TWI865549B - Cleaning method and use of cleaning agent composition - Google Patents

Abstract

The present invention provides a cleaning method in one embodiment that can reduce the impact on the substrate and has excellent resin mask removal performance.

The present invention relates to a cleaning method in one embodiment, which comprises the step of removing a resin mask from a cleaned object to which the resin mask is attached using a cleaning agent composition, wherein the cleaning agent composition comprises an alkali (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 solvent having two or more selected from A compound containing at least one of carboxyl and phosphonic acid groups, the content of component B in the above-mentioned cleaning agent composition when used is 1 mass % to 12 mass %, the content of component D in the above-mentioned cleaning agent composition when used is 65 mass % to 95 mass %, and the object to be cleaned has undergone the following steps, namely, at least one of the steps of welding and plating with a resin mask.

Description

Cleaning method and use of cleaning agent composition

The present invention relates to a cleaning method, a manufacturing method of electronic components using the cleaning method, and its use.

In recent years, in personal computers and various electronic devices, low power consumption, high processing speed, and miniaturization have been continuously developed, and the wiring of the package substrates mounted therein has been miniaturized year by year. In the formation of such fine wiring and connecting terminals such as pillars or bumps, the metal mask method has been mainly used so far, but because of its low versatility or difficulty in coping with the miniaturization of wiring, it is changing to other new methods.

As one of the new methods, there is a known method of using dry film photoresist instead of metal mask as thick film resin mask. The resin mask is eventually stripped and removed, and as a cleaning agent used for stripping and removing, there is a known cleaning agent for stripping resin mask containing alkali and water.

For example, Japanese Patent Publication No. 2007-254555 (Patent Document 1) discloses an alkaline cleaner capable of stripping and cleaning hardened photoresists such as color photoresists, black matrix resins, polyimide alignment films, and photospacers on color filter substrates for liquid crystal displays in a short time. The cleaner composition contains the following ingredients: one or more selected from the group consisting of specific quaternary ammonium salts and specific polycarboxylic acid salts, a hydrophilic organic solvent, and an alkaline component. Furthermore, in the embodiment, a cleaning agent is described, which includes 2.5 parts of tetrasodium ethylenediaminetetraacetate, 5 parts of diethylene glycol diethyl ether, 20 parts of diethylene glycol monomethyl ether, 10 parts of tetramethylammonium hydroxide and water as the remainder, totaling 100 parts.

In Japanese Patent Publication No. 2015-79244 (Patent Document 2), a cleaning agent composition for a resin mask layer containing a specific quaternary ammonium hydroxide, a water-soluble amine, an acid or its ammonium salt, and water is described as a cleaning agent that can promote the removal of the resin mask layer after the heat treatment of the solder bump and inhibit solder corrosion, and can improve the reliability of the solder connection. In addition, in an embodiment, a cleaning agent composition is described, which includes 1 mass part of tetramethylammonium hydroxide, 5 mass parts of monoethanolamine, 1 mass part of ammonium formate, 85 mass parts of water, 4 mass parts of diethylene glycol butyl ether, and 4 mass parts of dimethyl sulfoxide.

Japanese Patent Publication No. 2006-173566 (Patent Document 3) discloses a stripper composition having a low environmental load, excellent stripping properties of photoresist residues and metal oxide products from metal wirings after ashing even under low temperature and short time cleaning conditions, and excellent corrosion resistance to metal wirings. The stripper composition comprises an organic amine content of 0.2-30 wt %, an organic phosphonic acid content of 0.05-10 wt %, and water content of 60-99.7 wt %, and the pH value of the composition at 20° C. is 9-13. Furthermore, in the embodiment, a stripping agent composition is described, which 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.

WO2018/043440 (Patent Document 4) describes a treatment liquid for semiconductor components, which contains a hydroxylamine compound, an alkaline compound, and at least one selected from the group consisting of a reducing agent and a chelating agent, and has a pH value of 10 or more. In addition, in an embodiment, a treatment liquid is described, which contains 10.0% hydroxylamine, 10% tetrahydrofurfurylamine, 40% 3-methoxy-3-methyl-1-butanol, 5.0% diethylenetriaminepentaacetic acid, 1% 5-MBTA5-methyl-1H-benzotriazole, and water as the remainder (34%).

The present invention relates to a cleaning method in one embodiment, which comprises the step of removing a resin mask from a cleaned object to which the resin mask is attached using a cleaning agent composition, wherein the cleaning agent composition contains an alkali (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 solvent having two or more selected from A compound containing at least one of carboxyl and phosphonic acid groups, the content of component B in the above-mentioned cleaning agent composition when used is 1 mass % to 12 mass %, the content of component D in the above-mentioned cleaning agent composition when used is 65 mass % to 95 mass %, and the object to be cleaned has undergone the following steps, namely, at least one of the steps of welding and plating with a resin mask.

The present invention in one embodiment relates to a method for manufacturing electronic components, which includes the step of using the cleaning method of the present invention to peel off a resin mask from an object to be cleaned to which the resin mask is attached.

The present invention relates to a use of a cleaning agent composition in one embodiment, wherein the cleaning agent composition is used as a stripping agent when stripping a resin mask from a cleaned object, wherein the cleaned object is subjected to at least one of a welding process and a plating process using a resin mask; the cleaning agent composition contains an alkali (component A), an organic solvent (component B), a chelating agent, and a solvent. The composition comprises a solvent (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. 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.

After forming fine wiring on a printed circuit board, etc., in order to reduce the residue of the resin mask and the residue of the additives contained in the solder or plating liquid used to form the fine wiring or bumps, the cleaning agent composition is required to have higher cleanliness.

The so-called resin mask is formed using a photoresist, and the physical properties of the photoresist such as solubility relative to the developer are changed by light or electron beams. Photoresists are generally divided into negative and positive types according to the reaction method with light or electron beams. Negative photoresists have the characteristic that their solubility relative to the developer decreases when exposed to light, and a layer containing negative photoresists (hereinafter also referred to as a "negative photoresist layer") uses the exposed part as a resin mask after exposure and development. Positive photoresist has the property that its solubility in developer increases when exposed. After exposure and development, the exposed portion of the layer containing positive photoresist (hereinafter, also referred to as "positive photoresist layer") is removed, and the unexposed portion is used as a resin mask. By using a resin mask with such a property, fine connection portions of circuit boards such as metal wiring, metal pillars or solder bumps can be formed.

However, as wiring becomes finer, it becomes difficult to remove the resin mask in the fine gaps. In addition, if the cleaning power is only enhanced, there is a concern that the substrate surface may be dissolved, deteriorated, etc., causing damage to the substrate. That is, the cleaning agent composition is required not only to have a higher resin mask removal performance, but also to have less impact on the substrate.

In this regard, the present invention provides a cleaning method in one embodiment that can reduce the impact on the substrate and has excellent resin mask removal performance.

[Cleaning method]

The present invention relates to a cleaning method (hereinafter, also referred to as "the cleaning method of the present invention"), which comprises the step of removing a resin mask from a cleaned object to which the resin mask is attached using a cleaning agent composition, wherein the cleaning agent composition contains an alkali (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, the content of component B in the above-mentioned cleaning agent composition when used is 1 mass % to 12 mass %, the content of component D in the above-mentioned cleaning agent composition when used is 65 mass % to 95 mass %, and the object to be cleaned has undergone the following steps, that is, at least one of the steps of welding and plating treatment using a resin mask.

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

The details of the mechanism of action of the cleaning method of the present invention are still unclear, but it is presumed as follows.

There is a phenomenon that tiny residues of the resin mask are generated in the fine gaps of the circuit pattern formed by copper plating, etc.

In the present invention, it is believed that the alkali (component A), at least one organic solvent selected from glycol ethers and aromatic ketones (component B), and water (component D) penetrate into the resin mask, thereby promoting the dissociation of the alkali-soluble resin formulated in the resin mask, thereby causing charge repulsion and promoting the peeling of the resin mask. On the other hand, it is believed that in the presence of the alkali (component A), a specific chelating agent (component C) is adsorbed to the surface of the circuit pattern formed by copper plating, etc., so that the resin mask remaining in the fine gaps of the circuit pattern becomes easy to be removed. It is presumed that cleaning performance is improved by promoting the peeling of the resins and increasing the ease with which the resins can be released from the gaps.

Furthermore, it is believed that by setting the contents of component B and water (component D) contained in the cleaning method of the present invention within a specified range, the influence of component B and/or component C on the substrate is suppressed, and excellent cleaning performance is exhibited.

However, the present invention may be interpreted without being limited to this mechanism.

In the present invention, the resin mask to be peeled off or removed refers to a mask used to protect the surface of a material during self-etching, plating, heating, etc., that is, a mask that functions as a protective film. As the resin mask, in one or more embodiments, a photoresist layer after exposure and development steps, a photoresist layer subjected to at least one of exposure and development (hereinafter, also referred to as "exposed and/or developed"), or a hardened photoresist layer can be listed. As the resin material for forming the resin mask, in one or more embodiments, a film-like photosensitive resin, a photoresist film, or a photoresist can be listed. The photoresist film can use a general-purpose one.

The cleaning method of the present invention includes the step of using a cleaning agent composition to peel off the resin mask from the object to be cleaned to which the resin mask is attached, and the object to be cleaned has undergone the following steps, that is, at least one of the steps of welding and plating using the resin mask.

In the cleaning method of the present invention, the step of stripping the resin mask from the object to be cleaned includes, in one or more embodiments, the step of bringing the object to be cleaned with the resin mask attached thereto into contact with the cleaning agent composition of the present invention. Hereinafter, the cleaning agent 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 referred to as the "cleaning agent composition of the present invention". Therefore, the present invention, in one aspect, relates to a cleaning method using a cleaning agent composition for resin mask stripping (the cleaning agent composition of the present invention), wherein the cleaning agent composition contains an alkali (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 at least two acid groups selected from carboxyl groups and phosphonic acid groups, the content of component B when used is 1 mass % to 12 mass %, and the content of component D when used is 65 mass % to 95 mass %. According to the cleaning agent composition of the present invention, a cleaning method capable of reducing the impact on the substrate and having excellent resin mask removal performance can be provided in one or more embodiments.

As a method of using the cleaning agent composition of the present invention to remove the resin mask from the object to be cleaned, or a method of bringing the cleaning agent composition of the present invention into contact with the object to be cleaned, for example, there can be listed: a method of bringing the object into contact by immersing it in a cleaning bath containing the cleaning agent composition, a method of bringing the object into contact by ejecting the cleaning agent composition in a spray form (shower type), an ultrasonic cleaning method of irradiating the object with ultrasonic waves during immersion, etc. The cleaning agent composition of the present invention can be used directly for cleaning without dilution. As the object to be cleaned, there can be listed the above-mentioned objects to be cleaned.

The cleaning method of the present invention may include, in one or more embodiments, the steps of bringing the object to be cleaned into contact with the cleaning agent composition, then rinsing with water, and drying. The cleaning method of the present invention may include, in one or more embodiments, the steps of bringing the object to be cleaned into contact with the cleaning agent composition, then rinsing with water.

From the perspective of making it easier to exert the cleaning power of the cleaning agent composition of the present invention, the cleaning method of the present invention is preferably to irradiate the cleaning agent composition of the present invention with ultrasound when it is in contact with the object to be cleaned, and more preferably the ultrasound has a relatively high frequency. From the same point of view, the irradiation conditions of the above-mentioned ultrasound are preferably 26~72kHz, 80~1500W, and more preferably 36~72kHz, 80~1500W.

In the cleaning method of the present invention, from the perspective of easily exerting the cleaning power of the cleaning agent composition of the present invention, the temperature of the cleaning agent composition is preferably above 40°C, more preferably above 50°C, and from the perspective of reducing the impact on the substrate, it is preferably below 70°C, more preferably below 60°C.

[Ingredient A: Alkaline]

As the alkali contained in the cleaning agent composition of the present invention (hereinafter also referred to as "component A"), in one or more embodiments, at least one selected from inorganic bases and organic bases can be listed. From the perspective of reducing the wastewater treatment load, inorganic bases are preferred. Component A can be one or a combination of two or more.

As the inorganic base, in one or more embodiments, hydroxides, carbonates, or silicates of alkali metals or alkali earth metals can be listed. Specifically, at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and potassium silicate can be listed. From the viewpoint of improving the resin mask removal performance, among these, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate is preferred, and at least one of sodium hydroxide and potassium hydroxide is more preferred, and potassium hydroxide is further preferred. In the present invention, the inorganic base does not include ammonia.

As an organic base, in one or more embodiments, quaternary ammonium hydroxide represented by the following formula (I), amine represented by the following formula (II), etc. can be listed. As component A, in one or more embodiments, from the perspective of improving the resin mask removal performance, it is preferred to use a combination of a quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II). In addition, from the perspective of improving the resin mask removal performance, component A is preferably a quaternary ammonium hydroxide represented by the following formula (I).

In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently at least one selected from the group consisting of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl.

環。 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, and R ⁷ is at least one selected from an aminoethyl group, a hydroxyethyl group or a hydroxypropyl group, or in formula (II), R ⁵ is at least one selected from a methyl group, an ethyl group, an aminoethyl group, a hydroxyethyl group or a hydroxypropyl group, and R ⁶ and R ⁷ are bonded to each other and form a pyrrolidine ring or a piperidine ring together with the N atom in formula (II).

ring.

As the quaternary ammonium hydroxide represented by formula (I), for example, salts containing quaternary ammonium cations and hydroxides can be cited. As specific examples of the quaternary ammonium hydroxide, there can be cited tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropyl hydroxide, At least one of ammonium, bis(2-hydroxyethyl)dimethylammonium hydroxide, bis(2-hydroxyethyl)diethylammonium hydroxide, bis(2-hydroxyethyl)dipropylammonium hydroxide, tri(2-hydroxyethyl)methylammonium hydroxide, tri(2-hydroxyethyl)ethylammonium hydroxide, tri(2-hydroxyethyl)propylammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide, and tetra(2-hydroxypropyl)ammonium hydroxide. From the viewpoint of improving the removability of the resin mask, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred, and tetramethylammonium hydroxide is more preferred.

、1-(2-羥乙基)吡咯啶、1-(2-羥乙基)哌

、乙二胺及二伸乙基三胺中之至少一種。從提昇樹脂遮罩去除性之觀點而言，該等之中較佳為單乙醇胺及二乙醇胺，更佳為單乙醇胺。 As the amine represented by formula (II), for example, alkanolamines, mono- to tri-amines, and heterocyclic compounds can be listed. As specific examples of amines, there can be listed those 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-methylpiperidin ...

, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperidin

At least one of ethylenediamine, ethylenediamine and diethylenetriamine. From the perspective of improving the resin mask removal performance, monoethanolamine and diethanolamine are preferred, and monoethanolamine is more preferred.

As for the content of component A in the cleaning agent composition of the present invention when used, from the perspective of improving the resin mask removal performance, it is preferably 1 mass% or more, more preferably 4 mass% or more, and further preferably 6 mass% or more, and from the same perspective, it is preferably 20 mass% or less, more preferably 16 mass% or less, and further preferably 12 mass% or less. More specifically, the content of component A in the cleaning agent composition of the present invention when used is preferably 1 mass% or more and 20 mass% or less, more preferably 4 mass% or more and 16 mass% or less, and further preferably 6 mass% or more and 16 mass% or less. When component A is a combination of two or more, the content of component A refers to the total content of such components.

The "content of each component of the cleaning agent composition when it is used" in the present invention refers to the content of each component at the time of cleaning, that is, the time point when the cleaning agent composition is used for cleaning.

[Ingredient B: organic solvent]

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

As glycol ethers, from the perspective of improving the removability of the resin mask and reducing the impact on the substrate, compounds having a structure in which 1 mol to 3 mol of ethylene glycol are added to an alcohol having 1 to 8 carbon atoms can be cited. As specific examples of glycol ethers, 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 can be cited.

As aromatic ketones, acetophenone and the like can be cited from the perspective of improving the removability of resin masks and reducing the impact on substrates.

As for the content of component B in the cleaning agent composition of the present invention when used, from the perspective of improving the resin mask removal performance, it is 1 mass% or more, preferably 1.5 mass% or more, and more preferably 2 mass% or more, and from the perspective of reducing the drainage treatment load and reducing the impact on the substrate, it is 12 mass% or less, preferably 8 mass% or less, and more preferably 4 mass% or less. More specifically, the content of component B when used is 1 mass% or more and 12 mass% or less, preferably 1.5 mass% or more and 8 mass% or less, and more preferably 2 mass% or more and 4 mass% or less. When component B is a combination of two or more, the content of component B refers to the total content of them.

[Ingredient C: Chelating agent]

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

From the perspective of improving the removability of the resin mask, the molecular weight of component C is preferably 1000 or less, and more preferably 500 or less.

As for the content of component C in the cleaning agent composition of the present invention when used, from the perspective of improving the resin mask removal performance, it is preferably 0.5 mass% or more, more preferably 1 mass% or more, and from the same perspective, it is preferably 5 mass% or less, more preferably 3 mass% or less. More specifically, the content of component C when used is preferably 0.5 mass% or more and 5 mass% or less, more preferably 1 mass% or more and 3 mass% or less. When component C is a combination of two or more, the content of component C refers to the total content of such components.

In the cleaning agent composition of the present invention, the mass ratio (C/B) of component C relative to component B is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.4 or more from the perspective of improving the resin mask removal performance and reducing the impact on the substrate. From the same perspective, it is preferably 1 or less, more preferably 0.8 or less, and further 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 further preferably 0.4 or more and 0.7 or less.

In the cleaning agent composition of the present invention, 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 from the perspective of improving the resin mask removal performance and reducing the impact on the substrate. From the same perspective, it is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less. More specifically, 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.

[Ingredient D: Water]

As water contained in the cleaning agent composition of the present invention (hereinafter also referred to as "component D"), in one or more embodiments, ion exchange water, RO (reverse osmosis) water, distilled water, pure water, ultrapure water, etc. can be listed.

The content of component D in the cleaning agent composition of the present invention can be set to the remainder excluding component A, component B, component C and any of the following components. Specifically, the content of component D in the cleaning agent composition of the present invention when used is 65% by mass or more, preferably 75% by mass or more, and more preferably 82% by mass or more from the viewpoint of improving the resin mask removal performance, reducing the drainage treatment load, and reducing the impact on the substrate. In addition, from the viewpoint of improving the resin mask removal performance, 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 agent composition of the present invention when used is 65 mass% to 95 mass% in one or more embodiments, preferably 75 mass% to 90 mass% and more preferably 82 mass% to 87 mass%. The content of component D in the cleaning agent composition of the present invention when used is 82 mass% to 95 mass% in one or more embodiments, preferably 82 mass% to 90 mass% and more preferably 82 mass% to 97 mass%.

In the cleaning agent composition of the present invention, the mass ratio (D/B) of component D relative to component B is preferably 5 or more, more preferably 13 or more, and further preferably 25 or more from the perspective of improving the resin mask removal performance, reducing the drainage treatment load, and reducing the impact on the substrate. Moreover, from the perspective of improving the resin mask removal performance, it is preferably 45 or less, more preferably 40 or less, and further 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 further preferably 25 or more and 35 or less.

In the cleaning agent composition of the present invention, 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 from the perspective of improving the resin mask removal performance, reducing the drainage treatment load, and reducing the impact on the substrate. Moreover, from the perspective of improving the resin mask removal performance, it 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.

[Ingredient E: ammonium salt of ammonia or organic acid]

In one or more embodiments of the cleaning agent composition of the present invention, from the perspective of resin mask removal, it is preferred to further include 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, it is preferably an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms, and more preferably ammonium formate. Component E may be one or a combination of two or more.

As for the content of component E in the cleaning agent composition of the present invention when used, from the perspective of improving the resin mask removal performance, it is preferably 0.1 mass% to 2 mass%, more preferably 0.2 mass% to 1.5 mass%, and more preferably 0.3 mass% to 1 mass%. When component E is a combination of two or more, the content of component E refers to the total content of these components.

[Other ingredients]

In addition to the above-mentioned components A to E, the cleaning agent composition of the present invention may also contain other components as needed. As other components, components that can be used in ordinary cleaning agents can be listed, for example, organic solvents other than component B, surfactants, chelating agents other than component C, thickeners, dispersants, rust inhibitors, polymer compounds, solubilizers, antioxidants, preservatives, defoaming agents, antibacterial agents, etc. can be listed.

The content of other ingredients in the cleaning agent composition of the present invention when used is preferably 0% by mass to 2% by mass, more preferably 0% by mass to 1.5% by mass, further preferably 0% by mass to 1.3% by mass, further preferably 0% by mass to 1% by mass.

The cleaning agent composition of the present invention may be free of hydroxylamine and/or its salt in one or more embodiments.

The cleaning agent composition of the present invention may be substantially free of straight-chain sugar alcohols in one or more embodiments. For example, the straight-chain sugar alcohol content of the cleaning agent composition of the present invention during use is less than 0.1% by weight in one or more embodiments.

As for the total content of organic matter from component A, component B, component C and any component of the cleaning agent composition of the present invention when used, from the viewpoint of reducing the drainage treatment load and reducing the impact on the substrate, it is preferably 30 mass % or less, more preferably 25 mass % or less, further preferably 20 mass % or less, further preferably 16 mass % or less, and from the viewpoint of improving the resin mask removability, it is preferably 2 mass % or more, more preferably 4 mass % or more, further preferably 8 mass % or more, further preferably 12 mass % or more. More specifically, the total content of organic matter from component A, component B, component C and any component in the cleaning agent composition of the present invention when used is preferably 2 mass% to 30 mass%, more preferably 4 mass% to 25 mass%, further preferably 8 mass% to 20 mass%, further preferably 12 mass% to 16 mass%.

As for the pH value of the cleaning agent composition of the present invention during use, from the perspective of improving the resin mask removal performance and reducing the impact on the substrate, it is preferably 10 or more, more preferably 11 or more, further preferably 12 or more, and further preferably 13 or more. In the present invention, the so-called "pH value during use" refers to the pH value at 25°C, which can be measured using a pH meter. Specifically, it can be measured by the method described in the embodiment.

[Manufacturing method of cleaning agent composition]

The cleaning agent composition of the present invention can be manufactured by blending the above-mentioned components A to D and the above-mentioned arbitrary components as needed using a known method. For example, the cleaning agent composition of the present invention can be formed by blending at least the above-mentioned components A to D. Therefore, the present invention is related to a method for manufacturing a cleaning agent composition comprising at least the step of blending the above-mentioned components A to D. In the present invention, the so-called "blending" includes the step of mixing the components A to D and the above-mentioned arbitrary components as needed at the same time or in any order. In the method for manufacturing the cleaning agent composition of the present invention, the preferred blending amount of each component can be set to be the same as the preferred content of each component of the above-mentioned cleaning agent composition of the present invention.

The cleaning agent composition of the present invention can be separated or precipitated to prepare a concentrate with a reduced amount of water (component D) within a range that does not impair storage stability. As for the concentrate of the cleaning agent composition, from the viewpoint of transportation and storage, it is preferably prepared as a concentrate with a dilution ratio of 3 times or more, and from the viewpoint of storage stability, it is preferably prepared as a concentrate with a dilution ratio of 30 times or less. The concentrate of the cleaning agent composition can be diluted with water (component D) when used so that the components A to D and the optional components are used at the above content (i.e., the content during cleaning). Furthermore, the concentrate of the cleaning agent composition can also be used by adding each component separately when it is used. In the present invention, the "when using" or "when cleaning" of the cleaning agent composition as a concentrated liquid refers to the state of the concentrated cleaning agent composition after dilution.

The cleaning agent composition of the present invention can be used as a stripping agent in one or more embodiments, and the stripping agent is used to strip the resin mask from the object to be cleaned, and the object to be cleaned has undergone the following steps, that is, at least one of the steps of welding and plating using a resin mask.

That is, the present invention relates to a use of a cleaning agent composition in one embodiment, wherein the cleaning agent composition is used as a stripping agent when stripping a resin mask from a cleaned object, wherein the cleaned object has been subjected to at least one of welding and plating treatments using a resin mask; the cleaning agent composition contains an alkali (component A), an organic solvent (component B) , chelating agent (ingredient C) and water (ingredient D), ingredient B is at least one solvent selected from glycol ethers and aromatic ketones, ingredient C is a compound having at least two acid groups selected from carboxyl groups and phosphonic acid groups, the content of ingredient B when used is 1 mass% to 12 mass%, and the content of ingredient D when used is 65 mass% to 95 mass%.

[Things to be cleaned]

The cleaning agent composition of the present invention can be used to clean an object to be cleaned with a resin mask in one or more embodiments. As the object to be cleaned, in one or more embodiments, an object to be cleaned having a metal part on the surface can be listed, for example, electronic parts and their manufacturing intermediates can be listed. As the electronic parts, for example, at least one part selected from metal plates such as printed circuit boards, wafers, copper plates and aluminum plates can be listed. The above-mentioned manufacturing intermediates are intermediate products in the manufacturing steps of electronic parts, including intermediate products after resin mask treatment.

As a specific example of the object to be cleaned with a resin mask attached, for example, electronic parts with wiring or connection terminals formed on the surface of a substrate can be listed by performing at least one of the steps of soldering and plating (copper plating, aluminum plating, nickel plating, etc.) using a resin mask. In the present invention, soldering refers to making solder exist on the part of the substrate where the resin mask does not exist, and forming solder bumps by heating. In the present invention, plating refers to performing at least one plating treatment selected from copper plating, aluminum plating, and nickel plating on the part of the substrate where the resin mask does not exist. The so-called resin mask non-existing portion refers to the portion where the resin mask is removed by developing the anti-corrosion pattern formed by developing the resin mask laminated on the substrate. Therefore, the present invention, in one aspect, is related to the use of the cleaning agent composition of the present invention as a cleaning agent in the manufacture of electronic parts. In one or more embodiments, the object to be cleaned has undergone the following steps, that is, at least one of welding and plating treatment on a substrate having an anti-corrosion pattern, and the above-mentioned anti-corrosion pattern is formed by developing the resin mask laminated on the substrate. For example, as the object to be cleaned, there can be cited a substrate having the following parts: a part where a resin mask exists as a hardened photoresist layer formed on the substrate, and a part where a solder bump or a coating layer is formed in a part where the resin mask does not exist.

In one or more embodiments, the cleaning agent composition of the present invention can be preferably used for cleaning an object to which a resin mask is attached or a resin mask that has been subjected to a coating treatment and/or a heat treatment is applied. The resin mask can be, for example, a negative resin mask or a positive resin mask. In the present invention, the so-called negative resin mask refers to one formed using a negative photoresist, for example, a negative photoresist layer that has been subjected to an exposure and/or development treatment. In the present invention, the so-called positive resin mask refers to one formed using a positive photoresist, for example, a positive photoresist layer that has been exposed and/or developed.

[Manufacturing method of electronic parts]

The present invention, in one embodiment, relates 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 the step of stripping a resin mask from an object to be cleaned to which the resin mask is attached using the cleaning method of the present invention. The above-mentioned objects to be cleaned can be cited as the 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 making it possible to manufacture electronic components with higher reliability. Furthermore, by performing the cleaning method of the present invention, it becomes easier to remove the resin mask attached to the electronic components, thereby shortening the cleaning time and thus improving the manufacturing efficiency of the electronic components.

[Set]

The present invention, in one embodiment, relates to a kit for use in any one of the cleaning method of the present invention and the method for manufacturing electronic components of the present invention (hereinafter, also referred to as the "kit of the present invention"). The kit of the present invention is a kit for manufacturing the cleaning agent composition of the present invention in one or more embodiments. The kit of the present invention can obtain a cleaning agent composition that can reduce the impact on the substrate and has excellent resin mask removal performance.

As an embodiment of the kit of the present invention, the following kit (three-liquid cleaning agent composition) can be listed, which contains the above solutions in a state where the solution containing component A (first liquid), the solution containing component B (second liquid), and the solution containing component C (third liquid) are not mixed with each other, and at least one selected from the first liquid, the second liquid, and the third liquid further contains a part or all of component D, and the first liquid, the second liquid, and the third liquid are mixed when used. After the first liquid, the second liquid, and the third liquid are mixed, they can be diluted with component C (water) as needed. In each of the first liquid, the second liquid, and the third liquid, any of the above components can be included as needed.

As another embodiment of the kit of the present invention, the following kit (two-liquid cleaning agent composition) can be cited, which contains the above solutions in a state where the solution containing component A and component C (first liquid) and the solution containing component B (second liquid) are not mixed with each other, and at least one of the first liquid and the second liquid further contains a part or all of component D (water), and the first liquid and the second liquid are mixed when used. After the first liquid and the second liquid are mixed, they can be diluted with component D (water) as needed. In each of the first liquid and the second liquid, any of the above components can be included as needed.

The present invention further relates to one or more of the following implementation methods.

<1> A cleaning agent composition for stripping resin masks, which contains an alkali (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, and the content of component B when used is 1 mass % to 12 mass %, and the content of component D when used is 65 mass % to 95 mass %.

<2> The cleaning agent composition of <1>, wherein the content of component C when used is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less. More specifically, the content of component C when used 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.

<3> The cleaning agent composition of <1> or <2>, wherein the mass ratio (C/B) of component C to component B is preferably 0.1 or more, more preferably 0.3 or more, and further preferably 0.4 or more, and is preferably 1 or less, more preferably 0.8 or less, and further 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 further preferably 0.4 or more and 0.7 or less.

<4> A cleaning agent composition as described in any one of <1> to <3>, wherein the mass ratio (D/B) of component D relative to component B is preferably 5 or more, more preferably 13 or more, and further preferably 25 or more, and preferably 45 or less, more preferably 40 or less, and further 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 further preferably 25 or more and 35 or less.

<5> The pH value of the cleaning agent composition as described in any one of <1> to <4> at 25°C is preferably 10 or more, more preferably 11 or more, further preferably 12 or more, further preferably 13 or more.

<6> A cleaning agent composition as described in any one of <1> to <5>, wherein component B is preferably a compound having a structure in which 1 mol to 3 mol of ethylene glycol is 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.

<7> The cleaning agent composition of any one of <1> to <6> preferably further comprises at least one of ammonia and an ammonium salt of an organic acid (component E), more preferably further comprises an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms, and more preferably further comprises ammonium formate.

<8> A cleaning agent composition as described in any one of <1> to <7>, wherein component A is at least one selected from an inorganic base and an organic base, and the inorganic base is preferably a hydroxide, carbonate or silicate of an alkali metal or alkali earth metal, and more preferably selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, At least one of calcium oxide, sodium carbonate, potassium carbonate, sodium silicate and potassium silicate, preferably one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferably at least one of sodium hydroxide and potassium hydroxide, preferably potassium hydroxide.

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

In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently at least one selected from the group consisting of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl.

<10> The cleaning agent composition of 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).

In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently at least one selected from the group consisting of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl.

環。 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, and R ⁷ is at least one selected from an aminoethyl group, a hydroxyethyl group or a hydroxypropyl group, or in the formula (II), R ⁵ is at least one selected from a methyl group, an ethyl group, an aminoethyl group, a hydroxyethyl group or a hydroxypropyl group, and R ⁶ and R ⁷ are bonded to each other and form a pyrrolidine ring or a piperidine ring together with the N atom in the formula (II).

ring.

<11> The cleaning agent composition as described in <9> or <10>, wherein the quaternary ammonium hydroxide represented by formula (I) is preferably at least one selected from tetramethylammonium hydroxide and tetraethylammonium hydroxide, and more preferably tetramethylammonium hydroxide.

<12> The cleaning agent composition as described in <10>, wherein the amine represented by formula (II) is preferably at least one selected from monoethanolamine and diethanolamine, more preferably monoethanolamine.

<13> A cleaning agent composition as described in any one of <1> to <12>, wherein the content of component A in the cleaning agent composition when used is preferably 1 mass % or more, more preferably 4 mass % or more, and further preferably 6 mass % or more, and, from the same point of view, is preferably 20 mass % or less, more preferably 16 mass % or less, and further preferably 12 mass % or less. More specifically, the content of component A in the cleaning agent composition of the present invention when used is preferably 1 mass % or more and 20 mass % or less, more preferably 4 mass % or more and 16 mass % or less, and further preferably 6 mass % or more and 16 mass % or less.

<14> A cleaning agent composition as described in any one of <1> to <13>, wherein ingredient B is acetophenone.

<15> A cleaning agent composition as described in any one of <1> to <14>, wherein the content of component B when used is preferably 1.5% by mass or more, more preferably 2% by mass or more, and preferably 8% by mass or less, more preferably 4% by mass or less. More specifically, the content of component B when used 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.

<16> A cleaning agent composition as described in any one of <1> to <15>, wherein component C is preferably a compound having at least 4 acid groups selected from carboxyl groups and phosphonic acid groups, more preferably aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid, and further preferably 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid.

<17> A cleaning agent composition as described in any one of <1> to <16>, wherein the molecular weight of component C is preferably less than 1000, more preferably less than 500.

<18> A cleaning agent composition as described in 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.

<19> A cleaning agent composition as described in any one of <1> to <18>, wherein the content of component D when used 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, and more preferably 87% by mass or less. More specifically, the content of component D when used is 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.

<20> The cleaning agent composition of 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 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.

<21> A cleaning agent composition as described in any one of <1> to <20>, wherein the content of component E when used is preferably 0.1 mass % to 2 mass %, more preferably 0.2 mass % to 1.5 mass %, and even more preferably 0.3 mass % to 1 mass %.

<22> A cleaning agent composition as described in any one of <1> to <21>, wherein the content of straight-chain sugar alcohol when used in one or more embodiments is preferably less than 0.1% by weight, and more preferably substantially free of straight-chain sugar alcohol.

<23> The cleaning agent composition of any one of <1> to <22>, wherein the total content of organic matter from component A, component B, component C and any component when used is preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less, further preferably 16 mass% or less, and preferably 2 mass% or more, more preferably 4 mass% or more, further preferably 8 mass% or more, further preferably 12 mass% or more. More specifically, the total content of organic matter from component A, component B, component C and any component when used is preferably 2 mass% or more and 30 mass% or less, more preferably 4 mass% or more and 25 mass% or less, further preferably 8 mass% or more and 20 mass% or less, further preferably 12 mass% or more and 16 mass% or less.

<24> A cleaning agent composition as described in 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 other components other than components A to E in the cleaning agent composition is preferably 0% by mass to 2% by mass, more preferably 0% by mass to 1.5% by mass, further preferably 0% by mass to 1.3% by mass, further preferably 0% by mass to 1% by mass.

<25> A method for manufacturing electronic components, comprising the step of stripping a resin mask from an object to be cleaned to which the resin mask is attached, using a cleaning agent composition as described in any one of <1> to <24>.

<26> A method for manufacturing electronic components as in <25>, wherein the electronic components are at least one component selected from a printed circuit board, a wafer, and a metal plate.

<27> A cleaning method, comprising the step of stripping a resin mask from an object to be cleaned to which a resin mask is attached, using a cleaning agent composition as described in any one of <1> to <24>, wherein the object to be cleaned has undergone at least one of welding and plating treatments using a resin mask.

<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 at least one of soldering and plating treatment using a resin mask.

<29> A cleaning method as in <27> or <28>, wherein the object to be cleaned has undergone the following steps, namely, at least one of welding and plating treatments on a substrate having an anti-corrosion pattern, wherein the anti-corrosion pattern is formed by developing a resin mask laminated on the substrate.

<30> A cleaning method as described in any one of <27> to <29>, wherein the step of stripping the resin mask from the object to be cleaned preferably includes the step of bringing the object to be cleaned with the resin mask attached thereto into contact with a cleaning agent composition.

<31> A cleaning method as in <30>, wherein the method of bringing the cleaning agent composition of the present invention into contact with the object to be cleaned is preferably one or more of the following methods: a method of bringing the object into contact by immersing the object in a cleaning bath containing the cleaning agent composition, a method of bringing the object into contact by ejecting the cleaning agent composition in the form of a spray (shower type), and an ultrasonic cleaning method of irradiating the object with ultrasonic waves during immersion.

<32> A cleaning method as described in any one of <27> to <31>, wherein the temperature of the cleaning agent composition is preferably above 40°C, more preferably above 50°C, and preferably below 70°C, more preferably below 60°C.

<33> A use of a cleaning agent composition as described in any one of <1> to <24>, which is used as a cleaning agent for an object to be cleaned with a resin mask attached thereto.

<34> A use of a cleaning agent composition as described in any one of <1> to <24>, which is used as a stripping agent when stripping a resin mask from an object to be cleaned, wherein the object to be cleaned has been subjected to at least one of welding and plating treatments using a resin mask.

[Implementation example]

The present invention is described in detail below based on the embodiments, but the present invention is not limited to the embodiments.

1. Preparation of cleaning agent compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2

According to the conversion of active ingredients, component A, component B, component C, component D, and other components are prepared in the composition ratio shown in Table 1, and they are stirred and mixed to prepare the cleaning agent compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2. The composition in Table 1 is the amount of solid components. The pH value of each cleaning agent composition shown in Table 1 at 25°C is the value measured using a pH meter (Toa Electron Industries Co., Ltd., HM-30G), which is the value after the electrode of the pH meter is immersed in the cleaning agent composition for 3 minutes.

The following are used as components of the cleaning agent compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2.

(Ingredient A)

Tetramethylammonium hydroxide [Showa Denko Co., Ltd., TMAH (25%)]

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

Monoethanolamine [manufactured by Japan Catalyst Co., Ltd.]

1,2-Propylenediamine [Fuji Film Wako Pure Chemical Industries, Ltd.]

(Non-ingredient A)

Hydroxylamine [Fuji Film Wako Pure Chemical Industries, Ltd., Grade I, 50% aqueous solution]

(Ingredient B)

Diethylene glycol monobutyl ether [made by Japan Emulsifier Co., Ltd., diethylene glycol monobutyl ether]

Ethylene glycol monobenzyl ether [manufactured by Japan Emulsifier Co., Ltd., ethylene glycol monobenzyl ether]

Diethylene glycol monohexyl ether [made by Japan Emulsifier Co., Ltd., diethylene glycol monohexyl ether]

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

Diethylene glycol diethyl ether [Fuji Film Wako Pure Chemical Industries, Ltd., Grade 1, diethylene glycol Diethyl ether]

Acetophenone [Fuji Film Wako Pure Chemical Industries, Ltd., special grade]

(Ingredient C)

Etidronic acid [Italmatch Japan Co., Ltd., Dequest2010, content 60%]

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

Aminotrimethylenephosphonic acid [Italmatch Japan Co., Ltd., Dequest2000, content 50%]

(Ingredient D)

Water [pure water below 1μS/cm produced by the pure water device G-10DSTSET manufactured by Organo Co., Ltd.]

(Ingredient E)

Ammonium formate [Fushan Pharmaceutical Industry Co., Ltd.]

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

(Other ingredients)

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

2. Evaluation of cleaning agent composition

The cleaning agent compositions prepared in Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2 were evaluated as follows.

[Preparation of test pieces]

A photosensitive film (Photek RY-5560, 60μm thick, negative dry film photoresist) for forming a PKG substrate (Package Substrate) circuit was laminated on the surface of the electroless plated polyimide under the following conditions, and the exposed part was selectively exposed to harden (exposure step), and the unexposed part was removed by developing (development step), thereby obtaining a substrate with an anti-corrosion pattern (negative resin mask in the shape of the pattern). Then, the area where the unexposed part was removed by the above-mentioned development was copper-plated (50μm thick), thereby obtaining test pieces (30mm×50mm and 120mm×120mm).

(1) Lamination: Use a clean 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.

(2) Exposure: Exposure was performed using a direct drawing device for printed substrates (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.) at an exposure dose of 15 mJ/ ^cm2 .

(3) Pattern shape: L/S=20μm/20μm texture pattern

(4) Development: Use a substrate development device (manufactured by Yambo Technology Co., Ltd., LT-980366) and a 1% sodium carbonate aqueous solution at 30°C. Set the spray pressure to 0.2MPa and remove the resin mask from the unexposed area.

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

8mm×25mm)以600rpm之轉速進行攪拌後，於該狀態下將試片浸漬10分鐘。繼而，於100mL 玻璃燒杯中添加水100g將其作為沖洗槽，浸漬於該沖洗槽中進行沖洗後，藉由氮吹進行乾燥。 100 g of each cleaning agent composition of Examples 1-11, Comparative Examples 1-5 and Reference Examples 1-2 was added to a tall 200 mL glass beaker, heated to 50° C., and a rotor (fluororesin (PTFE (Polytetrafluoroethylene)) was used to rotate the beaker.

8mm×25mm) was stirred at 600rpm and the specimen was immersed for 10 minutes. Then, 100g of water was added to a 100mL glass beaker as a rinse tank, and the specimen was immersed in the rinse tank for rinsing and then dried by nitrogen blowing.

Using an optical microscope "Digital Microscope VHX-2000" (manufactured by Keyence Corporation) at 300 times magnification, visually check the presence or absence of resin mask remaining on the boundary of the fine line and solid part of the specific pattern area of the test piece after the cleaning test, and count the number of residues. The results are shown in Table 1. In the case where the number of residues is significantly large, such as the resin mask remaining continuously, it is recorded as ">50" in Table 1.

Furthermore, the test piece is 30mm×50mm in size and includes a copper circuit pattern with a thin line portion and a solid portion. The thickness of the pattern is 50μm, the width of the thin line portion is 20μm, and the width of the solid portion is 300~1500μm.

[Cleaning test, evaluation of the peeling start speed of the resin mask]

8mm×25mm)以600rpm之轉速進行攪拌後，於該狀態下浸漬試片。藉由目視觀察測定當確認到樹脂遮罩被剝離並於清潔劑組合物內漂浮之時間，如下所示地進行判定。將結果示於表1。 In a tall 200 mL glass beaker, 100 g of each cleaning agent composition of Examples 1-11, Comparative Examples 1-5 and Reference Examples 1-2 was added, heated to 50°C, and a rotor (fluororesin (PTFE),

8mm×25mm) was stirred at 600 rpm and then immersed in the test piece. The time when the resin mask was peeled off and floated in the cleaning agent composition was measured by visual observation and judged as follows. The results are shown in Table 1.

Furthermore, the test piece used is of the same shape as the immersion condition in the cleaning test.

<Evaluation criteria>

A: Within 5 minutes

B: Longer than 5 minutes, but less than 10 minutes

C: Longer than 10 minutes and less than 15 minutes

D: Longer than 15 minutes

[Evaluation of substrate damage]

Before and after the cleaning test under the above immersion conditions, visually check whether there is any change in the color of the pattern part in the appearance of the substrate, and the evaluation results based on the following evaluation criteria are shown in Table 1.

<Evaluation criteria>

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

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

As shown in Table 1, the results of the cleaning test under immersion conditions are as follows: compared with Reference Examples 1-2 without component C, Comparative Examples 1 and 4 without component B, Comparative Example 2 without component A, and Comparative Examples 3 and 5 where the contents of components B and D are not within the specified range, the cleaning agent compositions of Examples 1-11 can reduce the impact on the substrate and have excellent resin mask removal performance.

Furthermore, 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.

Furthermore, the cleaning agent compositions of Examples 1-2 and Reference Example 2 were subjected to a cleaning test under the conditions of continuous immersion and showering as shown below to evaluate the resin mask removal performance.

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

8mm×25mm)以300rpm之轉速進行攪拌後，於該狀態下將試片浸漬3分鐘。將另外準備之10L不鏽鋼燒杯作為儲槽，添加10kg與1L玻璃燒杯相同之清潔劑組合物，加溫至50℃。並且，藉由安裝有單流體噴嘴(扇形)VVP9060(池內股份有限公司製)作為噴霧嘴之盒型噴霧清潔機，將儲槽中之清潔劑組合物對試片進行2分鐘之噴霧(壓力：0.1MPa，噴霧距離：10cm)。再者，將所噴出之清潔劑組合物回收於儲槽中而循環再使用。其次，於1L玻璃燒杯中添加水1kg，將其作為沖洗槽，浸漬於該沖洗槽中進行沖洗後，藉由氮吹進行乾燥。 The immersion and showering were performed continuously according to the following points. 1 kg of each cleaning agent composition of Examples 1-2 and Reference Example 2 was added to a 1L glass beaker, heated to 50°C, and a rotor (fluororesin (PTFE),

8mm×25mm) was stirred at 300rpm, and the specimen was immersed in this state for 3 minutes. A 10L stainless steel beaker prepared separately was used as a storage tank, 10kg of the same cleaning agent composition as the 1L glass beaker was added, and the temperature was heated to 50°C. In addition, the cleaning agent composition in the storage tank was sprayed on the specimen for 2 minutes by a box-type spray cleaner equipped with a single-fluid nozzle (fan-shaped) VVP9060 (manufactured by Ikeuchi Co., Ltd.) as a spray nozzle (pressure: 0.1MPa, spray distance: 10cm). Furthermore, the sprayed cleaning agent composition is recovered in a storage tank and recycled. Next, 1 kg of water is added to a 1L glass beaker, which is used as a rinse tank. After immersion in the rinse tank for rinsing, the sample is dried by nitrogen blowing.

Using an optical microscope "Digital Microscope VHX-2000" (manufactured by Keyence Corporation) at 300 times magnification, visually check the presence or absence of resin mask remaining at the boundary between the fine line part and the solid part of the specific pattern area of the test piece after the cleaning test, and count the number of residues. The results are shown in Table 2.

Furthermore, the test piece has the same circuit pattern as the test piece under immersion condition except that its size is 120mm×120mm.

As shown in Table 2, the results of the cleaning test under immersion and shower conditions are: compared with Reference Example 2 which does not contain Component C, the cleaning agent composition of Examples 1-2 has excellent resin mask removal performance.

[Industrial availability]

According to the present invention, a cleaning agent composition for resin mask stripping can be provided, which can reduce the impact on the substrate and has excellent resin mask removal performance. Therefore, the cleaning method using the cleaning agent composition of the present invention can be used in the manufacturing steps of electronic components, which can shorten the cleaning steps of electronic components with resin masks attached and improve the performance and reliability of the manufactured electronic components, and can improve the productivity of semiconductor devices.

Claims (15)

A cleaning method, comprising the step of using a cleaning agent composition to remove a resin mask from a cleaned object to which the resin mask is attached, wherein the cleaning agent composition contains an alkali (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 solvent having two or more selected from carboxyl groups and phosphonic acid groups. The compound contains at least one acid group in the base, the content of component B in the above-mentioned cleaning agent composition when used is 1 mass % to 12 mass %, the content of component D in the above-mentioned cleaning agent composition when used is 65 mass % to 95 mass %, the object to be cleaned has undergone the following steps, namely, at least one of the steps of welding and plating with a resin mask. The cleaning method of claim 1, wherein the content of component C in the cleaning agent composition during use is greater than 0.5 mass % and less than 5 mass %. The cleaning method of claim 1 or 2, wherein the mass ratio of component C to component B (C/B) is greater than or equal to 0.1 and less than or equal to 1. The cleaning method of claim 1 or 2, wherein the mass ratio of component D to component B (D/B) is 5 to 45. The cleaning method of claim 1 or 2, wherein the pH value of the cleaning agent composition at 25°C is greater than 10. The cleaning method of claim 1 or 2, wherein component B is a compound having a structure in which 1 mol to 3 mol of ethylene glycol is added to an alcohol having 1 to 8 carbon atoms. The cleaning method of claim 1 or 2, wherein component A is a quaternary ammonium hydroxide represented by the following formula (I), In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently at least one selected from the group consisting of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl. A cleaning method as claimed in claim 1 or 2, wherein the cleaning agent composition further comprises at least one of ammonia and an ammonium salt of an organic acid (component E), and the content of other components other than components A to E in the cleaning agent composition is greater than 0 mass % and less than 2 mass %. The cleaning method of claim 1 or 2, wherein the total content of organic matter from component A, component B, component C and any component in the cleaning agent composition when used is less than 30 mass %. The cleaning method of claim 1 or 2, wherein the content of component D in the cleaning composition during use is 82 mass % to 95 mass %. The cleaning method of claim 1 or 2, wherein the mass ratio of component D to component C (D/C) is 30 to 90. A cleaning method as claimed in claim 1 or 2, wherein the object to be cleaned has undergone at least one of a welding and a plating process on a substrate, and the substrate has an anti-corrosion pattern formed by developing a resin mask laminated on the substrate. A method for manufacturing electronic components, comprising the step of stripping a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning method as described in any one of claims 1 to 12. A method for manufacturing an electronic component as claimed in claim 13, wherein the electronic component is a printed circuit board. A use of a cleaning agent composition, wherein the cleaning agent composition is used as a stripping agent when stripping a resin mask from a cleaned object, wherein the cleaned object has been subjected to at least one of welding and plating treatments using a resin mask; the cleaning agent composition contains an alkali (component A), an organic solvent (component B), a chelating agent (component C ) and water (ingredient D), ingredient B is at least one solvent selected from glycol ethers and aromatic ketones, ingredient C is a compound having at least two acid groups selected from carboxyl groups and phosphonic acid groups, the content of ingredient B when used is 1 mass % to 12 mass % and the content of ingredient D when used is 65 mass % to 95 mass %.