Cleaning method

Abstract

In one embodiment, the present invention provides a cleaning method that reduces the impact on substrates and exhibits excellent resin mask removability. In one embodiment, the present invention relates to a cleaning method comprising the step of removing the resin mask from an object to be cleaned, to which the resin mask is attached, using a cleaning composition. The cleaning composition comprises an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C), and water (component D), wherein component B is at least one solvent selected from glycol ethers and aromatic ketones, and component C is a compound having two or more acid groups selected from at least one of carboxyl groups and phosphonic acid groups. The content of component B in the cleaning composition during use is from 1% to 12% by mass, and the content of component D in the cleaning composition during use is from 65% to 95% by mass. The object to be cleaned has undergone a step of performing at least one of soldering and plating using the resin mask.

Description

Technical Field

[0001] The present invention relates to a cleaning method, a method for manufacturing an electronic component using the cleaning method, and an application thereof. Background Art

[0002] In recent years, personal computers and various electronic devices have been driven by the pursuit of lower power consumption, faster processing speeds, and smaller sizes. Consequently, the wiring on the package substrates and other components used in these devices has become increasingly miniaturized. The metal mask method has been the primary method used to form these fine wiring and connecting terminals such as studs and bumps. However, due to its limited versatility and inability to accommodate the miniaturization of wiring, new methods are being adopted.

[0003] One of the new methods is the use of dry film resist as a thick film resin mask instead of a metal mask. This resin mask is ultimately stripped and removed, and a resin mask stripping cleaning agent containing an alkaline agent and water is known as a cleaning agent for stripping and removing the resin mask.

[0004] For example, Japanese Patent Application Laid-Open No. 2007-254555 (Patent Document 1) describes a cleaning agent composition comprising at least one selected from a specific quaternary ammonium salt and a specific polycarboxylate, a hydrophilic organic solvent, and an alkaline component as an alkaline cleaning agent capable of quickly stripping and cleaning cured photoresists such as color resists, black matrix resins, polyimide-based alignment films, and photospacers from color filter substrates for liquid crystal displays. Furthermore, in an example, a cleaning agent is described comprising 2.5 parts of tetrasodium ethylenediaminetetraacetic acid, 5 parts of diethylene glycol diethyl ether, 20 parts of diethylene glycol monomethyl ether, 10 parts of tetramethylammonium hydroxide, and the remainder, water, for a total of 100 parts.

[0005] Japanese Patent Application Laid-Open No. 2015-79244 (Patent Document 2) describes a resin mask cleaning composition containing a specific quaternary ammonium hydroxide, a water-soluble amine, an acid or its ammonium salt, and water as a cleaning agent that can simultaneously promote the removal of the resin mask layer after heat treatment of solder bumps and suppress solder corrosion, thereby improving solder connection reliability. Furthermore, an example describes a cleaning composition comprising 1 part by mass of tetramethylammonium hydroxide, 5 parts by mass of monoethanolamine, 1 part by mass of ammonium formate, 85 parts by mass of water, 4 parts by mass of diethylene glycol butyl ether, and 4 parts by mass of dimethyl sulfoxide.

[0006] Japanese Patent Application Laid-Open No. 2006-173566 (Patent Document 3) describes a stripper composition that has a low environmental load, exhibits excellent stripping properties against resist residue and metal oxidation products from metal wiring generated after ashing, even under low-temperature, short-time cleaning conditions, and exhibits excellent corrosion protection against metal wiring. The composition comprises an organic amine content of 0.2 to 30% by weight, an organic phosphonic acid content of 0.05 to 10% by weight, and a water content of 60 to 99.7% by weight, and has a pH of 9 to 13 at 20°C. Furthermore, in an example, a stripper composition is described that contains 7.3% by weight of 1,2-propylenediamine, 2.0% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid, and 90.7% by weight of water.

[0007] WO2018 / 043440 (Patent Document 4) describes a semiconductor device treatment liquid containing a hydroxylamine compound, an alkaline compound, and at least one selected from a reducing agent and a chelating agent, with a pH of 10 or higher. Furthermore, in the Examples, a treatment liquid is described containing 10.0% hydroxylamine, 10% tetrahydrofurfurylamine, 40% 3-methoxy-3-methyl-1-butanol, 5.0% diethylenetriaminepentaacetic acid, 1% 5-MBTA (5-methyl-1H-benzotriazole), and the remainder (34%) water. Summary of the Invention

[0008] In one embodiment, the present invention relates to a cleaning method comprising the step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using a cleaning composition.

[0009] The cleaning composition contains an alkaline agent (ingredient A), an organic solvent (ingredient B), a chelating agent (ingredient C) and water (ingredient D).

[0010] Component B is at least one solvent selected from glycol ethers and aromatic ketones,

[0011] Component C is a compound having two or more at least one acid group selected from carboxyl groups and phosphonic acid groups,

[0012] The content of component B in the cleaning composition during use is 1% by mass or more and 12% by mass or less.

[0013] The content of component D in the cleaning composition during use is 65% by mass or more and 95% by mass or less.

[0014] The object to be cleaned has undergone a process of performing at least one of soldering and plating using a resin mask.

[0015] In one embodiment, the present invention relates to a method for manufacturing an electronic component, including a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning method of the present invention.

[0016] In one embodiment, the present invention relates to use of a cleaning composition as a stripping agent when stripping a resin mask from an object to be cleaned, the object to be cleaned having undergone a step of at least one of soldering and plating using a resin mask;

[0017] The cleaning composition contains an alkaline agent (ingredient A), an organic solvent (ingredient B), a chelating agent (ingredient C) and water (ingredient D).

[0018] Component B is at least one solvent selected from glycol ethers and aromatic ketones,

[0019] Component C is a compound having two or more at least one acid group selected from carboxyl groups and phosphonic acid groups,

[0020] The content of component B when used is 1% by mass or more and 12% by mass or less.

[0021] The content of Component D when used is 65% by mass or more and 95% by mass or less. DETAILED DESCRIPTION

[0022] After fine wiring is formed on a printed circuit board or the like, cleaning compositions are required to have high cleaning properties in order to reduce the residue of resin mask and to reduce the residue of auxiliary agents such as solder and plating liquid used to form fine wiring and bumps.

[0023] Among them, a resin mask refers to a material formed using a resist whose physical properties such as solubility in a developer are changed by light, electron beams, etc. Resists are generally divided into negative and positive types based on how they react to light or electron beams. Negative resists have the characteristic of decreasing solubility in a developer when exposed to light. For a layer containing a negative resist (hereinafter also referred to as a "negative resist layer"), after exposure and development, the exposed portion is used as a resin mask. Positive resists have the characteristic of increasing solubility in a developer when exposed to light. For a layer containing a positive resist (hereinafter also referred to as a "positive resist layer"), after exposure and development, the exposed portion is removed and the unexposed portion is used as a resin mask. By using a resin mask with this characteristic, it is possible to form fine connections on circuit boards such as metal wiring, metal columns, and solder bumps.

[0024] However, as wiring becomes increasingly miniaturized, removing resin masks located in minute gaps becomes increasingly difficult. Furthermore, simply enhancing cleaning power can lead to damage to the substrate, such as dissolving or deteriorating the substrate surface. Specifically, cleaning compositions are required to not only have high resin mask removal properties but also minimize impact on the substrate.

[0025] In view of this, one embodiment of the present invention provides a cleaning method that can reduce the influence on the substrate and has excellent resin mask removability.

[0026] [Cleaning method]

[0027] In one embodiment, the present invention relates to a cleaning method (hereinafter also referred to as “the cleaning method of the present invention”), comprising the step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using a cleaning composition.

[0028] The cleaning composition contains an alkaline agent (ingredient A), an organic solvent (ingredient B), a chelating agent (ingredient C) and water (ingredient D).

[0029] Component B is at least one solvent selected from glycol ethers and aromatic ketones,

[0030] Component C is a compound having two or more at least one acid group selected from carboxyl groups and phosphonic acid groups,

[0031] The content of component B in the cleaning composition during use is 1% by mass or more and 12% by mass or less.

[0032] The content of component D in the cleaning composition during use is 65% by mass or more and 95% by mass or less.

[0033] The object to be cleaned has undergone a process of performing at least one of soldering and plating using a resin mask.

[0034] According to the present invention, a cleaning method can be provided in one embodiment that can reduce the impact on the substrate and has excellent resin mask removal properties. In one or more embodiments, the cleaning method of the present invention can reduce the impact on the substrate being cleaned and efficiently remove the resin mask from the cleaned object. Furthermore, by using the cleaning method of the present invention, high-quality electronic components can be obtained with high yield. Furthermore, by using the cleaning composition of the present invention, electronic components with fine wiring patterns can be efficiently manufactured.

[0035] The details of the mechanism of action of the effect of the cleaning method of the present invention are still unclear, but are presumed as follows.

[0036] In minute gaps of a circuit pattern formed by copper plating or the like, minute residues of the resin mask may be generated.

[0037] In the present invention, it is believed that the alkali agent (Component A), at least one organic solvent selected from glycol ethers and aromatic ketones (Component B), and water (Component D) penetrate the resin mask, promoting the dissociation of the alkali-soluble resin incorporated into the resin mask, thereby causing charge repulsion and facilitating the removal of the resin mask. Furthermore, it is believed that the presence of the alkali agent (Component A) causes a specific chelating agent (Component C) to adsorb onto the surface of the circuit pattern formed by copper plating, for example, thereby facilitating the removal of the resin mask remaining in the fine gaps within the circuit pattern. It is presumed that this facilitated removal of the resin and the improved ease of removal from the gaps improves cleaning performance.

[0038] Furthermore, it is considered that by setting the contents of component B and water (component D) contained in the cleaning method of the present invention within predetermined ranges, the influence of component B and / or component C on the substrate is suppressed, and excellent cleaning properties are exhibited.

[0039] However, the present invention should not be construed as being limited to this mechanism.

[0040] In the present invention, the resin mask to be stripped and removed refers to a mask for protecting the surface of a material during treatments such as etching, plating, and heating, that is, a mask that functions as a protective film. As a resin mask, in one or more embodiments, a resist layer after exposure and development steps, a resist layer subjected to at least one of exposure and development processes (hereinafter also referred to as "exposed and / or developed"), or a cured resist layer can be cited. As a resin material for forming the resin mask, in one or more embodiments, a film-like photosensitive resin, a resist film, or a photoresist can be cited. The resist film can use a general-purpose resist film.

[0041] The cleaning method of the present invention includes a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached using a cleaning composition, wherein the object to be cleaned has been subjected to at least one of soldering and plating using the resin mask.

[0042] In the cleaning method of the present invention, in one or more embodiments, the step of stripping the resin mask from the object to be cleaned includes the step of contacting the object to be cleaned with the resin mask attached thereto with the cleaning composition of the present invention. Hereinafter, the cleaning composition used in the step of stripping the resin mask from the object to be cleaned in the cleaning method of the present invention is also referred to as the "cleaning composition of the present invention." Therefore, in one embodiment, the present invention relates to a cleaning method using a cleaning composition for stripping a resin mask (the cleaning composition of the present invention), the cleaning composition comprising an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C), and water (component D), wherein component B is at least one solvent selected from glycol ethers and aromatic ketones, and component C is a compound having at least two acid groups selected from carboxyl groups and phosphonic acid groups, wherein the content of component B when used is 1% by mass or more and 12% by mass or less, and the content of component D when used is 65% by mass or more and 95% by mass or less. According to the cleaning composition of the present invention, in one or more embodiments, a cleaning method can be provided that reduces the impact on the substrate and has excellent resin mask removability.

[0043] Examples of methods for removing a resin mask from an object to be cleaned using the cleaning composition of the present invention, or methods for contacting the object to be cleaned with the cleaning composition of the present invention include methods of contacting the object by immersing the object in a cleaning bath containing the cleaning composition, methods of contacting the object by spraying the cleaning composition (spraying), and ultrasonic cleaning methods involving irradiation with ultrasonic waves during immersion. The cleaning composition of the present invention can be used for cleaning without dilution. Examples of the object to be cleaned include the above-mentioned objects.

[0044] In one or more embodiments, the cleaning method of the present invention may include the steps of contacting the object to be cleaned with the cleaning composition, followed by rinsing with water, and then drying. In one or more embodiments, the cleaning method of the present invention may include the steps of contacting the object to be cleaned with the cleaning composition, followed by rinsing with water.

[0045] To facilitate the cleaning power of the cleaning composition of the present invention, the cleaning method of the present invention preferably involves irradiating the cleaning composition of the present invention with ultrasonic waves while it is in contact with the object being cleaned. More preferably, the ultrasonic waves have a relatively high frequency. From the same perspective, the ultrasonic irradiation conditions are preferably, for example, 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

[0046] In the cleaning method of the present invention, the temperature of the cleaning composition is preferably 40°C or higher, more preferably 50°C or higher, from the perspective of easily exerting the cleaning power of the cleaning composition of the present invention. From the perspective of reducing the impact on the substrate, the temperature is preferably 70°C or lower, more preferably 60°C or lower.

[0047] [Ingredient A: Alkaline agent]

[0048] The alkaline agent (hereinafter also referred to as "Component A") contained in the cleaning composition of the present invention may, in one or more embodiments, be at least one selected from an inorganic base and an organic base. From the perspective of reducing the wastewater treatment load, an inorganic base is preferred. Component A may be a single agent or a combination of two or more agents.

[0049] In one or more embodiments, examples of the inorganic base include hydroxides, carbonates, or silicates of alkali metals or alkaline earth metals. Specifically, the inorganic base includes at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and potassium silicate. From the perspective of improving resin mask removability, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate is preferred. At least one of sodium hydroxide and potassium hydroxide is more preferred, and potassium hydroxide is even more preferred. In the present invention, the inorganic base does not include ammonia.

[0050] In one or more embodiments, examples of the organic base include quaternary ammonium hydroxides represented by the following formula (I), amines represented by the following formula (II), and the like. As component A, in one or more embodiments, from the perspective of improving the removability of the resin mask, a combination of a quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II) is preferably used. Furthermore, from the perspective of improving the removability of the resin mask, component A is preferably a quaternary ammonium hydroxide represented by the following formula (I).

[0051] [Chemical Formula 1]

[0052]

[0053] In the above formula (I), R 1 、R 2 、R 3 and R 4 Each is independently at least one selected from the group consisting of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl.

[0054] [Chemical Formula 2]

[0055]

[0056] In the above formula (II), R 5 represents a hydrogen atom, a methyl group, an ethyl group or an aminoethyl group, R 6 is at least one selected from a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group or an ethyl group, R 7 is at least one selected from aminoethyl, hydroxyethyl or hydroxypropyl, or in formula (II), R 5is at least one selected from methyl, ethyl, aminoethyl, hydroxyethyl or hydroxypropyl, R 6 With R 7 They bond to each other to form a pyrrolidine ring or a piperazine ring together with the nitrogen atom in formula (II).

[0057] As the quaternary ammonium hydroxide represented by formula (I), for example, salts containing quaternary ammonium cations and hydroxide groups can be cited. Specific examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, bis(2-hydroxyethyl)dimethylammonium hydroxide, bis(2-hydroxyethyl)diethylammonium hydroxide, bis(2-hydroxyethyl)dipropylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide, and tetra(2-hydroxypropyl)ammonium hydroxide. From the perspective of improving the removability of the resin mask, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred, and tetramethylammonium hydroxide is more preferred.

[0058] Examples of the amine represented by formula (II) include alkanolamines, primary and tertiary amines, and heterocyclic compounds. Specific examples of the amine include at least one selected from monoethanolamine, monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, 1-methylpiperazine, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperazine, ethylenediamine, and diethylenetriamine. From the viewpoint of improving the resin mask removability, monoethanolamine and diethanolamine are preferred among these, and monoethanolamine is more preferred.

[0059] The content of Component A in the cleaning composition of the present invention during use is preferably 1% by mass or more, more preferably 4% by mass or more, and even more preferably 6% by mass or more, from the perspective of improving resin mask removability. From the same perspective, it is preferably 20% by mass or less, more preferably 16% by mass or less, and even more preferably 12% by mass or less. More specifically, the content of Component A in the cleaning composition of the present invention during use is preferably 1% by mass or more and 20% by mass or less, more preferably 4% by mass or more and 16% by mass or less, and even more preferably 6% by mass or more and 16% by mass or less. When Component A is a combination of two or more, the content of Component A refers to the total content of these components.

[0060] In the present invention, "the content of each component of the cleaning composition at the time of use" refers to the content of each component at the time of cleaning, that is, the time when the cleaning composition starts to be used for cleaning.

[0061] [Component B: organic solvent]

[0062] In one or more embodiments, the organic solvent (hereinafter also referred to as "Component B") contained in the cleaning composition of the present invention is at least one solvent selected from glycol ethers and aromatic ketones. Component B may be one or a combination of two or more.

[0063] From the perspective of improving resin mask removability and reducing the impact on the substrate, glycol ethers include compounds having a structure in which 1 or more and 3 or less ethylene glycol are added to an alcohol having 1 or more and 8 or less carbon atoms. Specific examples of glycol ethers include at least one selected from diethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether.

[0064] As the aromatic ketone, acetophenone and the like can be mentioned from the viewpoint of improving the resin mask removability and reducing the influence on the substrate.

[0065] The content of Component B in the cleaning composition of the present invention during use is 1% by mass or more, preferably 1.5% by mass or more, and more preferably 2% by mass or more, from the perspective of improving resin mask removability. Furthermore, from the perspective of reducing the wastewater treatment load and the impact on the substrate, it is 12% by mass or less, preferably 8% by mass or less, and more preferably 4% by mass or less. More specifically, the content of Component B during use is 1% by mass or more and 12% by mass or less, preferably 1.5% by mass or more and 8% by mass or less, and more preferably 2% by mass or less and 4% by mass or less. When Component B is a combination of two or more, the content of Component B refers to the total content of these components.

[0066] [Ingredient C: Chelating agent]

[0067] The chelating agent (hereinafter also referred to as "component C") contained in the cleaning composition of the present invention is a compound having at least one acid group selected from a carboxyl group and a phosphonic acid group. In addition, from the viewpoint of improving the removability of the resin mask, component C is preferably a compound having 4 or less of the above-mentioned acid groups. As component C, in one or more embodiments, aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid, etc. can be listed. From the viewpoint of reducing the environmental load, 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid, etc., which are compounds that do not contain nitrogen atoms, are preferred among these. Component C may be one or a combination of two or more.

[0068] From the viewpoint of improving the resin mask removability, the molecular weight of Component C is preferably 1000 or less, more preferably 500 or less.

[0069] The content of Component C in the cleaning composition of the present invention during use is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the perspective of improving resin mask removability. From the same perspective, it is preferably 5% by mass or less, more preferably 3% by mass or less. More specifically, the content of Component C during use is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less. When Component C is a combination of two or more, the content of Component C refers to the total content of these components.

[0070] In the cleaning composition of the present invention, the mass ratio of component C to component B (C / B) is preferably 0.1 or greater, more preferably 0.3 or greater, and even more preferably 0.4 or greater, from the perspective of improving resin mask removability and reducing the impact on the substrate. From the same perspective, it is preferably 1 or less, more preferably 0.8 or less, and even more preferably 0.7 or less. More specifically, the mass ratio (C / B) is preferably 0.1 or greater and 1 or less, more preferably 0.3 or greater and 0.8 or less, and even more preferably 0.4 or greater and 0.7 or less.

[0071] In the cleaning composition of the present invention, the mass ratio of component A to component C (A / C) is preferably 1 or greater, more preferably 1.5 or greater, and even more preferably 2 or greater, from the viewpoint of improving the resin mask removability and reducing the impact on the substrate. From the same viewpoint, it is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. More specifically, the mass ratio (A / C) is preferably 1 or greater and 10 or less, more preferably 1.5 or greater and 8 or less, and even more preferably 2 or greater and 6 or less.

[0072] [Ingredient D: Water]

[0073] Examples of the water (hereinafter also referred to as "component D") contained in the cleaning composition of the present invention include, in one or more embodiments, ion-exchanged water, RO water, distilled water, pure water, and ultrapure water.

[0074] The content of Component D in the cleaning composition of the present invention can be the remainder excluding Component A, Component B, Component C, and any of the following components. Specifically, the content of Component D in the cleaning composition of the present invention during use is 65% by mass or more, preferably 75% by mass or more, and more preferably 82% by mass or more, from the perspective of improving resin mask removability, reducing wastewater treatment load, and reducing the impact on the substrate. From the perspective of improving resin mask removability, it is 95% by mass or less, preferably 90% by mass or less, and more preferably 87% by mass or less. More specifically, the content of Component D in the cleaning composition of the present invention during use is, in one or more embodiments, 65% by mass or more and 95% by mass or less, preferably 75% by mass or more and 90% by mass or less, and more preferably 82% by mass or more and 87% by mass or less. The content of Component D in the cleaning composition of the present invention during use is, in one or more embodiments, preferably 82% by mass or more and 95% by mass or less, more preferably 82% by mass or more and 90% by mass or less, and even more preferably 82% by mass or more and 97% by mass or less.

[0075] In the cleaning composition of the present invention, the mass ratio of component D to component B (D / B) is preferably 5 or more, more preferably 13 or more, and even more preferably 25 or more from the viewpoint of improving resin mask removability, reducing wastewater treatment load, and reducing the impact on the substrate. Furthermore, from the viewpoint of improving resin mask removability, it is preferably 45 or less, more preferably 40 or less, and even more preferably 35 or less. More specifically, the mass ratio (D / B) is preferably 5 or more and 45 or less, more preferably 13 or more and 40 or less, and even more preferably 25 or more and 35 or less.

[0076] In the cleaning composition of the present invention, the mass ratio of component D to component C (D / C) is preferably 30 or more, more preferably 35 or more, and even more preferably 40 or more from the viewpoint of improving resin mask removability, reducing wastewater treatment load, and reducing the impact on the substrate. Furthermore, from the viewpoint of improving resin mask removability, it is preferably 90 or less, more preferably 65 or less, and even more preferably 55 or less. More specifically, the mass ratio (D / C) is preferably 30 or more and 90 or less, more preferably 35 or more and 65 or less, and even more preferably 40 or more and 55 or less.

[0077] [Component E: ammonia or ammonium salt of organic acid]

[0078] In one or more embodiments of the cleaning composition of the present invention, from the perspective of resin mask removal performance, it is preferred that the cleaning composition further contain at least one of ammonia and an ammonium salt of an organic acid (hereinafter also referred to as "Component E"). As the ammonium salt of an organic acid, from the perspective of resin mask removal performance, an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms is preferred, with ammonium formate being more preferred. Component E may be a single species or a combination of two or more species.

[0079] The content of Component E in the cleaning composition of the present invention during use is preferably from 0.1% to 2% by mass, more preferably from 0.2% to 1.5% by mass, and even more preferably from 0.3% to 1% by mass, from the perspective of improving the resin mask removability. When Component E is a combination of two or more, the content of Component E refers to the total content of these components.

[0080] [Other ingredients]

[0081] The cleaning composition of the present invention may contain other ingredients as needed in addition to the aforementioned ingredients A to E. Examples of these other ingredients include those commonly used in cleaning agents, such as organic solvents other than ingredient B, surfactants, chelating agents other than ingredient C, thickeners, dispersants, rust inhibitors, polymers, solubilizers, antioxidants, preservatives, defoaming agents, and antimicrobial agents.

[0082] The content of other components in the cleaning composition of the present invention during use is preferably from 0% by mass to 2% by mass, more preferably from 0% by mass to 1.5% by mass, even more preferably from 0% by mass to 1.3% by mass, and even more preferably from 0% by mass to 1% by mass.

[0083] In one or more embodiments, the cleaning composition of the present invention may not contain hydroxylamine and / or its salt.

[0084] In one or more embodiments, the cleaning composition of the present invention may be substantially free of linear sugar alcohols. For example, in one or more embodiments, the cleaning composition of the present invention may contain less than 0.1% by weight of linear sugar alcohols when in use.

[0085] The total content of organic matter derived from Component A, Component B, Component C, and any optional components in the cleaning composition of the present invention during use is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and even more preferably 16% by mass or less, from the perspective of reducing the wastewater treatment load and reducing the impact on the substrate. Furthermore, from the perspective of improving the removability of the resin mask, it is preferably 2% by mass or more, more preferably 4% by mass or more, even more preferably 8% by mass or more, and even more preferably 12% by mass or more. More specifically, the total content of organic matter derived from Component A, Component B, Component C, and any optional components during use in the cleaning composition of the present invention is preferably 2% by mass or more and 30% by mass or less, more preferably 4% by mass or more and 25% by mass or less, even more preferably 8% by mass or more and 20% by mass or less, and even more preferably 12% by mass or more and 16% by mass or less.

[0086] The pH of the cleaning composition of the present invention during use is preferably 10 or higher, more preferably 11 or higher, even more preferably 12 or higher, and even more preferably 13 or higher, from the perspective of improving resin mask removability and reducing the impact on the substrate. In the present invention, the "pH during use" refers to the pH at 25°C and can be measured using a pH meter. Specifically, it can be measured by the method described in the Examples.

[0087] [Method for producing cleaning composition]

[0088] The cleaning composition of the present invention can be produced by blending the above-mentioned components A to D and, if necessary, the above-mentioned optional components using a known method. For example, the cleaning composition of the present invention can be formed by blending at least the above-mentioned components A to D. Therefore, the present invention relates to a method for producing a cleaning composition comprising at least the step of blending the above-mentioned components A to D. In the present invention, "blending" includes the operation of mixing components A to D and, if necessary, the above-mentioned optional components simultaneously or in any order. In the method for producing the cleaning composition of the present invention, the preferred blending amount of each component can be the same as the preferred content of each component of the cleaning composition of the present invention described above.

[0089] The cleaning composition of the present invention can be prepared as a concentrate with a reduced amount of water (component D) within a range that does not cause separation, precipitation, etc. and impair storage stability. Regarding the concentrate of the cleaning composition, it is preferably prepared as a concentrate with a dilution ratio of 3 times or more from the viewpoint of transportation and storage, and preferably prepared as a concentrate with a dilution ratio of 30 times or less from the viewpoint of storage stability. The concentrate of the cleaning composition can be diluted with water (component D) at the time of use so that the components A to D and the optional components are at the above-mentioned content (i.e., the content at the time of cleaning) and used. Furthermore, the concentrate of the cleaning composition can also be used by adding each component separately at the time of use. In the present invention, "at the time of use" or "at the time of cleaning" of the cleaning composition as a concentrated solution refers to the state in which the concentrate of the cleaning composition is diluted.

[0090] In one or more embodiments, the cleaning composition of the present invention can be used as a stripper for stripping a resin mask from an object to be cleaned that has undergone at least one of soldering and plating using a resin mask.

[0091] Specifically, the present invention relates in one embodiment to a use of a cleaning composition as a stripping agent when stripping a resin mask from an object to be cleaned, the object to be cleaned having undergone a step of at least one of soldering and plating using a resin mask.

[0092] The cleaning composition contains an alkaline agent (ingredient A), an organic solvent (ingredient B), a chelating agent (ingredient C) and water (ingredient D).

[0093] Component B is at least one solvent selected from glycol ethers and aromatic ketones,

[0094] Component C is a compound having two or more at least one acid group selected from carboxyl groups and phosphonic acid groups,

[0095] The content of component B when used is 1% by mass or more and 12% by mass or less.

[0096] The content of Component D when used is 65% by mass or more and 95% by mass or less.

[0097] [Objects to be cleaned]

[0098] In one or more embodiments, the cleaning composition of the present invention can be used to clean an object to be cleaned to which a resin mask is attached. Examples of the object to be cleaned, in one or more embodiments, include objects having metal portions on their surfaces, such as electronic components and intermediates thereof. Examples of electronic components include at least one component selected from metal plates such as printed circuit boards, wafers, copper plates, and aluminum plates. The intermediates are intermediate products in the manufacturing process of electronic components, including those after resin masking.

[0099] As a specific example of the object to be cleaned with a resin mask attached, for example, an electronic component having wiring, connecting terminals, etc. formed on the surface of the substrate by a process of performing the following treatment can be cited, and the treatment is at least one of soldering and plating treatment (copper plating, aluminum plating, nickel plating, etc.) using a resin mask. In the present invention, soldering refers to making solder present in a resin mask non-existent portion on the substrate, and forming a solder bump by heating. In the present invention, plating treatment refers to performing at least one plating treatment selected from copper plating, aluminum plating and nickel plating on a resin mask non-existent portion on the substrate. The resin mask non-existent portion refers to a portion in which the resin mask is removed by developing a resist pattern formed by developing a resin mask stacked on a substrate. Therefore, the present invention relates to the use of the cleaning agent composition of the present invention as a cleaning agent in the manufacture of electronic components in one embodiment. In one or more embodiments, the object to be cleaned has undergone a process of performing at least one of soldering and plating treatment on a substrate, and the substrate has a resist pattern formed by developing a resin mask stacked on a substrate. For example, the object to be cleaned may be a substrate having a portion where a resin mask exists as a cured resist layer is formed on the substrate, and a portion where a solder bump or a plating layer is formed in a portion where the resin mask does not exist.

[0100] In one or more embodiments, the cleaning composition of the present invention can be suitably used for cleaning an object to which a resin mask is attached or to which a resin mask has been plated and / or heated, from the perspective of cleaning effect. The resin mask may be, for example, a negative resin mask or a positive resin mask. In the present invention, a negative resin mask refers to a resin mask formed using a negative resist, and examples thereof include a negative resist layer that has been exposed and / or developed. In the present invention, a positive resin mask refers to a resin mask formed using a positive resist, and examples thereof include a positive resist layer that has been exposed and / or developed.

[0101] [Method for manufacturing electronic components]

[0102] The present invention relates in one embodiment to a method for manufacturing an electronic component (hereinafter also referred to as “the method for manufacturing an electronic component of the present invention”), which includes a step of peeling off a resin mask from an object to be cleaned to which the resin mask is attached using the cleaning method of the present invention. Examples of the object to be cleaned include the above-mentioned objects to be cleaned. The method for manufacturing an electronic component of the present invention can effectively remove the resin mask attached to the electronic component by cleaning using the cleaning method of the present invention, thereby manufacturing an electronic component with high reliability. Furthermore, by performing the cleaning method of the present invention, it becomes easy to remove the resin mask attached to the electronic component, thereby shortening the cleaning time and improving the manufacturing efficiency of the electronic component.

[0103] [Set]

[0104] In one embodiment, the present invention relates to a kit for use in either the cleaning method of the present invention or the method for manufacturing an electronic component of the present invention (hereinafter also referred to as the "kit of the present invention"). In one or more embodiments, the kit of the present invention is a kit for producing the cleaning composition of the present invention. The kit of the present invention can provide a cleaning composition that can reduce the impact on the substrate and has excellent resin mask removal properties.

[0105] One embodiment of the kit of the present invention includes a three-component cleaning composition comprising: a solution containing component A (first liquid), a solution containing component B (second liquid), and a solution containing component C (third liquid), in a non-mixable state. At least one of the first, second, and third liquids further contains a portion or all of component D, and the first, second, and third liquids are mixed during use. After mixing the first, second, and third liquids, they can be diluted with component D (water) as needed. Each of the first, second, and third liquids can contain any of the aforementioned components as needed.

[0106] Another embodiment of the kit of the present invention includes a two-component cleaning composition comprising: a solution containing components A and C (a first liquid) and a solution containing component B (a second liquid), both of which are immiscible. At least one of the first and second liquids further contains a portion or all of component D (water), and the first and second liquids are mixed during use. After mixing the first and second liquids, the mixture can be diluted with component D (water) as needed. Each of the first and second liquids can contain any of the aforementioned components as needed.

[0107] The present invention also relates to one or more of the following embodiments.

[0108] <1> A cleaning agent composition for stripping a resin mask, comprising an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C), and water (component D), wherein component B is at least one solvent selected from glycol ethers and aromatic ketones, and component C is a compound having two or more acid groups selected from at least one acid group selected from carboxyl groups and phosphonic acid groups, wherein the content of component B when used is from 1% by mass to 12% by mass, and the content of component D when used is from 65% by mass to 95% by mass.

[0109] <2> The cleaning composition according to <1>, wherein the content of Component C at the time of use is preferably 0.5% by mass or more, more preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less. More specifically, the content of Component C at the time of use is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less.

[0110] <3> The cleaning composition according to <1> or <2>, wherein the mass ratio of component C to component B (C / B) is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.4 or more, and is preferably 1 or less, more preferably 0.8 or less, and even more preferably 0.7 or less. More specifically, the mass ratio (C / B) is preferably 0.1 or more and 1 or less, more preferably 0.3 or more and 0.8 or less, and even more preferably 0.4 or more and 0.7 or less.

[0111] <4> The cleaning composition according to any one of <1> to <3>, wherein the mass ratio of component D to component B (D / B) is preferably 5 or more, more preferably 13 or more, and even more preferably 25 or more, and is preferably 45 or less, more preferably 40 or less, and even more preferably 35 or less. More specifically, the mass ratio (D / B) is preferably 5 or more and 45 or less, more preferably 13 or more and 40 or less, and even more preferably 25 or more and 35 or less.

[0112] <5> The cleaning composition according to any one of <1> to <4>, wherein the pH at 25°C is preferably 10 or higher, more preferably 11 or higher, further preferably 12 or higher, and even more preferably 13 or higher.

[0113] <6> A cleaning composition as described in any one of <1> to <5>, wherein component B is preferably a compound having a structure in which 1 mole or more and 3 moles of ethylene glycol are added to an alcohol having 1 to 8 carbon atoms, and more preferably at least one selected from diethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether.

[0114] <7> The cleaning composition according to any one of <1> to <6>, preferably further comprising at least one of ammonia and an ammonium salt of an organic acid (Component E), more preferably further comprising an ammonium salt of a C1-5 carboxylic acid, and even more preferably further comprising ammonium formate.

[0115] <8> The cleaning composition according to any one of <1> to <7>, wherein component A is at least one selected from an inorganic base and an organic base, the inorganic base is preferably a hydroxide, carbonate or silicate of an alkali metal or alkaline earth metal, more preferably at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and potassium silicate, further preferably one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, further preferably at least one of sodium hydroxide and potassium hydroxide, further preferably potassium hydroxide.

[0116] <9> The cleaning composition according to any one of <1> to <7>, wherein component A is a quaternary ammonium hydroxide represented by the following formula (I),

[0117] [Chemical Formula 3]

[0118]

[0119] In the above formula (I), R 1 、R 2 、R 3 and R 4 Each is independently at least one selected from the group consisting of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl.

[0120] <10> The cleaning composition according to any one of <1> to <7>, wherein component A is at least one selected from an inorganic base and an organic base, and the organic base is preferably at least one of a quaternary ammonium hydroxide represented by the following formula (I) and an amine represented by the following formula (II), and more preferably a combination of a quaternary ammonium hydroxide represented by the following formula (I) and an amine represented by the following formula (II).

[0121] [Chemical Formula 4]

[0122]

[0123] In the above formula (I), R 1 、R 2 、R 3 and R 4 Each is independently at least one selected from methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl,

[0124] [Chemical Formula 5]

[0125]

[0126] In the above formula (II), R 5 represents a hydrogen atom, a methyl group, an ethyl group or an aminoethyl group, R 6 is at least one selected from a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group or an ethyl group, R 7 is at least one selected from aminoethyl, hydroxyethyl or hydroxypropyl, or in formula (II), R 5 is at least one selected from methyl, ethyl, aminoethyl, hydroxyethyl or hydroxypropyl, R 6 With R 7 They bond to each other to form a pyrrolidine ring or a piperazine ring together with the nitrogen atom in formula (II).

[0127] <11> The cleaning composition according to <9> or <10>, wherein the quaternary ammonium hydroxide represented by formula (I) is preferably at least one selected from tetramethylammonium hydroxide and tetraethylammonium hydroxide, more preferably tetramethylammonium hydroxide.

[0128] <12> The cleaning composition according to <10>, wherein the amine represented by formula (II) is preferably at least one selected from monoethanolamine and diethanolamine, more preferably monoethanolamine.

[0129] <13> The cleaning composition according to any one of <1> to <12>, wherein the content of Component A in the cleaning composition during use is preferably 1% by mass or more, more preferably 4% by mass or more, and even more preferably 6% by mass or more. From the same viewpoint, it is preferably 20% by mass or less, more preferably 16% by mass or less, and even more preferably 12% by mass or less. More specifically, the content of Component A in the cleaning composition of the present invention during use is preferably 1% by mass or more and 20% by mass or less, more preferably 4% by mass or more and 16% by mass or less, and even more preferably 6% by mass or more and 16% by mass or less.

[0130] <14> The cleaning composition according to any one of <1> to <13>, wherein component B is acetophenone.

[0131] <15> The cleaning composition according to any one of <1> to <14>, wherein the content of Component B at the time of use is preferably 1.5% by mass or more, more preferably 2% by mass or more, and is preferably 8% by mass or less, more preferably 4% by mass or less. More specifically, the content of Component B at the time of use is preferably 1.5% by mass or more and 8% by mass or less, more preferably 2% by mass or more and 4% by mass or less.

[0132] <16> The cleaning composition according to any one of <1> to <15>, wherein component C is preferably a compound having four or fewer acid groups selected from carboxyl groups and phosphonic acid groups, more preferably aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, or etidronic acid, and even more preferably 2-phosphonobutane-1,2,4-tricarboxylic acid or etidronic acid.

[0133] <17> The cleaning composition according to any one of <1> to <16>, wherein the molecular weight of component C is preferably 1000 or less, and more preferably 500 or less.

[0134] <18> The cleaning composition according to any one of <1> to <17>, wherein the mass ratio (A / C) of component A to component C is preferably 1 or more, more preferably 1.5 or more, and further preferably 2 or more, and is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less. The mass ratio (A / C) is preferably 1 or more and 10 or less, more preferably 1.5 or more and 8 or less, and further preferably 2 or more and 6 or less.

[0135] <19> The cleaning composition according to any one of <1> to <18>, wherein the content of component D at the time of use is preferably 75% by mass or more, more preferably 82% by mass or more, and is 95% by mass or less, preferably 90% by mass or less, more preferably 87% by mass or less. More specifically, the content of component D at the time of use is preferably 75% by mass or more and 90% by mass or less, more preferably 82% by mass or more and 87% by mass or less.

[0136] <20> The cleaning composition according to any one of <1> to <19>, wherein the mass ratio (D / C) of component D to component C is preferably 30 or more, more preferably 35 or more, and further preferably 40 or more, and is preferably 90 or less, more preferably 65 or less, and further preferably 55 or less. More specifically, the mass ratio (D / C) is preferably 30 or more and 90 or less, more preferably 35 or more and 65 or less, and further preferably 40 or more and 55 or less.

[0137] <21> The cleaning composition according to any one of <1> to <20>, wherein the content of Component E during use is preferably from 0.1% by mass to 2% by mass, more preferably from 0.2% by mass to 1.5% by mass, and even more preferably from 0.3% by mass to 1% by mass.

[0138] <22> The cleaning composition according to any one of <1> to <21>, wherein the content of the linear sugar alcohol during use is preferably less than 0.1% by weight in one or more embodiments, and more preferably contains substantially no linear sugar alcohol.

[0139] <23> The cleaning composition according to any one of <1> to <22>, wherein the total content of organic matter derived from component A, component B, component C, and optional components at the time of use is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and even more preferably 16% by mass or less, and is preferably 2% by mass or more, more preferably 4% by mass or more, further preferably 8% by mass or more, and even more preferably 12% by mass or more. More specifically, the total content of organic matter derived from component A, component B, component C, and optional components at the time of use is preferably 2% by mass or more and 30% by mass or less, more preferably 4% by mass or more and 25% by mass or less, further preferably 8% by mass or more and 20% by mass or less, and even more preferably 12% by mass or more and 16% by mass or less.

[0140] <24> The cleaning composition according to any one of <1> to <23>, further comprising at least one of ammonia and an ammonium salt of an organic acid (component E), wherein the content of the other components other than components A to E in the cleaning composition is preferably from 0% by mass to 2% by mass, more preferably from 0% by mass to 1.5% by mass, further preferably from 0% by mass to 1.3% by mass, and even more preferably from 0% by mass to 1% by mass.

[0141] <25> A method for producing an electronic component, comprising the step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning composition according to any one of <1> to <24>.

[0142] <26> The method for manufacturing an electronic component according to <25>, wherein the electronic component is at least one component selected from a printed circuit board, a wafer, and a metal plate.

[0143] <27> A cleaning method comprising the step of peeling a resin mask from an object to be cleaned to which the resin mask is attached using the cleaning composition according to any one of <1> to <24>,

[0144] The object to be cleaned has been subjected to a process of performing at least one of soldering and plating using a resin mask.

[0145] <28> A cleaning method as in <26>, wherein the object to be cleaned with a resin mask attached thereto is preferably an electronic component having at least one of wiring and connection terminals formed on the surface of a substrate by undergoing a process of performing the following treatment, the treatment being at least one of soldering and plating treatment using a resin mask.

[0146] <29> The cleaning method of <27> or <28>, wherein the object to be cleaned has undergone at least one of soldering and plating treatments on a substrate having a resist pattern formed by developing a resin mask laminated on the substrate.

[0147] <30> The cleaning method according to any one of <27> to <29>, wherein the step of peeling the resin mask from the object to be cleaned preferably includes a step of bringing the object to be cleaned, to which the resin mask is attached, into contact with a cleaning composition.

[0148] <31> A cleaning method as described in <30>, wherein the method for bringing the cleaning composition of the present invention into contact with the object to be cleaned is preferably one or more methods selected from the following methods: a method of bringing the object into contact by immersing the object in a cleaning bath containing the cleaning composition, a method of bringing the object into contact by spraying the cleaning composition (spraying method), and an ultrasonic cleaning method in which ultrasonic irradiation is performed during immersion.

[0149] <32> The cleaning method according to any one of <27> to <31>, wherein the temperature of the cleaning composition is preferably 40°C or higher, more preferably 50°C or higher, and preferably 70°C or lower, more preferably 60°C or lower.

[0150] <33> Use of the cleaning composition according to any one of <1> to <24> as a cleaning agent for an object to be cleaned having a resin mask attached thereto.

[0151] <34> A cleaning composition for use as a stripping agent when stripping a resin mask from an object to be cleaned, wherein the object to be cleaned has undergone a process of at least one of soldering and plating using a resin mask, and the cleaning composition is any one of <1> to <24>.

[0152] Example

[0153] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

[0154] 1. Preparation of the cleaning compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2

[0155] Component A, Component B, Component C, Component D, and other components were blended in the composition ratios listed in Table 1, calculated as active ingredients, and stirred and mixed to prepare the cleaning compositions of Examples 1-11, Comparative Examples 1-5, and Reference Examples 1-2. The compositions in Table 1 are expressed as solids. The pH values of the cleaning compositions shown in Table 1 at 25°C were measured using a pH meter (HM-30G, Toa Denpa Kogyo Co., Ltd.) after immersing the pH meter electrode in the cleaning composition for 3 minutes.

[0156] The following components were used as components of the cleaning compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 and 2.

[0157] (ingredient A)

[0158] Tetramethylammonium hydroxide [Showa Denko K.K., TMAH (25%)]

[0159] Potassium hydroxide [manufactured by Kanto Chemical Co., Ltd., special grade, solid content 48% by mass]

[0160] Monoethanolamine [manufactured by Nippon Shokubai Co., Ltd.]

[0161] 1,2-Propanediamine [Fujifilm Wako Pure Chemical Industries, Ltd.]

[0162] (Non-ingredient A)

[0163] Hydroxylamine [Fujifilm Wako Pure Chemical Industries, Ltd., Grade 1, 50% aqueous solution]

[0164] (Ingredient B)

[0165] Diethylene glycol monobutyl ether [manufactured by Nippon Emulsifier Co., Ltd., diethylene glycol monobutyl ether]

[0166] Ethylene glycol monobenzyl ether [manufactured by Nippon Emulsifier Co., Ltd., Ethylene glycol monobenzyl ether]

[0167] Diethylene glycol monohexyl ether [manufactured by Nippon Emulsifier Co., Ltd., diethylene glycol monohexyl ether]

[0168] Phenoxyethanol [Fujifilm Wako Pure Chemical Industries, Ltd., special grade, ethylene glycol monophenyl ether]

[0169] Diethylene glycol diethyl ether [Fujifilm Wako Pure Chemical Industries, Ltd., Grade 1, diethylene glycol diethyl ether]

[0170] Acetophenone [Fujifilm Wako Pure Chemical Industries, Ltd., special grade]

[0171] (Ingredient C)

[0172] Etidronic acid [manufactured by Italmatch Japan Co., Ltd., Dequest 2010, content 60%]

[0173] 2-Phosphonobutane-1,2,4-tricarboxylic acid [Dequest7000 (CN), manufactured by Italmatch Japan Co., Ltd., content: 50%)

[0174] Aminotrimethylenephosphonic acid [Dequest2000, manufactured by Italmatch Japan Co., Ltd., content 50%)

[0175] (ingredient D)

[0176] Water [pure water with a concentration of 1 μS / cm or less produced by a pure water device G-10DSTSET manufactured by Organo Co., Ltd.]

[0177] (Ingredient E)

[0178] Ammonium formate [Toyama Pharmaceutical Industry Co., Ltd.]

[0179] Ammonia [Fujifilm Wako Pure Chemical Industries, Ltd., Grade 1, 25% aqueous solution]

[0180] (Other ingredients)

[0181] 5-Methyl-1H-benzotriazole [Tokyo Chemical Industry Co., Ltd.]

[0182] 2. Evaluation of cleaning agent compositions

[0183] The prepared cleaning compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 and 2 were evaluated as follows.

[0184] [Preparation of test pieces]

[0185] A photosensitive film for forming circuits on a PKG substrate (Package Substrate) (Photek RY-5560, 60 μm thick, negative dry film resist) was laminated onto the surface of the electroless-plated polyimide under the following conditions. After selective exposure to cure the exposed areas (exposure step), the unexposed areas were removed by development (development step), resulting in a substrate having a resist pattern (a negative resin mask with a patterned shape). The areas where the unexposed areas had been removed by development were then copper-plated (50 μm thick) to produce test pieces (30 mm × 50 mm and 120 mm × 120 mm).

[0186] (1) Lamination: Lamination was performed using a cleaning roller (RY-505Z, manufactured by Rayon Industries, Ltd.) and a vacuum applicator (VA7024 / HP5, manufactured by Rohm and Haas Company) at a roller temperature of 50° C. and a roller pressure of 1.4 bar.

[0187] (2) Exposure: A direct drawing apparatus for printed circuit boards (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.) was used at 15 mJ / cm 2 Exposure is performed with the exposure amount set.

[0188] (3) Pattern shape: L / S = 20 μm / 20 μm stripe pattern

[0189] (4) Development: Using a substrate developing device (manufactured by Yangbo Technology Co., Ltd., LT-980366) and a 1% sodium carbonate aqueous solution at 30° C., the spray pressure was set to 0.2 MPa to remove the resin mask of the unexposed portion.

[0190] [Cleaning Test, Evaluation of Resin Mask Residues (Immersion Conditions)]

[0191] In a tall 200mL glass beaker, 100g of each cleaning composition from Examples 1-11, Comparative Examples 1-5, and Reference Examples 1-2 was added. The mixture was heated to 50°C and stirred at 600rpm using a rotor (fluororesin (PTFE, polytetrafluoroethylene), φ8mm x 25mm). The test piece was then immersed in this state for 10 minutes. Next, 100g of water was added to a 100mL glass beaker to serve as a rinse tank. The test piece was then immersed in this rinse tank for rinsing and then dried by blowing nitrogen gas.

[0192] Using a VHX-2000 digital microscope (Keyence Corporation) at 300x magnification, the presence of residual resin mask at the boundary between the thin line and solid areas of the specific patterned area of the test piece after the cleaning test was visually inspected. The number of residuals was counted. The results are shown in Table 1. In cases where the number of residual resin mask was significantly high, such as when the residual resin mask remained continuously, it is recorded as ">50" in Table 1.

[0193] The test piece was 30 mm × 50 mm in size and contained a copper circuit pattern having thin line portions and solid portions. The pattern had a thickness of 50 μm, a width of 20 μm for the thin line portions, and a width of 300 to 1500 μm for the solid portions.

[0194] [Cleaning Test, Evaluation of Resin Mask Peeling Start Speed]

[0195] In a tall 200 mL glass beaker, 100 g of each cleaning composition from Examples 1-11, Comparative Examples 1-5, and Reference Examples 1-2 was added. The mixture was heated to 50°C and stirred at 600 rpm using a rotor (fluororesin (PTFE), φ8 mm × 25 mm). The test piece was then immersed in the mixture. Visual observation was performed to determine the time it took for the resin mask to be peeled off and float within the cleaning composition. The results are shown in Table 1.

[0196] In addition, the test piece used had the same form as the immersion conditions in the cleaning test.

[0197] <Evaluation Criteria>

[0198] A: Within 5 minutes

[0199] B: Longer than 5 minutes, but less than 10 minutes

[0200] C: Longer than 10 minutes but less than 15 minutes

[0201] D: Longer than 15 minutes

[0202] [Evaluation of substrate damage]

[0203] Before and after the cleaning test under the above-described immersion conditions, the presence or absence of changes in the color of the pattern portion in the appearance of the substrate was visually confirmed, and the results of evaluation based on the following evaluation criteria are shown in Table 1.

[0204] <Evaluation Criteria>

[0205] A: No changes were found before and after the cleaning test.

[0206] B: Changes were found before and after the cleaning test.

[0207] [Table 1]

[0208]

[0209] As shown in Table 1, the results of the cleaning test under immersion conditions show that the cleaning compositions of Examples 1 to 11 have reduced effects on the substrate and are superior in resin mask removal properties compared to Reference Examples 1 to 2 which do not contain Component C, Comparative Examples 1 and 4 which do not contain Component B, Comparative Example 2 which does not contain Component A, and Comparative Examples 3 and 5 in which the contents of Components B and D are outside the specified ranges.

[0210] It should be noted that Comparative Example 3 is an example according to the embodiment of Patent Document 4, and Comparative Example 4 is an example according to the embodiment of Patent Document 3.

[0211] Furthermore, a cleaning test was conducted on the cleaning compositions of Examples 1 and 2 and Reference Example 2 under the conditions of continuous immersion and showering described below to evaluate the resin mask removability.

[0212] [Cleaning test, evaluation of the number of resin mask residues (immersion + spray conditions)]

[0213] The immersion and spraying were performed continuously according to the following points. 1 kg of each cleaning composition of Examples 1 to 2 and Reference Example 2 was added to a 1L glass beaker, heated to 50°C, and stirred at a speed of 300 rpm using a rotor (fluororesin (PTFE), φ8mm×25mm), and the test piece was immersed in this state for 3 minutes. A 10L stainless steel beaker prepared separately was used as a storage tank, and 10 kg of the same cleaning composition as the 1L glass beaker was added and heated to 50°C. In addition, a box-type spray cleaning machine equipped with a single-fluid nozzle (fan-shaped) VVP9060 (manufactured by Ikeuchi Co., Ltd.) as a spray nozzle was used to spray the cleaning composition in the storage tank onto the test piece for 2 minutes (pressure: 0.1MPa, spraying distance: 10cm). It should be noted that the sprayed cleaning composition was recovered in the storage tank and recycled. Next, 1 kg of water was added to a 1 L glass beaker to serve as a rinse tank. The sample was immersed in the rinse tank for rinsing and then dried by blowing nitrogen gas.

[0214] Using an optical microscope (VHX-2000 Digital Microscope, manufactured by KEYENCE Corporation) at 300x magnification, the presence of residual resin mask at the boundary between the thin line portion and the solid portion of the specific pattern region of the test piece after the cleaning test was visually inspected, and the amount of residual resin mask was counted. The results are shown in Table 2.

[0215] The test piece had the same circuit pattern as the test piece for the immersion condition, except that the size was 120 mm×120 mm.

[0216] [Table 2]

[0217]

[0218] As shown in Table 2, the results of the cleaning test under the immersion and shower conditions show that the cleaning compositions of Examples 1 and 2 are superior in resin mask removability compared to Reference Example 2 which does not contain Component C.

[0219] Industrial applicability

[0220] The present invention provides a resin mask stripping cleaning composition that reduces the effects on substrates and exhibits excellent resin mask removal properties. Therefore, a cleaning method using the cleaning composition of the present invention is useful in the manufacturing process of electronic components, shortening the cleaning process for electronic components with resin masks attached, improving the performance and reliability of the manufactured electronic components, and enhancing the productivity of semiconductor devices.

Claims

1. A cleaning method comprising the step of peeling a resin mask from an object to be cleaned to which the resin mask is attached using a cleaning composition, The cleaning composition contains: an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C), and water (component D). Component B is at least one solvent selected from glycol ethers and aromatic ketones, Component C is a compound having two or more at least one acid group selected from carboxyl groups and phosphonic acid groups, The content of component B in the cleaning composition during use is 1% by mass or more and 12% by mass or less. The content of component D in the cleaning composition during use is 65% by mass or more and 95% by mass or less. The mass ratio D / B of component D to component B is 12.5 or more and 45 or less, The pH value of the cleaning composition at 25° C. is greater than 10, The object to be cleaned has undergone a process of performing at least one of soldering and plating using a resin mask.

2. The cleaning method according to claim 1, wherein The content of Component C in the cleaning composition during use is 0.5% by mass or more and 5% by mass or less.

3. The cleaning method according to claim 1 or 2, wherein The content of Component A in the cleaning composition during use is 1% by mass or more and 20% by mass or less.

4. The cleaning method according to claim 1 or 2, wherein The mass ratio C / B of component C to component B is 0.1 or more and 1 or less.

5. The cleaning method according to claim 1 or 2, wherein Component B is a compound having a structure in which 1 mol or more and 3 mol or less of ethylene glycol are added to an alcohol having 1 to 8 carbon atoms.

6. The cleaning method according to claim 1 or 2, wherein Component B is at least one selected from diethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol diethyl ether, and acetophenone.

7. The cleaning method according to claim 1 or 2, wherein: Component A is at least one selected from an inorganic base and an organic base. The inorganic base is a hydroxide, carbonate or silicate of an alkali metal or an alkaline earth metal.

8. The cleaning method according to claim 1 or 2, wherein Component A is a quaternary ammonium hydroxide represented by the following formula (I), In the formula (I), R 1 、R 2 、R 3 and R 4 Each independently represents at least one selected from the group consisting of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl.

9. The cleaning method according to claim 1 or 2, wherein: Component A is a combination of a quaternary ammonium hydroxide represented by the following formula (I) and an amine represented by the following formula (II), In the formula (I), R 1 、R 2 、R 3 and R 4 Each is independently at least one selected from methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl, In the formula (II), R 5 represents a hydrogen atom, a methyl group, an ethyl group or an aminoethyl group, R 6 is at least one selected from a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group or an ethyl group, R 7 is at least one selected from aminoethyl, hydroxyethyl or hydroxypropyl, or In formula (II), R 5 is at least one selected from methyl, ethyl, aminoethyl, hydroxyethyl or hydroxypropyl, R 6 With R 7 They bond to each other to form a pyrrolidine ring or a piperazine ring together with the nitrogen atom in formula (II).

10. The cleaning method according to claim 9, wherein The quaternary ammonium hydroxide represented by formula (I) is at least one selected from tetramethylammonium hydroxide and tetraethylammonium hydroxide.

11. The cleaning method according to claim 9, wherein The amine represented by formula (II) is at least one selected from monoethanolamine and diethanolamine.

12. The cleaning method according to claim 1 or 2, wherein Component C is a compound having four or less at least one acid group selected from carboxyl groups and phosphonic acid groups.

13. The cleaning method according to claim 1 or 2, wherein: Component C is one or more compounds selected from aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and etidronic acid.

14. The cleaning method according to claim 1 or 2, wherein: The molecular weight of component C is 1,000 or less.

15. The cleaning method according to claim 1 or 2, wherein: The cleaning composition further comprises: at least one of ammonia and an ammonium salt of an organic acid, namely component E, The content of the other components in the cleaning composition other than components A to E is 0% by mass or more and 2% by mass or less.

16. The cleaning method according to claim 15, wherein Component E is an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms.

17. The cleaning method according to claim 15, wherein: The content of Component E in the cleaning composition during use is 0.1% by mass or more and 2% by mass or less.

18. The cleaning method according to claim 1 or 2, wherein: The total content of organic matter derived from component A, component B, component C, and optional components in the cleaning composition during use is 30% by mass or less.

19. The cleaning method according to claim 1 or 2, wherein: The content of straight-chain sugar alcohol when used is less than 0.1% by weight.

20. The cleaning method according to claim 1 or 2, wherein: The content of Component D in the cleaning composition during use is 82% by mass or more and 95% by mass or less.

21. The cleaning method according to claim 1 or 2, wherein The mass ratio D / C of component D to component C is 30 or more and 90 or less.

22. The cleaning method according to claim 1 or 2, wherein: The object to be cleaned has undergone a process of performing at least one of soldering and plating on a substrate having a resist pattern formed by developing a resin mask laminated on the substrate.

23. The cleaning method according to claim 1 or 2, wherein: The object to be cleaned is an electronic component having at least one of wiring and connection terminals formed on a substrate surface through a process of performing at least one of soldering and plating using a resin mask.

24. The cleaning method according to claim 1 or 2, wherein: The temperature of the cleaning composition is 40° C. or higher and 70° C. or lower. 25 . A method for manufacturing an electronic component, comprising the step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning method according to claim 1 .

26. The method for manufacturing an electronic component according to claim 25, wherein: The electronic component is a printed circuit board.

27. Use of a cleaning composition as a stripping agent when stripping a resin mask from an object to be cleaned, the object to be cleaned having been subjected to a process of at least one of soldering and plating using a resin mask; The cleaning composition comprises: an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C), and water (component D). Component B is at least one solvent selected from glycol ethers and aromatic ketones, Component C is a compound having two or more at least one acid group selected from carboxyl groups and phosphonic acid groups, The content of component B when used is 1% by mass or more and 12% by mass or less. The content of component D when used is 65% by mass or more and 95% by mass or less, The mass ratio D / B of component D to component B is 12.5 or more and 45 or less, The pH value of the cleaning composition at 25° C. is greater than 10.

Images