxyethanol and phenyl glycol which are organic solvents (β), and water are mixed to prepare a resist stripping liquid. At this time, the contents of potassium hydroxide, 2-butoxyethanol, and phenylglycol (phenyl glycol) were 6% by mass, 3.3% by mass, and 1.1% by mass, respectively, relative to the total mass of the resist stripping solution.

[Preparation Example 2] Prepare resist stripping solution. Specifically, a mixture of tetramethylammonium hydroxide (TMAH) and methylethylamine (MEA) which are basic compounds (α), 1,2,4-triazole and phenylethylene glycol which are organic solvents (β) Alcohol (phenyl glycol), and water, to prepare a resist stripping solution. At this time, the contents of TMAH, MEA, 1,2,4-triazole, and phenylglycol (phenyl glycol) were 2% by mass, 6% by mass, and 0.12% by mass, respectively, relative to the total mass of the resist stripping solution. , and 3% by mass.

The resist stripping solution prepared in Preparation Examples 1-2 is shown in Table 4 below.

[Table 4] Basic compound (α) Organic solvent (β) type Content (mass%) type Content (mass%) Preparation Example 1 Potassium hydroxide 6 2-butoxyethanol phenyl glycol (phenyl glycol) 3.3 1.1 Preparation example 2 TMAH MEA 2 6 1,2,4-triazole phenyl glycol (phenyl glycol) 0.12 3

＜Substrate＞ [manufacturing example 1] RD-1215-comb type (L/S=12μm/12μm) RD-1215 (Showa Denko Materials Co., Ltd.) with a negative dry film resist laminated on a copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd. "CCL-HL832NS (MT-FL)") as a substrate system, thickness: 15μm), and the exposed part is hardened by exposure treatment. Then, the unexposed part was removed with a developing solution (1wt% sodium carbonate aqueous solution), and the board|substrate on which the resist pattern was formed was obtained. The formed resist pattern is a comb-shaped pattern with a line/space of 12 μm/12 μm (exposure treatment is parallel lines). Then, a copper plating process was performed on the substrate exposed by development, and copper wiring with a thickness of 10 μm was constructed. Thereby, the board|substrate which has copper wiring (thickness: 10 micrometers) and the resist (thickness 15 micrometers) arrange|positioned between copper wirings was manufactured.

[Manufacturing example 2] RD-1215-comb type (L/S=15μm/15μm) The board|substrate was manufactured by the method similar to manufacture example 1 except having set line/space to 15 micrometers/15 micrometers.

[Manufacturing example 3] UFP-151-comb type (L/S=12μm/12μm) A board|substrate was manufactured by the method similar to manufacture example 1 except having used UFP-151 (made by Asahi Kasei Co., Ltd., thickness: 15 micrometers) as a negative dry type thin film resist.

[Manufacturing example 4] UFP-151-comb type (L/S=15μm/15μm) The board|substrate was manufactured by the method similar to manufacture example 3 except having set line/space to 15 micrometers/15 micrometers.

[Manufacturing example 5] ADH-158-comb type (L/S=12μm/12μm) A board|substrate was manufactured by the method similar to manufacture example 1 except having used ADH-158 (made by Asahi Kasei Co., Ltd., thickness: 15 micrometers) as a negative dry type thin film resist.

[Manufacturing example 6] ADH-158-comb type (L/S=15μm/15μm) The board|substrate was manufactured by the method similar to manufacture example 5 except having set line/space to 15 micrometers/15 micrometers.

[Manufacturing example 7] RD-1225-dot type (dot diameter φ=200μm) RD-1225 (manufactured by Showa Denko Co., Ltd., thickness: 25 μm) which is a negative dry film resist was laminated on the substrate, and the exposed portion was cured by exposure treatment. Then, the unexposed part was removed with a developing solution (1wt% sodium carbonate aqueous solution), and the board|substrate on which the resist pattern was formed was obtained. The formed resist pattern was a dot pattern with a dot diameter φ (diameter) of 200 μm (exposure treatment was performed in the form of water droplets). Then, copper plating was performed on the substrate exposed by development, and copper wiring with a thickness of 17 μm was constructed. Thereby, the board|substrate which has copper wiring (thickness: 17 micrometers) and the resist (thickness 25 micrometers) arrange|positioned between copper wirings was manufactured.

[Manufacturing example 8] UFP-251-dot type (dot diameter φ=200μm) A board|substrate was manufactured by the method similar to manufacture example 7 except having used UFP-251 (made by Asahi Kasei Co., Ltd., thickness: 25 micrometers) as a negative dry type thin film resist.

[Manufacturing example 9] ADH-258-dot type (dot diameter φ=200μm) A board|substrate was manufactured by the method similar to manufacture example 7 except having used ADH-258 (made by Asahi Kasei Co., Ltd., thickness: 25 micrometers) as a negative dry type thin film resist.

The fabricated substrates are shown in Table 5 below.

[table 5] Negative Dry Film Resist copper wiring pattern Product name Thickness (μm) Thickness (μm) type L(μm)/S(μm) Spot diameter (μm) Manufacturing example 1 RD-1215 15 10 Comb type 12/12 - Manufacturing example 2 RD-1215 15 10 Comb type 15/15 - Manufacturing example 3 UFP-151 15 10 Comb type 12/12 - Manufacturing example 4 UFP-151 15 10 Comb type 15/15 - Manufacturing Example 5 ADH-158 15 10 Comb type 12/12 - Manufacturing example 6 ADH-158 15 10 Comb type 15/15 - Manufacturing example 7 RD-1225 25 17 point type - 200 Manufacturing Example 8 UFP-251 25 17 point type - 200 Manufacturing Example 9 ADH-258 25 17 point type - 200

[Example 2-1~2-66] Use the resist stripping pretreatment solution prepared in Examples 1-1~1-12 and Comparative Examples 1-1~1-2 (Table 1), and the resist stripping solution prepared in Preparation Examples 1~2 (Table 4 ), the resists of the substrates (Table 5) manufactured in Manufacturing Examples 1 to 9 were peeled off.

Specifically, under the conditions of reduced pressure (0.15MPa), predetermined temperature, and predetermined time, 500 mL of resist stripping pretreatment solution (A) is sprayed by nozzle spraying method to pretreat the substrate . After the pre-treated substrate is washed with water, it is dried, and then sprayed with the resist stripping solution (B) at a predetermined temperature and for a predetermined time. The substrate after dipping was washed with water and dried to manufacture a printed wiring board.

Regarding the substrates (comb-teeth type) of Production Examples 1 to 6, the peelability was evaluated according to the following criteria using an optical microscope MX-63L (manufactured by Olympus Co., Ltd.). The results obtained are shown in Tables 6 and 7 below.

5: The resist is completely stripped 4: There are only residues of microresist 3: The stripping rate of resist is 50~95% 2: The stripping rate of the resist does not reach 50% 1: The resist has not been stripped

Moreover, with respect to the board|substrate (dot type) of manufacture example 7-9, the number of peeling residues was measured using the optical microscope MX-63L (made by Olympus Co., Ltd.). The results obtained are shown in Table 8 below.

[Table 6] Pretreatment solution for resist stripping (A) Resist Stripper (B) Substrate peel off type Processing temperature processing time type Processing temperature processing time Example 2-1 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 5 Example 2-2 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 2 5 Example 2-3 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 5 Example 2-4 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 4 5 Example 2-5 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 5 Example 2-6 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 6 5 Example 2-7 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 5 Example 2-8 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 2 5 Example 2-9 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 5 Example 2-10 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 4 5 Example 2-11 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 5 Example 2-12 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 6 5 Example 2-13 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 5 Example 2-14 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 2 5 Example 2-15 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 5 Example 2-16 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 4 5 Example 2-17 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 5 Example 2-18 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 6 5 Example 2-19 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 5 Example 2-20 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 2 5 Example 2-21 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 5 Example 2-22 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 4 5 Example 2-23 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 5 Example 2-24 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 6 5 Example 2-25 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 5 Example 2-26 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 2 5 Example 2-27 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 5 Example 2-28 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 4 5 Example 2-29 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 5 Example 2-30 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 6 5 Comparative example 2-1 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 3 Comparative example 2-2 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 2 3 Comparative example 2-3 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 3 Comparative example 2-4 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 4 3 Comparative example 2-5 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 5 Comparative example 2-6 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 6 5

[Table 7] Pretreatment solution for resist stripping (A) Resist Stripper (B) Substrate peel off type Processing temperature processing time type Processing temperature processing time Example 2-31 Example 1-1 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 1 5 Example 2-32 Example 1-1 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 2 4 Example 2-33 Example 1-1 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 3 5 Example 2-34 Example 1-1 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 4 5 Example 2-35 Example 1-1 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing Example 5 4 Example 2-36 Example 1-1 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 6 5 Example 2-37 Example 1-4 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 1 5 Example 2-38 Example 1-4 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 2 5 Example 2-39 Example 1-4 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 3 5 Example 2-40 Example 1-4 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 4 5 Example 2-41 Example 1-4 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing Example 5 4 Example 2-42 Example 1-4 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 6 5 Example 2-43 Examples 1-12 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 1 5 Examples 2-44 Examples 1-12 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 2 5 Example 2-45 Examples 1-12 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 3 5 Example 2-46 Examples 1-12 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 4 5 Example 2-47 Examples 1-12 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing Example 5 5 Example 2-48 Examples 1-12 50℃ 1 minute Preparation Example 1 50℃ 10 seconds Manufacturing example 6 5

[Table 8] Pretreatment solution for resist stripping (A) Resist Stripper (B) Substrate residue type Processing temperature processing time type Processing temperature processing time Example 2-49 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 0 Example 2-50 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 0 Example 2-51 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 0 Example 2-52 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 0 Example 2-53 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 0 Example 2-54 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 0 Example 2-55 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 0 Example 2-56 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 0 Example 2-57 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 0 Example 2-58 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 0 Example 2-59 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 0 Example 2-60 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 0 Example 2-61 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 0 Example 2-62 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 0 Example 2-63 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 0 Example 2-58 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 0 Example 2-59 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 0 Example 2-60 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 0 Example 2-61 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 0 Example 2-62 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 8 0 Example 2-63 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 0 Comparative example 2-7 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 0 Comparative example 2-8 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 12 Comparative example 2-9 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 9 0 Example 2-64 Example 1-4 50℃ 2 minutes Preparation example 2 50℃ 25 seconds Manufacturing example 7 0 Example 2-65 Example 1-4 50℃ 2 minutes Preparation example 2 50℃ 20 seconds Manufacturing example 8 0 Example 2-66 Example 1-4 50℃ 2 minutes Preparation example 2 50℃ 50 seconds Manufacturing example 9 0 Comparative example 2-10 - 50℃ 2 minutes Preparation example 2 50℃ 25 seconds Manufacturing example 7 124 Comparative example 2-11 - 50℃ 2 minutes Preparation example 2 50℃ 20 seconds Manufacturing example 8 0 Comparative example 2-12 - 50℃ 2 minutes Preparation example 2 50℃ 50 seconds Manufacturing Example 9 17

[Evaluation of Lifting Time (L.T.: Lifting Time)] The peeling times of Examples and Comparative Examples shown in Table 9 below were measured.

Specifically, in Examples and Comparative Examples, the time from immersing the substrate in the resist stripping solution (B) to the end of stripping was measured as the stripping time. In addition, "peeling termination" means that the entire surface of the substrate contact surface of the resist is detached from the substrate. At this time, the termination of peeling was judged visually. The results obtained are shown in Table 9 below. [Table 9] Pretreatment solution for resist stripping (A) Resist Stripper (B) Substrate LT (seconds) type Processing temperature processing time type Processing temperature processing time Example 2-1 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 15 Example 2-3 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 16 Example 2-5 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 18 Example 2-49 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 44 Example 2-50 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 32 Example 2-51 Example 1-1 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 9 30 Example 2-7 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 16 Example 2-9 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 16 Example 2-11 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 18 Example 2-52 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 44 Example 2-53 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 33 Example 2-54 Example 1-4 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 9 37 Example 2-13 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 18 Example 2-15 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 2 17 Example 2-17 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 19 Example 2-55 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 40 Example 2-56 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 36 Example 2-57 Example 1-5 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 29 Example 2-19 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 20 Example 2-21 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 18 Example 2-23 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 twenty two Example 2-58 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 54 Example 2-59 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 8 37 Example 2-60 Examples 1-6 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 30 Example 2-25 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 8 Example 2-27 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 8 Example 2-29 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 8 Example 2-61 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 25 Example 2-62 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 8 16 Example 2-63 Examples 1-12 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 9 12 Comparative example 2-1 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 1 32 Comparative example 2-3 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 3 34 Comparative example 2-5 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 5 25 Comparative example 2-7 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 7 87 Comparative example 2-8 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing Example 8 54 Comparative example 2-9 - 50℃ 2 minutes Preparation Example 1 50℃ 2 minutes Manufacturing example 9 98 Example 2-64 Example 1-4 50℃ 2 minutes Preparation example 2 50℃ 25 seconds Manufacturing example 7 28 Example 2-65 Example 1-4 50℃ 2 minutes Preparation example 2 50℃ 20 seconds Manufacturing example 8 twenty three Example 2-66 Example 1-4 50℃ 2 minutes Preparation example 2 50℃ 50 seconds Manufacturing example 9 34 Comparative example 2-10 - 50℃ 2 minutes Preparation example 2 50℃ 25 seconds Manufacturing example 7 34 Comparative example 2-11 - 50℃ 2 minutes Preparation example 2 50℃ 20 seconds Manufacturing example 8 28 Comparative example 2-12 - 50℃ 2 minutes Preparation example 2 50℃ 50 seconds Manufacturing Example 9 40

Claims (26)

A method of manufacturing a printed wiring board, comprising the following steps: In the pretreatment step, the substrate having the metal wiring and the resist arranged between the metal wiring is exposed to the resist containing the oxidizing agent (a), the chelating agent (b) containing nitrogen atoms, and water and the pH is 3-10. Pretreatment solution (A); In the resist removal step, the substrate obtained in the pretreatment step is brought into contact with a resist stripping solution (B) containing a basic compound (α), an organic solvent (β), and water to remove the resist. The manufacturing method of a printed wiring board as claimed in claim 1, wherein the oxidizing agent (a) includes hydrogen peroxide, persulfuric acid, permanganic acid, percarbonic acid, perboric acid, percarboxylic acid, halogen oxyacid, and Salt, and at least one member of the group consisting of organic peroxide, but the organic peroxide does not include percarboxylic acid and its salt. The method of manufacturing a printed wiring board according to claim 1 or 2, wherein the content of the oxidizing agent (a) is 5 to 30% by mass relative to the total mass of the resist stripping pretreatment liquid (A). The method for producing a printed wiring board according to any one of claims 1 to 3, wherein the nitrogen-atom-containing chelating agent (b) includes a phosphonic acid-based chelating agent. The method for producing a printed wiring board according to Claim 4, wherein the phosphonic acid-based chelating agent includes diethylenetriaminepentamethylenephosphonic acid and/or 1,2-propylenediaminetetramethylenephosphonic acid. The method for manufacturing a printed wiring board according to any one of claims 1 to 5, wherein the content of the nitrogen-containing chelating agent (b) is 0.0001 to 0.1 with respect to the total mass of the resist stripping pretreatment solution (A) quality%. The method for manufacturing a printed wiring board according to any one of Claims 1 to 6, wherein the resist stripping pretreatment solution (A) further includes a basic compound (c). The method of manufacturing a printed wiring board according to claim 7, wherein the basic compound (c) includes an inorganic basic compound. The method for producing a printed wiring board according to any one of claims 1 to 8, wherein the basic compound (α) contains potassium hydroxide and/or sodium hydroxide. The method for producing a printed wiring board according to any one of claims 1 to 9, wherein the organic solvent (β) contains glycol ethers. The method for manufacturing a printed wiring board as claimed in any one of claims 1 to 10, wherein the organic solvent (β) comprises ethylene glycol monoethyl ether, 2-butoxyethanol, phenylglycol (phenylglycol), At least one member selected from the group consisting of propylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and diethylene glycol monophenyl ether. The method of manufacturing a printed wiring board according to any one of claims 1 to 11, wherein the line/space of the printed wiring board is 50 μm or less/50 μm or less. The method for manufacturing a printed wiring board according to any one of Claims 1 to 12, wherein the resist is a dry film resist. The method of manufacturing a printed wiring board according to any one of claims 1 to 13, wherein the metal wiring contains Cu and/or Co. A stripping method of resist, comprising the following steps: In the pretreatment step, the substrate having the metal wiring and the resist arranged between the metal wiring is exposed to the resist containing the oxidizing agent (a), the chelating agent (b) containing nitrogen atoms, and water and the pH is 3-10. Pretreatment solution (A); In the resist removal step, the substrate obtained in the pretreatment step is brought into contact with a resist stripping solution (B) containing a first basic compound (α), an organic solvent (β), and water to remove the resist. A resist stripping pretreatment liquid, which is a resist stripping pretreatment liquid (A) used before stripping the resist from a substrate having metal wiring and a resist arranged between the metal wirings using the resist stripping liquid, which Features are: comprising an oxidizing agent (a), a nitrogen-containing chelating agent (b), and water, and The pH is 3~10. The resist stripping pretreatment solution as claimed in item 16, wherein the oxidizing agent (a) comprises hydrogen peroxide, persulfuric acid, permanganic acid, percarbonic acid, perboric acid, percarboxylic acid, halogen oxyacid, their At least one member selected from the group consisting of a salt and an organic peroxide. The pre-treatment liquid for resist stripping according to claim 16 or 17, wherein the content of the oxidizing agent (a) is 5-30% by mass relative to the total mass of the pre-treatment liquid (A) for resist stripping. The resist stripping pretreatment solution according to any one of claims 16 to 18, wherein the nitrogen-atom-containing chelating agent (b) includes a phosphonic acid-based chelating agent. According to claim 19, the resist stripping pretreatment solution, wherein the phosphonic acid-based chelating agent includes diethylenetriaminepentamethylenephosphonic acid and/or 1,2-propylenediaminetetramethylenephosphonic acid. The resist stripping pretreatment solution according to any one of claims 16 to 20, wherein the content of the nitrogen-containing chelating agent (b) is 0.0001 to 0.1 with respect to the total mass of the resist stripping pretreatment solution (A) quality%. The resist stripping pretreatment solution according to any one of claims 16 to 21, further comprising a basic compound (c). The resist stripping pretreatment solution according to claim 22, wherein the basic compound (c) includes an inorganic basic compound. The resist stripping pretreatment solution according to any one of claims 16 to 23, wherein the metal wiring width/resist width of the substrate is 50 μm or less/50 μm or less. The resist stripping pretreatment solution according to any one of claims 16 to 24, wherein the resist is a dry film resist. The resist stripping pretreatment liquid according to any one of Claims 16 to 25, wherein the metal wiring contains Cu and/or Co.