Photoresist removal composition and photoresist removal method

Abstract

To provide a photoresist removal composition enabling efficient removal of a photoresist and enabling suppression of clogging occurring in a nozzle and a filter of an apparatus.SOLUTION: The foregoing problem is solved by a composition for stripping a photoresist for forming a pattern containing copper after formation of the pattern. When the composition is subjected to separation with a sieve having an opening of 2000 μm, stripped fragments that do not pass through the sieve are 55 mass% or more relative to a total mass of the composition.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] BACKGROUND ART In recent years, electronic devices have become smaller and more functional, and printed wiring boards used in such electronic devices are also required to be smaller and more functional. To meet these demands, the following methods have been adopted for manufacturing printed wiring boards and the like: For example, a metal layer called a seed layer is formed on an insulating layer partially containing copper wiring, a photoresist layer is formed on the surface of the seed layer, and a resist pattern is formed by exposure and development, after which copper plating is applied to the openings in the pattern, and then the photoresist and seed layer are removed to form a circuit pattern that will serve as the connection terminals for the copper wiring.

[0003] As described above, manufacturing methods for printed wiring boards and the like often include a step of removing photoresist, and in the photoresist removal step, an aqueous solution containing various components is usually used (Patent Document 1, etc.). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 022491 Summary of the Invention [Problem to be solved by the invention]

[0005] When conventional processing solutions are used in the photoresist removal process, the size of the peeled pieces becomes too small to be collected using a large mesh filter, resulting in the problem of clogging the nozzles of the equipment. Furthermore, when conventional processing solutions are used in the step of removing photoresist, yellow scum may be generated, which may cause clogging of the nozzles and filters of the equipment.

[0006] In view of the above, there is a need for a means that is excellent in the ability to remove photoresist as part of the manufacturing process of, for example, printed wiring boards, and that can also prevent clogging of the nozzles and filters of the equipment. [Means for solving the problem]

[0007] The present invention includes, for example, the following aspects. <1> A composition for stripping a photoresist for forming a copper-containing pattern after the pattern is formed, comprising: The composition is such that, when the composition is separated through a sieve with a mesh size of 2000 μm, the amount of peeled pieces that do not pass through the sieve after peeling is 55 mass % or more relative to the total mass of the composition. <2> When the composition is separated through a sieve with an opening of 45 μm, the amount of peeled pieces passing through the sieve after peeling is 9 mass % or less based on the total mass of the composition. <1> The composition is as described in <3> The above-mentioned composition contains an alkaline agent containing at least one selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic alkalis, an organic solvent, and an azole compound. <1> or <2> The composition is as described in <4> The composition contains, based on the total amount of the composition, 3.0 to 50% by mass of the alkaline agent, 0.1 to 30% by mass of the organic solvent, and 0.001 to 1.0% by mass of the azole compound. <3> The composition is as described in <5> The pattern is a circuit pattern that is formed on an insulating layer having copper wiring at least in a part thereof and serves as a connection terminal portion of the copper wiring. <1> ~ <4> The composition according to any one of the preceding claims. <6> For the photoresist for forming a copper-containing pattern, <1> ~ <5> a photoresist removal method comprising the step of contacting a photoresist with the composition according to any one of the above items. <7> For the photoresist for forming a copper-containing pattern, <1> ~ <5> The present invention relates to a method for producing a printed wiring board, a semiconductor device, or a semiconductor package, the method comprising a photoresist removal step of contacting a photoresist with the composition according to any one of the above items. [Effects of the Invention]

[0008] According to the present invention, there are provided a photoresist removing composition and the like that can efficiently remove photoresist and prevent clogging of the nozzles and filters of the equipment. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention relates to a composition for stripping a photoresist for forming a copper-containing pattern after the pattern has been formed, wherein when the composition is separated through a sieve with a mesh size of 2000 μm, the amount of peeled pieces that do not pass through the sieve after peeling is 55 mass % or more relative to the total mass of the composition. When the photoresist removing composition of the present invention is used in the step of removing photoresist, the size of the peeled pieces becomes relatively large and can be collected using a filter with a large mesh, which has the advantage of making it less likely for the nozzle of the equipment to become clogged. Furthermore, when the photoresist removing composition of the present invention is used in the step of removing photoresist, yellow scum is unlikely to occur, which is advantageous in that clogging of the nozzles and filters of the equipment is unlikely to occur. In the present invention, the method for measuring the weight distribution of the peeled pieces and the method for confirming whether or not yellow scum has occurred can be the method described in the examples below.

[0010] In the present invention, when the composition is separated with a sieve having a mesh size of 2000 μm, it is preferable that the peeled pieces after peeling that do not pass through the sieve are 70% by mass or more, more preferably 90% by mass or more, based on the total mass of the composition. On the other hand, in the present invention, when the composition is separated with a sieve having a mesh size of 45 μm, it is preferable that the peeled pieces after peeling that pass through the sieve are 9% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less, based on the total mass of the composition.

[0011] The composition of the present invention is suitably used for removing a photoresist after forming a pattern containing copper, and contains at least a predetermined alkali agent, an organic solvent, and an azole compound. Hereinafter, the composition will be described in detail.

[0012] [I. Composition] The composition is preferably water-soluble. That is, it is preferable that at least a part of the composition is soluble or suspended in water, and more preferably it can be uniformly mixed with water at an arbitrary ratio. Further, it is preferable that at least a part of the components other than water contained in the composition is soluble in water, and more preferably the components other than water contained in the composition and water can be uniformly mixed.

[0013] <I-1. (A) Alkali agent> The composition preferably contains 3.0 to 50% by mass of (A) an alkali agent (hereinafter also referred to as component (A)) based on its total mass. The content of the alkali agent in the composition is more preferably 4.0 to 40% by mass, still more preferably 5.0 to 30% by mass or 6.0 to 35% by mass, based on the total amount of the composition, and particularly preferably 7.0 to 15% by mass, 8.0 to 20% by mass or 9.0 to 12% by mass. In the composition containing component (A), the removability of the photoresist is improved, and an effect of suppressing damage to a circuit pattern containing copper, a copper alloy, etc., which are connection terminal portions of copper wiring, is recognized.

[0014] The alkaline agent (A) preferably contains at least one of (A-1) alkanolamine, (A-2) quaternary ammonium hydroxide, and (A-3) inorganic alkali, more preferably contains two of these, and particularly preferably contains all of (A-1) to (A-3).

[0015] (A-1) Alkanolamine The type of (A-1) alkanolamine that can be contained in the composition as component (A) is not particularly limited, but includes monoalkanolamines, dialkanolamines, trialkanolamines, and alkylated products thereof (N-alkylated products, O-alkylated products). Examples of alkanolamines (A) include 2-aminoethanol (monoethanolamine), N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, 1-amino-2-propanol (isopropanolamine), N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-amino-propan-1-ol, N-ethyl-2-amino-propan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, and N-methyl-2-aminobutan-1-ol. , N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4 Preferred examples of the methylaminopropane include 1,2-methylpentan-1-ol, 2-aminohexan-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2-(2-aminoethoxy)ethanol, etc. These may be used alone or in combination of two or more. Among these, the alkanolamine is preferably one or more selected from the group consisting of 2-aminoethanol (monoethanolamine) and 1-amino-2-propanol.

[0016] The content of the alkanolamine is preferably 1.0 to 50 mass%, more preferably 1.5 to 45 mass%, 1.5 to 42 mass%, 2.0 to 30 mass%, or 2.0 to 15 mass%, further preferably 3.0 to 12 mass%, and particularly preferably 4.0 to 8.0 mass%, or 5.0 to 9.0 mass%, based on the total amount of the composition.

[0017] (A-2) Quaternary ammonium hydroxide The type of (A-2) quaternary ammonium hydroxide that can be contained in the composition as component (A) is not particularly limited, and examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, triethylmethylammonium hydroxide, ethyltrimethylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, and triethyl(2-hydroxyethyl)ammonium hydroxide. These may be used alone or in combination of two or more. Among these, the quaternary ammonium hydroxide is preferably at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and triethylmethylammonium hydroxide.

[0018] The content of the quaternary ammonium hydroxide is preferably 0.3 to 12 mass%, more preferably 0.5 to 10 mass%, even more preferably 1.0 to 8.0 mass%, and particularly preferably 1.5 to 5.0 mass% or 2.0 to 6.0 mass%, based on the total amount of the composition.

[0019] (A-3) Inorganic alkali The types of (A-3) inorganic alkalis that can be included as component (A) in the composition are not particularly limited, and examples thereof include alkali metal compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and potassium silicate; alkaline earth metal compounds such as magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, calcium silicate, and magnesium silicate; transition metal compounds such as copper hydroxide and iron hydroxide; and ammonia. Among these, potassium hydroxide, sodium hydroxide, etc. are preferable as the inorganic alkali.

[0020] The content of the inorganic alkali is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, still more preferably 0.05 to 2.0% by mass, and particularly preferably 0.1 to 0.5% by mass or 0.2 to 1.0% by mass, etc., based on the total amount of the composition.

[0021] <I-2. (B) Organic Solvent> The composition preferably contains 0.1 to 30% by mass of (B) organic solvent (hereinafter also referred to as component (B)) based on its total mass. The content of the organic solvent in the composition is more preferably 0.5 to 25% by mass, still more preferably 1.0 to 20% by mass or 1.5 to 15% by mass, and particularly preferably 2.0 to 10% by mass, 2.2 to 5.0% by mass, or 2.5 to 4.0% by mass, etc., based on the total amount of the composition.

[0022] The composition contains at least an organic solvent within the range of a sphere with a radius of 3.60 MPa centered on the point where the coordinates of the Hansen solubility parameter (HSP) are δd = 16.0, δp = 8.7, and δh = 15.5 (hereinafter also referred to as the central point), that is, the distance from the central point in the HSP coordinates is 3.60 MPa 0.5 or less (hereinafter also referred to as a specific organic solvent), that is, the distance from the central point in the HSP coordinates is 3.60 MPa 0.5It is preferable that the composition contains an organic solvent having an HSP value where the distance from the center point on the coordinate system is small. In this way, a composition containing an organic solvent having an HSP value where the distance from the center point on the coordinate system is small is recognized to have an effect of improving the removability of the photoresist, particularly the ability to efficiently peel the photoresist from the metal layer rather than dissolving it in an aqueous solution. The formula for calculating the distance from the center point is shown below.

number

[0023] The following reasons can be cited for the observed effectiveness of resist stripping and removal. Specific organic solvents with HSP values ​​close to the center point on the HSP coordinate system tend to have low compatibility with the components of photoresists, such as dry films (described in detail below), and are therefore thought to have little effect on dissolving the photoresist. However, specific organic solvents can promote contact between the alkaline agent and water on photoresists, such as dry films, facilitating the reaction of the alkaline agent with the terminal carboxyl groups of the photoresist. The action of such specific organic solvents can cause a neutralization reaction between the terminal carboxyl groups of the photoresist and the alkaline agent, allowing the aqueous solution to penetrate between the photoresist and the metal layer, easily causing the photoresist to swell. As a result, the swollen photoresist can be easily stripped from the metal layer covering the surface.

[0024] Thus, it is believed that a specific organic solvent having a characteristic HSP value can remove photoresist more efficiently than an organic solvent having a different HSP value and having the ability to dissolve photoresist. This is because a relatively long time is required to dissolve the photoresist in a solution, whereas a composition that is easily immersed in the gap between the photoresist and the metal layer covering the photoresist can only act on a more limited range of the photoresist, allowing it to be removed by peeling.

[0025] For specific organic solvents, the distance from the center point in the HSP coordinate is 3.30 MPa 0.5The following is preferable: 3.00 MPa 0.5 The following is more preferable: 2.70 MPa 0.5 The following is more preferable: As the specific organic solvent, a solvent having a distance from the center point in the HSP coordinate system of 2.50 MPa 0.5 Below 2.30MPa 0.5 Below 2.00MPa 0.5 Below, 1.50MPa 0.5 or less or 1.00MPa 0.5 The following may also be used: In addition, as the specific organic solvent, a solvent having a distance from the center point in the HSP coordinate system of, for example, 0.70 MPa 0.5 ~3.50MPa 0.5 1.00MPa 0.5 ~3.30MPa 0.5 1.50MPa 0.5 ~3.00MPa 0.5 2.00MPa 0.5 ~2.70MPa 0.5 or the like may also be used.

[0026] Preferred specific examples of the specific organic solvent include the following, and Table 1 shows their compound names, HSP coordinates, and distances from the center point. First, the distance from the center point in the HSP coordinate system is 1.50 MPa. 0.5 Examples of the specific organic solvent include ethylene glycol monomethyl ether, methylhydrazine, trifluoroethanol such as 2,2,2-trifluoroethanol, diacetin, and chloropropanol such as 1-chloro-2-propanol.

[0027] The distance from the center point in HSP coordinates is 1.50MPa 0.5 Over 3.00MPa 0.5The following specific organic solvents include dimethylaminoethanol, ethylenediamine, nonanediols such as 1,9-nonanediol, bromoallyl alcohols such as 2-bromoallyl alcohol, dichloropropanols such as 2,3-dichloropropanol, furfuryl alcohol, adipic acid, ethylene chlorohydrin, N-formylethylamine, ethylene glycol monopropyl ether, chloroallyl alcohols such as 2-chloroallyl alcohol (2-chloro-2-propen-1-ol), 2-pyrrolidones having a 2-hydroxyethyl group such as 1-(2-hydroxyethyl)-2-pyrrolidone, diethylene glycol monovinyl ether, diethylenetriamine, dichloropropols such as 1,3-dichloro-2-propanol, and 2-ethoxyethanol. Examples include ethoxyethanol, chloroallyl alcohols such as 3-chloro-2-propen-1-ol, serotonin, hexanediols such as 1,6-hexanediol, cyclopentenols such as 2-cyclopenten-1-ol, methylamine, formic acid, ethylene glycol monoisopropyl ether, azidopropenes such as 3-azidopropene, 2,3-butadiene-1-ol, allyl alcohol, fluoropropenoic acids such as 2-fluoropropenoic acid, acetic acid, azidoethane, isocyanic acid, propanols such as n-propanol, butenols such as (E)-2-buten-1-ol, methyl salicylate, propanols such as 2-propanol, L-(-)-tyrosine, dipropylene glycol, ethyl carbamate, and 2,2-dimethyl-1-propanol.

[0028] Furthermore, the distance from the center point in the HSP coordinate system is 3.00 MPa 0.5 Over 3.60MPa 0.5Examples include 4'-hydroxyacetanilide, 1-butanol, 1-methoxymethanol, diethylene glycol monomethyl ether, 3-hydroxytetrahydrofuran, isobutyl alcohol, 2-butanol, ethyl lactate, triethylene glycol monomethyl ether, tetrahydrofurfuryl alcohol, 2-pentanol, glycerol formal, 1-aminocyclopropanecarboxylic acid, 1-pentanol, glycidol, 2-propyn-1-ol, 1,2-cyclohexanediol, diethylene glycol monoethyl ether, isooctyl alcohol, 3-chloro-1-propanol, 2-methyl-2-butanol, salicylic acid, 3-methoxy-3-methylbutanol, coniferyl alcohol, sinapyl alcohol, acetone cyanohydrin, crotonic acid, and the like.

Table 1

[0029] As the specific organic solvent contained in the composition, from the viewpoint of availability and the like, among the above specific examples, ethylene glycol monopropyl ether (distance from the center point is 2.00 MPa 0.5 ), n-propanol (distance from the center point is 2.69 MPa 0.5 ), etc. are more preferable.

[0030] As the specific organic solvent, one type may be used, or two or more types may be used. Also, as the component (B) organic solvent in the composition, those other than the specific organic solvent may be included. However, it is preferable that the organic solvent in the composition contains 30% by mass or more of the specific organic solvent based on the total amount of the organic solvent, more preferably 50% by mass or more, still more preferably 70% by mass or more, particularly preferably 90% by mass or more, and it is even more preferable that only the specific organic solvent is contained as the organic solvent in the composition.

[0031] <I-3. (C) Azole compound> The composition preferably contains 0.001 to 1.0 mass% of (C) an azole compound (hereinafter also referred to as component (C)) based on the total mass of the composition. The content of the azole compound in the composition is more preferably 0.005 to 0.80 mass%, even more preferably 0.01 to 0.60 mass%, or 0.015 to 0.70 mass%, and particularly preferably 0.02 to 0.40 mass%, 0.025 to 0.50 mass%, or 0.03 to 0.30 mass%, based on the total mass of the composition. In the composition containing component (C), the effect of protecting the metal layer containing copper or a copper alloy and reducing the etching rate of copper is observed. The azole compound in the composition preferably includes at least one of a triazole compound, an imidazole compound, a benzimidazole compound, and a pyrazole compound. The triazole compound is not particularly limited as long as it is a compound having a triazole ring, and examples thereof include triazoles which may be either 1,2,3-triazole or 1,2,4-triazole, triazoles having a substituent with 10 or less carbon atoms, triazoles such as tolyltriazole having an aromatic ring condensed to a triazole ring, and triazole salts thereof. The imidazole compound is not particularly limited as long as it is a compound having an imidazole ring, and examples thereof include imidazole, imidazole derivatives having a substituent having 10 or less carbon atoms, for example, 1-alkylimidazoles such as 1-methylimidazole, 4-alkylimidazoles such as 4-methylimidazole, mercaptoimidazoles such as 2-mercaptoimidazole, and imidazolium salts thereof. The benzimidazole compound is not particularly limited as long as it is a compound having a benzimidazole skeleton, and examples thereof include benzimidazole, benzimidazole derivatives having a substituent having 10 or less carbon atoms, such as 1-alkylbenzimidazole, 2-alkylbenzimidazole, 7-alkylbenzimidazole, and benzimidazolium salts thereof. Also, examples of the pyrazole compound include pyrazole, pyrazole having a substituent with 10 or fewer carbon atoms, 1-alkylpyrazoles such as 1-methylpyrazole, 3-alkylpyrazoles such as 3-methylpyrazole, 4-alkylpyrazoles such as 4-methylpyrazole, 5-alkylpyrazoles such as 5-methylpyrazole, and salts of these pyrazoles.

[0032] <I-4. Water> The composition preferably contains water. The type of water contained in the composition is not particularly limited, but water from which metal ions, organic impurities, particulate particles, etc. have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc. is preferred, pure water is more preferred, and especially ultrapure water is preferred. The water content in the composition is preferably 20% by mass or more, more preferably more than 20% by mass, more preferably in the range of 20 to 99% by mass, still more preferably 40 to 97% by mass, yet more preferably 60 to 95% by mass, and particularly preferably 70 to 95% by mass based on the total amount of the composition. In the composition in which the water content is adjusted in this way, the reactivity with the photoresist and the removability of the photoresist are improved.

[0033] <I-5. Other Components> The composition may contain other secondary components as necessary, as long as the above-described effects are not inhibited. Examples of other components include pH adjusters, surfactants, defoamers, etc. For example, organic acids (organic acid ions), ammonium ions, etc. may be added. When an organic acid or organic acid ions are added to the composition, the affinity of the composition for the dry film resist is improved. Also, when ammonium ions are added to the composition, the reactivity of the composition with respect to the carboxyl group of the dry film resist is improved. Also, carbonate ions, carbonates that generate carbonate ions, bicarbonates, etc. may be added to the composition. When carbonate ions or the like are added to the composition, the copper corrosion resistance is improved. Specific examples of the carbonate and bicarbonate include salts of ammonium ions, salts of alkali metals or alkaline earth metals, etc. By combining the above components, ammonium salts of organic acids such as ammonium benzoate, ammonium salts of carbonic acids such as tetramethylammonium carbonate, etc. may be added to the composition. The content of the secondary components in the composition is preferably 10% by mass or less, more preferably 5.0% by mass or less, still more preferably 3.0% by mass or less, and even more preferably 2.0% by mass or less, or 1.5% by mass or less, based on the total amount of the composition. In addition, the content of each component of the salt that generates organic acid (organic acid ion), ammonium ion, and carbonate ion in the composition is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, or 1.5% by mass or less, respectively. In addition, the composition is preferably a solution and preferably does not contain solid particles such as polishing particles.

[0034] <I-6. Method for Preparing the Composition> The composition of the present invention is prepared by adding component (A), component (B), component (C), water, and, if necessary, other components, and preferably stirring until it becomes completely uniform. In producing the composition, the order of addition and mixing of each component is not particularly limited. For example, a small amount of water may be added to any of the (A) components of (A-1) to (A-3), and other components other than water may be prepared as a concentrated solution, and they may be mixed at the site where the composition is used. In this way, any component may be transported in a concentrated state, that is, a state without water, and water may be added to prepare the composition.

[0035] <I-7. Properties of the Composition> The pH range of the composition of the present invention is not particularly limited, but in one embodiment, the pH value of the composition is 8 or more, preferably 10 or more, and more preferably 11 or more. The pH value can be measured by a general method using a pH meter.

[0036] According to the composition of the present invention, it is possible to suppress damage to copper and copper alloys. Therefore, the etching rate for copper can be suppressed to 0.050 μm / min or less. More preferably, the etching rate of copper is 0.040 μm / min or less, still more preferably 0.030 μm / min or less, and particularly preferably 0.020 μm / min or 0.015 μm / min or less.

[0037] According to the composition of the present invention, the photoresist can be effectively removed. Therefore, the value of L.P. (lifting point) regarding the peeling rate can be made 100 seconds or less. More preferably, the value of L.P. is 90 seconds or less, still more preferably 85 seconds or less, and particularly preferably 80 seconds or 75 seconds or less.

[0038] <I-8. Usage form of the composition> The temperature at which the composition is used for removing the photoresist is not particularly limited, but a temperature of 10 to 70°C is preferred, more preferably 20 to 65°C, and still more preferably 25 to 60°C. By using the composition within such a temperature range, the removability of the photoresist is improved, and the compositional change of the composition can be suppressed to easily maintain the photoresist removal conditions.

[0039] The treatment time of the photoresist with the composition is not particularly limited, but 20 to 600 seconds is preferred, 30 to 300 seconds is more preferred, and it may be 30 to 240 seconds. The treatment time is the time for bringing the composition into contact with the photoresist, and it may be appropriately selected according to various conditions such as the surface state of the photoresist to be removed, the concentration of the composition, the temperature, and the treatment method.

[0040] The method of bringing the composition of the present invention into contact with a photoresist is not particularly limited. For example, the composition of the present invention can be brought into contact with the photoresist to be removed by means such as dropping (single wafer spin coating) or spray spraying, or a method such as immersing the photoresist to be removed in the composition of the present invention can be adopted. In the present invention, any method may be adopted.

[0041] <II. Method for Removing Photoresist> The method for removing a photoresist of the present invention includes a photoresist removal step of bringing the above-described composition of the present invention into contact with a photoresist for forming a pattern containing copper. Hereinafter, the method for removing a photoresist will be described.

[0042] The composition of the present invention can be suitably used, for example, when removing a photoresist for forming a circuit pattern containing copper that serves as a connection terminal portion of a copper wiring on an insulating layer having at least a part of the copper wiring after forming the circuit pattern. Here, the "insulating layer having at least a part of the copper wiring" is not particularly limited as long as it is an insulating layer in which the copper wiring is embedded on the surface or inside, and examples include a printed wiring board, a package substrate for mounting semiconductor elements, and a silicon insulating layer of a semiconductor wafer. In addition, the "circuit pattern containing copper that serves as a connection terminal portion of the copper wiring" is, for example, for making an electrical connection with other members as a connection terminal portion of the copper wiring included in the insulating layer. In one embodiment of the present invention, the connection terminal portion is a connection terminal portion of the copper wiring in a printed wiring board. Also, in one embodiment of the present invention, the connection terminal portion is a connection terminal portion of the copper wiring in a package substrate for mounting semiconductor elements. Further, in one embodiment of the present invention, the connection terminal portion is a connection terminal portion of the copper wiring in a semiconductor element.

[0043] <III. Manufacturing Method of Printed Wiring Board, etc.> The method for producing a printed wiring board or the like of the present invention includes a photoresist removal step in which the composition of the present invention is brought into contact with a photoresist for forming a copper-containing pattern. In addition to printed wiring boards, the composition of the present invention can also be suitably used in the photoresist removal step in methods for producing semiconductor elements and semiconductor packages.

[0044] For example, the composition of the present invention can be suitably used in the process of producing a printed wiring board (e.g., a package substrate for mounting a semiconductor element) when removing a photoresist for forming a circuit pattern containing copper that will serve as a connection terminal for the copper wiring on an insulating layer at least partially containing copper wiring after the circuit pattern has been formed. Furthermore, the composition of the present invention can be suitably used in the process of manufacturing a semiconductor device when removing a photoresist for forming a circuit pattern on an insulating layer at least partially containing copper wiring, the circuit pattern containing copper, which will become a connection terminal portion of the copper wiring, and at least one selected from the group consisting of tin and a tin alloy, after the circuit pattern has been formed.

[0045] Photoresists used in printed wiring boards include, for example, compositions containing a binder polymer, a photopolymerizable monomer, a photopolymerization initiator, and other additives. Examples of binder polymers include those obtained by copolymerizing at least one of methacrylic acid and acrylic acid as an essential component with several types of vinyl monomers such as methacrylic acid esters, acrylic acid esters, and styrene. The photopolymerizable monomer is preferably at least one of methacrylic acid esters and acrylic acid esters. The photopolymerization initiator may be at least one selected from the group consisting of benzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-ethylanthraquinone, benzoin, benzoin methyl ether, 9-phenylacridine, benzil dimethyl ketal, and benzil diethyl ketal. Alternatively, a bimolecular system consisting of hexaarylbiimidazole and a hydrogen donor (2-mercaptobenzoxazal, N-phenylglycine) may be used. Other additives include a thermal polymerization initiator and a dye.

[0046] Preferred examples of photoresists used in semiconductor elements include a combination of a phenol-formaldehyde resin (collectively known as a "novolac resin") and a naphthoquinone diazide compound, which is a photosensitive component.

[0047] Furthermore, examples of the resist disposed between the metal wirings include dry film resist and liquid resist. Of these, the resist is preferably a dry film resist. Although there are no particular limitations on the dry film resist, it is preferable that the resist be formed from a photosensitive resin. Examples of the photosensitive resin include negative photosensitive resins and positive photosensitive resins.

[0048] The negative photosensitive resin is not particularly limited, but includes azide-based photosensitive resins, diazo-based photosensitive resins, acetylenic low-molecular-weight photosensitive resins, ethylenic low-molecular-weight photosensitive resins, insolubilized polymer-based photosensitive resins, and chromic acid-based photosensitive resins. These negative photosensitive resins may be used alone or in combination of two or more.

[0049] The positive photosensitive resin is not particularly limited, but examples thereof include quinone diazide photosensitive resins, solubilized polymer photosensitive resins, etc. These positive photosensitive resins may be used alone or in combination of two or more.

[0050] Of these, the dry film resist is preferably formed from a negative photosensitive resin. The negative photosensitive resin hardens during the exposure process during pattern formation, becoming insoluble in a developer, and the exposed portion (the portion where the negative photosensitive resin has hardened) remains as the dry film resist. Here, during exposure, the negative photosensitive resin tends to harden particularly in the surface portion exposed to light, and the surface portion of the resulting dry film resist may have a particularly dense structure. Therefore, even if an attempt is made to remove the dry film resist using a composition, the composition may have difficulty penetrating into the interior of the dry film resist. Furthermore, some compositions may not have sufficient resist removal ability, preventing the removal of the dry film resist. As a result, it may take a long time to remove the dry film resist. In contrast, the composition of the present invention easily penetrates into the dry film resist, and therefore the dry film resist can be quickly stripped and removed. [Example]

[0051] The present invention will be specifically described below with reference to examples, although the present invention is not limited to these examples in any way.

[0052] <Preparation of samples for evaluating peeling fragment distribution> A sample for evaluating the distribution of peeled off pieces was prepared as follows. First, a copper-clad laminate (Mitsubishi Gas Chemical Company, Inc., CCL-HL832NS (MT-FL) 0.1 mmtC / C) was chemically plated with copper to form a thin copper film (thickness: 1.0 μm). A dry film resist (Resonac Corporation, RY-5825, thickness: 25 μm) was attached to the surface of this thin copper film and exposed to light.

[0053] <Checking for the occurrence of yellow scum> 500 mL of the aqueous composition obtained in Example 1 and Comparative Example 2 was heated to 50°C, and 0.5 m of dry film resist (manufactured by Resonac Corporation, RD-3025, thickness: 25 µm) was applied. 2The mixture was immersed for 5 hours. After that, the mixture was filtered through a filter cloth with 200 μm openings, and the obtained filtrate was suction filtered through a filter paper with 4 μm openings. The presence or absence of yellow scum on the filter paper was confirmed visually.

[0054] <Measurement of weight distribution of peeled pieces> 200 g of the aqueous compositions obtained in Example 1 and Comparative Example 1 were heated to 50°C, and two of the above-mentioned samples for evaluating the distribution of peeled off particles, cut into 4 cm x 4 cm squares and weighed in advance, were immersed in the samples to peel off the dry film resist. The peeled off particles were separated using sieves with openings of 9500 μm, 4000 μm, 2000 μm, 1000 μm, 850 μm, 600 μm, 425 μm, 300 μm, 150 μm, 100 μm, and 45 μm, washed, and thoroughly dried. The weight of the peeled off particles remaining on each sieve was then measured, and the weight distribution of the peeled off particles was determined.

[0055] Example 1 To 741.4 g of pure water, monoethanolamine (MEA) was added in an amount to give a final concentration of 7% by mass (93.3 g of a 75% MEA aqueous solution), tetramethylammonium hydroxide (TMAH) in an amount to give a final concentration of 3% by mass (120.0 g of a 25% TMAH aqueous solution), potassium hydroxide (KOH) in an amount to give a final concentration of 0.3% by mass (3.0 g of a 48% KOH aqueous solution), ethylene glycol monopropyl ether in an amount to give a final concentration of 2.8% by mass (28.0 g), 3-methylpyrazole (3-MPZ) in an amount to give a final concentration of 0.03% by mass (0.3 g), and ammonium benzoate in an amount to give a final concentration of 1.4% by mass (14.0 g) to prepare an aqueous composition. The resulting aqueous composition was checked for the presence or absence of yellow scum, and no yellow scum was observed. On the other hand, when the weight distribution of peeled pieces was measured for the obtained aqueous composition, the amount of peeled pieces after peeling that did not pass through a 2000 μm sieve was 94.1 mass %. The results are shown in Tables 2 and 3 below.

[0056] (Comparative Example 1) An aqueous composition was prepared by adding monoethanolamine (MEA) (106.7 g of a 75% MEA aqueous solution), tetramethylammonium hydroxide (TMAH) (320.0 g of a 25% TMAH aqueous solution), ethylene glycol monophenyl ether (40.0 g), and 1,2,4-triazole (1,2,4-TRZ) (1.6 g) to 531.7 g of pure water to give a final concentration of 8% by mass. The weight distribution of the peeled pieces was measured for the resulting aqueous composition. The fraction of peeled pieces that did not pass through a 2000 μm sieve after peeling was 50.6% by mass. The results are shown in Table 3 below. The HSP values ​​of ethylene glycol monophenyl ether were δd = 17.8, δp = 5.7, and δh = 14.3, and the distance from the center point was 3.70 MPa. 0.5 is.

[0057] (Comparative Example 2) An aqueous composition was prepared by adding monoethanolamine (MEA) to 808.8 g of pure water in an amount that would result in a final concentration of 6% by weight (80.0 g of a 75% MEA solution), tetramethylammonium hydroxide (TMAH) to 2% by weight (80.0 g of a 25% TMAH solution), ethylene glycol monophenyl ether to 3.0% by weight (30.0 g), and 1,2,4-triazole (1,2,4-TRZ) to 0.12% by weight (1.2 g). The resulting aqueous composition was examined for the presence or absence of yellow scum, and yellow scum was observed. The results are shown in Table 2 below.

[0058] [Table 2]

[0059] [Table 3]

Claims

1. A composition for stripping a photoresist for forming a copper-containing pattern after the pattern is formed, comprising: A composition, wherein when the composition is separated through a sieve with a mesh size of 2000 μm, peeled pieces that do not pass through the sieve account for 55 mass % or more of the total mass of the composition.

2. The composition according to claim 1, wherein when the composition is separated through a sieve having an opening of 45 μm, the amount of peeled pieces passing through the sieve after peeling is 9 mass % or less relative to the total mass of the composition.

3. 3. The composition according to claim 1, comprising an alkaline agent comprising at least one selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic alkalis, an organic solvent, and an azole compound.

4. The composition according to claim 3, wherein the composition comprises, based on the total amount of the composition, 3.0 to 50 mass% of the alkaline agent, 0.1 to 30 mass% of the organic solvent, and 0.001 to 1.0 mass% of the azole compound.

5. 5. The composition according to claim 1, wherein the pattern is a circuit pattern that serves as a connection terminal portion of the copper wiring formed on an insulating layer that has copper wiring at least in part thereof.

6. A method for removing a photoresist, comprising a photoresist removal step of contacting the composition according to any one of claims 1 to 5 with a photoresist for forming a copper-containing pattern.

7. A method for producing a printed wiring board, a semiconductor element, or a semiconductor package, comprising a photoresist removal step of contacting the composition according to any one of claims 1 to 5 with a photoresist for forming a copper-containing pattern.

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