Method for cleaning a substrate

Abstract

The present application provides, in one embodiment, a cleaning method which is excellent in resin mask removal, and which can suppress corrosion and discoloration of copper. The present application relates, in one embodiment, to a cleaning method of a substrate, which includes a step of peeling a resin mask from a substrate having a copper-containing metal layer and the resin mask on a surface, using a cleaning agent composition containing an alkali agent (component A), an ammonium ion (NH4 + , component B), mercaptoacetic acid (component C), and water (component D), and the molar ratio (B / C) of component B to component C is 1.5 or more.

Description

TECHNICAL FIELD

[0001] The present application relates to a cleaning agent composition for resin mask peeling, a substrate cleaning method using the same, and an electronic component manufacturing method. BACKGROUND

[0002] In recent years, personal computers, various electronic devices, and the like are being increasingly developed in terms of low power consumption, high processing speed, and miniaturization. The wiring of a package substrate or the like mounted in these devices is also being increasingly developed in terms of miniaturization. In order to form such fine wiring and connection terminals such as pillars and bumps, a metal mask method has been mainly used in the past, but this method is being replaced by other new methods because of its low versatility and difficulty in coping with the miniaturization of wiring and the like.

[0003] As one of the new methods, a method of using a dry film resist instead of a metal mask to form a thick film resin mask is known. The resin mask is finally peeled off and removed, and a cleaning agent for peeling and removing the resin mask is known, which includes an alkali agent and water.

[0004] For example, in Japanese Patent Application Publication No. 2014-78009 (Patent Literature 1), a composition containing an alkanolamine, an organic solvent, water, a hydroxide, and an anticorrosive agent is described, which can effectively remove a film or a resist without damaging a substrate structure under the thick film or the resist.

[0005] In Japanese Patent Application Publication No. 2015-79244 (Patent Literature 2), as a cleaning agent that can improve solder connection reliability by giving consideration to both the promotion of removal of a resin mask layer after heat treatment of a solder bump and the suppression of solder corrosion, a resin mask layer cleaning agent composition containing a specific quaternary ammonium hydroxide, a water-soluble amine, an acid or an ammonium salt thereof, and water is described. SUMMARY

[0006] The present application relates to a substrate cleaning method including a step of peeling a resin mask from a substrate having a copper-containing metal layer and the resin mask on a surface using a cleaning agent composition containing an alkali agent (component A), an ammonium ion (NH4 + , component B), mercaptoacetic acid (component C), and water (component D), and a molar ratio (B / C) of component B to component C is 1.5 or more.

[0007] The present application relates to an electronic component manufacturing method including a step of peeling a resin mask from a substrate having a copper-containing metal layer and the resin mask on a surface using the substrate cleaning method of the present application.

[0008] The present application relates to a cleaning agent composition for resin mask peeling, which contains an alkali agent (component A), an ammonium ion (NH4+ , mercaptoacetic acid (component C), and water (component D), and the molar ratio (B / C) of component B to component C is 1.5 or more.

[0009] The present application relates to a use of a cleaning agent composition for cleaning a substrate having a copper-containing metal layer and a resin mask on a surface, the cleaning agent composition containing an alkali agent (component A), an ammonium ion (NH4 + , mercaptoacetic acid (component C), and water (component D), and the molar ratio (B / C) of component B to component C is 1.5 or more. DETAILED DESCRIPTION

[0010] After forming fine wiring on a printed substrate or the like, in order to reduce the residue of the resin mask and the residue of an additive or the like contained in solder, plating solution or the like used when forming fine wiring, bumps, or the like, a cleaning agent composition is required to have high cleaning performance.

[0011] Here, the so-called resin mask is formed using a resist whose solubility or the like in a developing solution changes due to light, electron beams or the like. The resist is roughly classified into a negative type and a positive type according to the reaction method with light, electron beams or the like. The negative resist has a property that the solubility in a developing solution decreases when exposed to light, and a layer containing the negative resist (hereinafter also referred to as "negative resist layer") is used as a resin mask after exposure and developing treatment, with the exposed portion being removed. The positive resist has a property that the solubility in a developing solution increases when exposed to light, and a layer containing the positive resist (hereinafter also referred to as "positive resist layer") is used as a resin mask after exposure and developing treatment, with the unexposed portion being removed. By using a resin mask having such a property, a fine connection portion of a circuit substrate such as a metal wiring, a metal pillar, a solder bump or the like can be formed. The resin mask must be removed after fine wiring, bump formation.

[0012] However, as the wiring is made finer, it becomes difficult to remove the resin mask in a fine gap, and a cleaning agent composition is required to have high resin mask removal performance. Furthermore, corrosion and discoloration of copper, which is used in most of the wiring and connection terminals, can cause a decrease in quality and value of a package substrate, and thus a cleaning agent composition is required to have high corrosion prevention performance and discoloration prevention performance. In addition, it is known that discoloration of copper is caused by, for example, the generation of sulfide on the surface of copper, and in the case where a copper removal process (for example, seed etching process) is performed after a cleaning process, it is difficult to remove the discolored copper.

[0013] Therefore, the present application provides, in one embodiment, a substrate cleaning method and a resin mask peeling cleaning agent composition which are excellent in resin mask removal performance and can suppress corrosion and discoloration of copper.

[0014] The present application is based on the recognition that by using a cleaning agent composition containing an ammonium ion and thioglycolic acid in a specific molar ratio, corrosion of copper can be inhibited, and resin masks can be efficiently removed from the surface of a substrate.

[0015] The present application relates to a cleaning method of a substrate (hereinafter also referred to as "the cleaning method of the present application") in one embodiment, which includes a step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface using a cleaning agent composition (hereinafter also referred to as "the cleaning agent composition of the present application"), the cleaning agent composition containing an alkali agent (component A), an ammonium ion (NH4 + , component B), thioglycolic acid (component C), and water (component D), and the molar ratio of component B to component C (B / C) is 1.5 or more.

[0016] According to the present application, a cleaning method that is excellent in resin mask removal, can inhibit corrosion and discoloration of copper, can be provided. Furthermore, by using the cleaning method of the present application, a high-quality electronic component can be obtained at a high yield. Furthermore, by using the cleaning method of the present application, an electronic component having a fine wiring pattern can be efficiently manufactured.

[0017] The detailed mechanism of the effect of the present application is not fully understood, but is presumed as follows.

[0018] It is considered that the alkali agent penetrates into the resin mask and promotes dissociation of the alkali-soluble resin incorporated in the resin mask, and further causes repulsion of the charges generated by the dissociation, thereby promoting peeling of the resin mask, whereby the resin mask removal is improved. On the other hand, it is considered that the alkali agent participates in etching (corrosion) of copper. It is considered that thioglycolic acid can inhibit etching of copper by the alkali agent, but forms a salt with copper to cause discoloration of copper. It is considered that by combining ammonium ion and thioglycolic acid in a specific ratio in the cleaning agent composition containing water, the formation of the copper salt of thioglycolic acid is inhibited by the excess of ammonium ion over thioglycolic acid, and etching (corrosion) inhibition of copper and good peeling performance can be exhibited in the presence of the alkali agent, and discoloration of copper is inhibited.

[0019] However, the present application can also be explained without being limited to this mechanism.

[0020] The resin mask peeled and removed in the present application is a mask for protecting the surface of a substance from processing such as etching, plating, heating, and the like, that is, a mask that functions as a protective film. As the resin mask, in one or more embodiments, a resist layer after an exposure and development step, a resist layer on which at least one of an exposure and development (hereinafter also referred to as "exposure and / or development processing") has been performed, or a cured resist layer can be cited. As a resin material that forms 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 resist film.

[0021] [Cleaning agent composition]

[0022] The cleaning agent composition of the present application is, in one or more embodiments, a cleaning agent composition for resin mask peeling, which contains an alkali agent (component A), an ammonium ion (component B), a mercaptoacetic acid (component C), and water (component D), and the molar ratio (B / C) of component B to component C is 1.5 or more. The cleaning agent composition according to the present application, in one or more embodiments, can exhibit corrosion inhibition of copper and good resin mask peeling performance, and can inhibit discoloration of copper. The cleaning agent composition according to the present application, in one or more embodiments, can efficiently peel and remove a resin mask located in a fine gap. The cleaning agent composition according to the present application, in one or more embodiments, can inhibit damage to a substrate resin. As the substrate resin, for example, a solder resist can be given.

[0023] [Alkali agent (component A)]

[0024] As the alkali agent (hereinafter also simply referred to as "component A") contained in the cleaning agent composition of the present application, in one or more embodiments, at least one selected from inorganic alkali and organic alkali can be given, and from the viewpoint of reducing the load on the drainage treatment, inorganic alkali is preferred. Component A can be one, or a combination of two or more.

[0025] As the inorganic alkali, in one or more embodiments, hydroxides, carbonates, or silicates of alkali metals or alkaline earth metals, etc. can be given, and 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 given. Among them, from the viewpoint of improving the resin mask removal performance, 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 application, the inorganic alkali does not include ammonia (NH3) and ammonium ion (NH4 + ).

[0026] As the organic alkali, in one or more embodiments, tetraalkylammonium hydroxide, organic amine, etc. can be given. As the tetraalkylammonium hydroxide, for example, quaternary ammonium hydroxide represented by the following formula (I) can be given. As the organic amine, for example, amine represented by the following formula (II) can be given. As component A, in one or more embodiments, from the viewpoint of improving the resin mask removal performance, the combination of quaternary ammonium hydroxide represented by formula (I) and amine represented by formula (II) is preferably used.

[0027] [Chemical formula 1]

[0028]

[0029] 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 a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0030] [Chemical Formula 2]

[0031]

[0032] 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 the group consisting of a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group, or an ethyl group, R 7 is at least one selected from the group consisting of an aminoethyl group, a hydroxyethyl group, or a hydroxypropyl group, or in formula (II), R 5 is at least one selected from the group consisting of a methyl group, an ethyl group, an aminoethyl group, a hydroxyethyl group, or a hydroxypropyl group, R 6 and R 7 are mutually bonded to form a pyrrolidine ring or a piperazine ring together with the N atom in formula (II).

[0033] As the quaternary ammonium hydroxide represented by formula (I), for example, a salt or the like containing a quaternary ammonium cation and a hydroxide can be given. As a specific example of the quaternary ammonium hydroxide, at least one selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltri- propylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltri- propylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide, and tetra(2-hydroxypropyl)ammonium hydroxide can be given. Among these, from the viewpoint of improving the resin mask removal properties, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred, and tetramethylammonium hydroxide is more preferred.

[0034] As the amine represented by formula (II), for example, alkanolamines, primary amines to tertiary amines, and heterocyclic compounds, etc. can be given. As specific examples of the amine, at least one selected from the group consisting of monoethanolamine, monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmono- isopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmono-isopropanolamine, 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 can be given. Among them, from the viewpoint of improving the resin mask removal, monoethanolamine and diethanolamine are preferred, and monoethanolamine is more preferred.

[0035] From the viewpoint of improving the resin mask removal and suppressing copper corrosion, the content of component A when the cleaning agent composition of the present application is used is preferably 0.5 mass% or more, more preferably 2 mass% or more, and from the same viewpoint, it is preferably 8 mass% or less, more preferably 6 mass% or less. More specifically, the content of component A when the cleaning agent composition of the present application is used is preferably 0.5 mass% or more and 8 mass% or less, more preferably 2 mass% or more and 6 mass% or less. In the case where component A is a combination of two or more, the content of component A refers to the total content thereof.

[0036] The "content of each component when the cleaning agent composition is used" in the present application refers to the content of each component at the time of cleaning, i.e., at the time when the cleaning agent composition is started to be used for cleaning.

[0037] [Ammonium ion: NH4 + (Component B)

[0038] The ammonium ion (hereinafter also referred to as "component B") contained in the cleaning agent composition of the present application is an ammonium ion represented by the chemical formula NH4 + .

[0039] As the supply source of component B, in one or more embodiments, as long as it is a source that can supply an ammonium ion (NH4 +The compound of the component B is not particularly limited, and at least one of ammonia and an ammonium salt of an organic acid can be exemplified from the viewpoint of the resin mask removal and the copper corrosion inhibition. Ammonia can also be used as a gas, but from the viewpoint of workability, it is preferable to use it in the form of an aqueous solution (ammonia water). As the ammonium salt of an organic acid, for example, an ammonium salt of mercaptoacetic acid (component C) or the like can be exemplified. From the viewpoint of the resin mask removal and the copper corrosion inhibition, the supply source of the component B is preferably a combination of ammonia and an ammonium salt of mercaptoacetic acid (component C), or a combination of ammonia and an ammonium salt of a carboxylic acid.

[0040] From the viewpoint of improving the resin mask removal and the copper corrosion inhibition, the content (mol / 100 g) of the component B with respect to 100 g of the cleaning agent composition when the cleaning agent composition of the present application is used is preferably 0.02 mol / 100 g or more, more preferably 0.04 mol / 100 g or more, and from the same viewpoint, it is preferably 0.08 mol / 100 g or less, more preferably 0.06 mol / 100 g or less. More specifically, the content (mol / 100 g) of the component B with respect to 100 g of the cleaning agent composition when the cleaning agent composition of the present application is used is preferably 0.02 mol / 100 g or more and 0.08 mol / 100 g or less, more preferably 0.04 mol / 100 g or more and 0.06 mol / 100 g or less.

[0041] [mercaptoacetic acid (component C)]

[0042] As the supply source of mercaptoacetic acid (component C) included in the cleaning agent composition of the present application, mercaptoacetic acid or a salt thereof can be exemplified. For example, an ammonium salt of mercaptoacetic acid can become the supply source of the component B and the component C. For example, a monoethanolamine salt of mercaptoacetic acid can become the supply source of the component A and the component C.

[0043] From the viewpoint of improving the resin mask removal and the copper corrosion inhibition, the content (mass %) of mercaptoacetic acid (hereinafter also referred to as "component C") when the cleaning agent composition of the present application is used is preferably 0.5 mass % or more, more preferably 1 mass % or more, and from the same viewpoint, it is preferably 3 mass % or less, more preferably 2 mass % or less. More specifically, the content of the component C when the cleaning agent composition of the present application is used is preferably 0.5 mass % or more and 3 mass % or less, more preferably 1 mass % or more and 2 mass % or less.

[0044] The content of component C with respect to 100 g of the cleaning agent composition when the cleaning agent composition of the present application is used is preferably 0.005 mol / 100 g or more, more preferably 0.01 mol / 100 g or more, and, in terms of the same viewpoint, preferably 0.03 mol / 100 g or less, more preferably 0.02 mol / 100 g or less. More specifically, the content of component C with respect to 100 g of the cleaning agent composition when the cleaning agent composition of the present application is used is preferably 0.005 mol / 100 g or more and 0.03 mol / 100 g or less, more preferably 0.01 mol / 100 g or more and 0.02 mol / 100 g or less.

[0045] In terms of the viewpoints of improving the resin mask removal property, suppressing copper corrosion, and suppressing copper discoloration, the molar ratio (B / C) of component B with respect to component C (the content of component B / the content of component C) in the cleaning agent composition of the present application is 1.5 or more, preferably 2 or more, more preferably 3 or more, and, in terms of the same viewpoint, preferably 5 or less, more preferably 4 or less. More specifically, the molar ratio (B / C) is preferably 2 or more and 5 or less, more preferably 3 or more and 4 or less.

[0046] [Water (Component D)]

[0047] As the water (hereinafter also referred to as "component D") included in the cleaning agent composition of the present application, ion-exchanged water, RO water, distilled water, pure water, ultrapure water, and the like can be exemplified in one or more embodiments.

[0048] The content of component D in the cleaning agent composition of the present application can be set to the balance other than component A, component B, component C, and any of the components described later. Specifically, in terms of the viewpoints of improving the resin mask removal property, suppressing copper corrosion, reducing the load on the drainage treatment, and reducing the influence on the substrate, the content of component D when the cleaning agent composition of the present application is used is preferably 45 mass% or more, more preferably 60 mass% or more, further preferably 80 mass% or more, and, in terms of the viewpoint of improving the resin mask removal property, preferably 99 mass% or less, more preferably 98 mass% or less, further preferably 97 mass% or less. More specifically, the content of component D when the cleaning agent composition of the present application is used is preferably 45 mass% or more and 99 mass% or less, more preferably 60 mass% or more and 98 mass% or less, further preferably 80 mass% or more and 97 mass% or less.

[0049] In terms of the viewpoints of improving the resin mask removal property and suppressing copper corrosion, the total amount of component A, component B, component C, and component D when the cleaning agent composition of the present application is used is preferably 60 mass% or more, more preferably 90 mass% or more, further preferably 95 mass% or more.

[0050] [Organic solvent (component E)]

[0051] The cleaning agent composition of the present application can further contain an organic solvent (hereinafter also referred to as "component E") in one or more embodiments. Component E can be one or a combination of two or more.

[0052] As component E, at least one solvent selected from the group consisting of glycol ethers and aromatic ketones can be exemplified in one or more embodiments.

[0053] As the glycol ether, from the viewpoint of improving the resin mask removal, suppressing copper corrosion, and reducing the influence on the substrate, a compound having a structure in which one mole or more and three moles or less of ethylene glycol is added to an alcohol having a carbon number of one or more and eight or less can be exemplified. As specific examples of the glycol ether, at least one selected from the group consisting of diethylene glycol monobutyl ether (BDG), ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether can be exemplified.

[0054] As the aromatic ketone, from the viewpoint of improving the resin mask removal, suppressing copper corrosion, and reducing the influence on the substrate, acetophenone and the like can be exemplified.

[0055] In the case where the cleaning agent composition of the present application contains component E, from the viewpoint of improving the resin mask removal, the content of component E when the cleaning agent composition of the present application is used is preferably one mass% or more, more preferably two mass% or more, and further preferably three mass% or more, and from the viewpoint of suppressing copper corrosion, reducing the load of the effluent treatment, and reducing the influence on the substrate, it is preferably 40 mass% or less, more preferably 20 mass% or less, and further preferably 6 mass% or less. More specifically, the content of component E when the cleaning agent composition of the present application is used is preferably one mass% or more and 40 mass% or less, more preferably two mass% or more and 20 mass% or less, and further preferably three mass% or more and 6 mass% or less. In the case where component E is a combination of two or more, the content of component E refers to the total content thereof.

[0056] [Chelating agent (component F)]

[0057] The cleaning agent composition of the present application can further contain a chelating agent (hereinafter also referred to as "component F") in one or more embodiments. Component F can be one or a combination of two or more.

[0058] As the component F, for example, a compound having 2 or more acid groups selected from a carboxyl group and a phosphonic acid group can be mentioned, and from the viewpoint of improving the resin resist removal properties and suppressing copper corrosion, a compound having preferably 4 or less of the above acid groups is preferable. As specific examples of the component F, in one or more embodiments, amino-trimethylene phosphonic acid, 2-phosphonobutane-l,2,4-tricarboxylic acid, etidronic acid (l-hydroxyethane-l,l-diphosphonic acid, HEDP), and the like can be mentioned. Among them, from the viewpoint of reducing the environmental load, 2-phosphonobutane-l,2,4-tricarboxylic acid, etidronic acid (HEDP), and the like, which are compounds not containing a nitrogen atom, are preferable.

[0059] From the viewpoint of improving the resin resist removal properties and suppressing copper corrosion, the molecular weight of the component F is preferably 1000 or less, more preferably 500 or less.

[0060] In the case where the cleaning agent composition of the present application contains the component F, from the viewpoint of improving the resin resist removal properties and suppressing copper corrosion, the content of the component F when the cleaning agent composition of the present application is used is preferably 0.5 mass% or more, more preferably 1 mass% or more, and from the same viewpoint, it is preferably 5 mass% or less, more preferably 3 mass% or less. More specifically, the content of the component F when the cleaning agent composition of the present application is used is preferably 0.5 mass% or more and 5 mass% or less, more preferably 1 mass% or more and 3 mass% or less. In the case where the component F is a combination of 2 or more, the content of the component F refers to the total content thereof.

[0061] [Other components]

[0062] The cleaning agent composition of the present application can contain other components as needed in addition to the above components A to F. As the other components, components that can be used in general cleaning agents can be mentioned, and for example, organic solvents other than the component E, surfactants, chelating agents other than the component F, thickening agents, dispersants, rust preventives, high molecular compounds, co-solvents, antioxidants, preservatives, antifoaming agents, antibacterial agents, and the like can be mentioned.

[0063] The other content when the cleaning agent composition of the present application is used is preferably 0 mass% or more and 2 mass% or less, more preferably 0 mass% or more and 1.5 mass% or less, further preferably 0 mass% or more and 1.3 mass% or less, and still further preferably 0 mass% or more and 1 mass% or less.

[0064] The cleaning agent composition of the present application can not contain a fluorine compound in one or more embodiments.

[0065] The total content of the organic substances derived from the component A, the component B, the component C, and the optional components (the component E, the component F, other components) in the cleaning agent composition of the present application is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and still further preferably 16% by mass or less, from the viewpoint of reducing the load on the wastewater treatment and reducing the influence on the substrate, and is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more, and still further preferably 6% by mass or more, from the viewpoint of improving the resin mask removal. More specifically, the total content of the organic substances derived from the component A, the component B, the component C, and the optional components (the component E, the component F, other components) in the cleaning agent composition of the present application is preferably 2% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, further preferably 4% by mass or more and 20% by mass or less, and still further preferably 6% by mass or more and 16% by mass or less.

[0066] [Method for producing the cleaning agent composition]

[0067] The cleaning agent composition of the present application can be produced by mixing the base agent (component A), the supply source of ammonium ions (component B), the mercaptoacetic acid (component C) or a salt thereof, water (component D), and the optional components described above, as necessary, using a publicly known method. For example, the cleaning agent composition of the present application can be produced by mixing the base agent (component A), the supply source of ammonium ions (component B), the mercaptoacetic acid (component C) or a salt thereof, and water (component D), in one or more embodiments.

[0068] Therefore, the present application relates to a method for producing a cleaning agent composition, which includes a step of mixing at least the base agent (component A), the supply source of ammonium ions (component B), the mercaptoacetic acid (component C) or a salt thereof, and water (component D). The "mixing" in the present application includes mixing the base agent (component A), the supply source of ammonium ions (component B), the mercaptoacetic acid (component C) or a salt thereof, water, and the optional components described above, simultaneously or in any order. In the method for producing the cleaning agent composition of the present application, the preferable mixing amounts of the components can be the same as the preferable contents of the components in the cleaning agent composition of the present application described above.

[0069] The cleaning agent composition of the present application can be prepared as a concentrate in which the amount of water (component D) is reduced within a range that does not cause separation, precipitation, or the like, and does not impair storage stability. From the viewpoint of transport and storage, the concentrate of the cleaning agent composition is preferably prepared as a concentrate having a dilution ratio of 3 or more, and from the viewpoint of storage stability, the concentrate is preferably prepared as a concentrate having a dilution ratio of 30 or less. The concentrate of the cleaning agent composition can be used by diluting with water (component D) at the time of use so that each component (component A, component B, component C, component D, component E, component F, and other components) becomes the above-mentioned content (i.e., the content at the time of cleaning). Furthermore, the concentrate of the cleaning agent composition can also be used by separately adding each component at the time of use. The "at the time of use" or "at the time of cleaning" of the cleaning agent composition as a concentrate in the present application means a state in which the concentrate of the cleaning agent composition has been diluted.

[0070] [Object to be cleaned]

[0071] The cleaning agent composition of the present application, in one or more embodiments, can be used for cleaning a substrate having a copper-containing metal layer and a resin mask on a surface. The copper-containing metal layer, in one or more embodiments, is a copper plating layer. The copper plating layer can be formed, for example, by an electroless copper plating method.

[0072] The cleaning agent composition of the present application, in another or more embodiments, can be used for cleaning an object to be cleaned having a resin mask attached thereto. As the object to be cleaned, in one or more embodiments, an object to be cleaned having a copper-containing metal portion on a surface can be mentioned, and for example, an electronic component and an intermediate in the production thereof can be mentioned. As the electronic component, for example, at least one component selected from a printed board, a wafer, a metal plate such as a copper plate and an aluminum plate, and the like can be mentioned. The above-mentioned intermediate is an intermediate in the production process of the electronic component, and includes an intermediate after a resin mask treatment. As a specific example of the object to be cleaned having a resin mask attached thereto, for example, an electronic component in which a wiring, a connection terminal, or the like is formed on a substrate surface by a process in which a resin mask is used to perform a soldering treatment, a plating treatment (copper plating, aluminum plating, nickel plating, or the like), or the like can be mentioned. Thus, the present application, in one embodiment, relates to the use of the cleaning agent composition of the present application as a cleaning agent in the production of an electronic component.

[0073] In addition, the cleaning agent composition of the present application, in one or more embodiments, has excellent resin mask removal properties in a fine gap. As the object to be cleaned, from the viewpoint of exerting the resin mask removal properties of the cleaning agent composition, a substrate having a fine gap and having a resin mask in the gap is preferred. As the substrate having a fine gap, a substrate having a wiring (line) of copper and having a minimum value of the interval (gap) of the wiring of preferably 1 μm or more and preferably 10 μm or less, and more preferably 6 μm or less can be mentioned.

[0074] In addition, the cleaning agent composition of the present application can inhibit damage to a substrate resin in one or more embodiments. As the object to be cleaned, a substrate having a resin on the surface, such as a substrate having a solder resist resin, is preferable.

[0075] As for the cleaning effect, the cleaning agent composition of the present application can be suitably used for cleaning an object to be cleaned having a resin mask attached thereto, or a resin mask subjected to further plating treatment and / or heat treatment, in one or more embodiments. As the resin mask, a negative type resin mask, for example, or a positive type resin mask can be used. The negative type resin mask in the present application is formed using a negative type resist, such as a negative type resist layer subjected to exposure and / or development treatment. The positive type resin mask in the present application is formed using a positive type resist, such as a positive type resist layer subjected to exposure and / or development treatment.

[0076] [Cleaning method]

[0077] The cleaning method of the present application can include a step of peeling a resin mask from a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on the surface using the cleaning agent composition of the present application (hereinafter also referred to as "peeling step") in one or more embodiments. The peeling step described above can include bringing the object to be cleaned into contact with the cleaning agent composition of the present application in one or more embodiments. According to the cleaning method of the present application, corrosion and discoloration of copper can be inhibited, and the resin mask can be efficiently peeled and removed. According to the cleaning method of the present application, the resin mask present in a fine gap can be efficiently peeled and removed in one or more embodiments. According to the cleaning method of the present application, damage to a substrate resin can be inhibited in one or more embodiments. As the substrate resin, a solder resist, for example, can be used.

[0078] As the method of peeling a resin mask from an object to be cleaned using the cleaning agent composition of the present application, or the method of bringing the cleaning agent composition of the present application into contact with an object to be cleaned, a method of bringing into contact by dipping in a cleaning bath tank into which the cleaning agent composition is put, a method of bringing into contact by spraying the cleaning agent composition (spray method), an ultrasonic cleaning method in which ultrasonic irradiation is performed in dipping, and the like can be used, for example. The cleaning agent composition of the present application can be used directly for cleaning without dilution. As the object to be cleaned, the object to be cleaned described above can be used.

[0079] The cleaning method of the present application can include a step of washing and drying the object to be cleaned with water after bringing the object to be cleaned into contact with the cleaning agent composition in one or more embodiments. The cleaning method of the present application can include a step of rinsing the object to be cleaned with water after bringing the object to be cleaned into contact with the cleaning agent composition in one or more embodiments.

[0080] As to the aspect of easily exerting the cleaning power of the cleaning agent composition of the present application, the cleaning method of the present application preferably irradiates ultrasonic waves, which are more preferably relatively high frequency, when the cleaning agent composition of the present application is in contact with the object to be cleaned. As to the same point, the irradiation conditions of the above-mentioned ultrasonic waves are, for example, preferably 26 to 72 kHz, 80 to 1500 W, and more preferably 36 to 72 kHz, 80 to 1500 W.

[0081] In the cleaning method of the present application, as to the aspect of easily exerting the cleaning power of the cleaning agent composition of the present application, the temperature of the cleaning agent composition is preferably 40°C or higher, and more preferably 50°C or higher, and as to the aspect of reducing the influence on the substrate, it is preferably 70°C or lower, and more preferably 60°C or lower.

[0082] [Method for manufacturing electronic component]

[0083] The present application relates to, in one embodiment, a method for manufacturing an electronic component (hereinafter also referred to as "the method for manufacturing an electronic component of the present application"), which includes a step (cleaning step) of cleaning a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on a surface using the cleaning method of the present application. As the object to be cleaned, the above-mentioned object to be cleaned can be given. The method for manufacturing an electronic component of the present application can include, in one or more embodiments, a step of etching the metal layer containing copper after the above-mentioned cleaning step.

[0084] As to the method for manufacturing an electronic component of the present application, by cleaning using the cleaning method of the present application, corrosion and discoloration of copper can be inhibited, and the resin mask adhered to the electronic component can be effectively removed, and thus the manufacturing of an electronic component with high reliability can be achieved. Furthermore, by performing the cleaning method of the present application, the resin mask adhered to the electronic component can be easily removed, and thus the cleaning time can be shortened, and the manufacturing efficiency of the electronic component can be improved.

[0085] [Kit]

[0086] The present application relates to, in one embodiment, a kit (hereinafter also referred to as "the kit of the present application") for any one of the cleaning method of the present application and the method for manufacturing an electronic component of the present application. The kit of the present application is, in one or more embodiments, a kit for manufacturing the cleaning agent composition of the present application. According to the kit of the present application, a cleaning agent composition with excellent resin mask removal properties, in which corrosion and discoloration of copper can be inhibited, can be obtained.

[0087] As one embodiment of the kit of the present application, a kit (three-liquid type cleaning agent composition) can be exemplified, in which a solution containing component A (1st liquid), a solution containing component B (2nd liquid), and a solution containing component C (3rd liquid) are contained in a state of not being mixed with each other, at least one selected from the 1st liquid, the 2nd liquid, and the 3rd liquid further contains a part or all of water (component D), and the 1st liquid, the 2nd liquid, and the 3rd liquid are mixed at the time of use. After mixing the 1st liquid, the 2nd liquid, and the 3rd liquid, dilution with water (component D) can also be performed as necessary. In each of the 1st liquid, the 2nd liquid, and the 3rd liquid, any of the above components can also be contained as necessary.

[0088] As another embodiment of the kit of the present application, a kit (two-liquid type cleaning agent composition) can be exemplified, in which a solution containing component A (1st liquid) and a solution containing component B and component C (2nd liquid) are contained in a state of not being mixed with each other, at least one of the 1st liquid and the 2nd liquid further contains a part or all of water (component D), and the 1st liquid and the 2nd liquid are mixed at the time of use. After mixing the 1st liquid and the 2nd liquid, dilution with water (component D) can also be performed as necessary. In each of the 1st liquid and the 2nd liquid, any of the above components can also be contained as necessary.

[0089] Examples

[0090] Hereinafter, the present application will be specifically described by way of examples, but the present application is not limited at all by these examples.

[0091] 1. Preparation of the cleaning agent compositions of Examples 1 to 9 and Comparative Examples 1 to 3

[0092] Each component shown in Tables 1 to 2 was prepared in the compounding amount (mass%, effective component) described in Tables 1 to 2, these were stirred and mixed, whereby the cleaning agent compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared. The content of ammonium ion (component B) (mol / 100 g, effective component), the content of mercaptoacetic acid (component C) (mass%, mol / 100 g, effective component), and the molar ratio of ammonium ion / mercaptoacetic acid (B / C) in each of the prepared cleaning agent compositions are shown in Tables 1 to 2.

[0093] The following substances were used in the preparation of the cleaning agent compositions of Examples 1 to 9 and Comparative Examples 1 to 3.

[0094] TMAH: tetramethylammonium hydroxide [manufactured by Showa Denko K.K., concentration 25%] (component A)

[0095] MEA: monoethanolamine [manufactured by Nikka Soda Co., Ltd.] (component A)

[0096] Ammonia [Fuji Photo Film and Drikold Co., Ltd., first grade, 25% aqueous solution] (source of supply of component B)

[0097] Ammonium thioglycolate [manufactured by Tokyo Chemical Industry Co., Ltd., 60% aqueous solution] (a source of Component B and Component C)

[0098] Water [pure water of 1 μS / cm or less manufactured by a pure water device G-10 DST SET manufactured by ORGANO Co., Ltd.] (Component D)

[0099] BDG: diethylene glycol butyl ether [manufactured by Nikko Chemicals Co., Ltd., diethylene glycol monobutyl ether] (Component E)

[0100] HEDP: etidronic acid [manufactured by Italmatch Japan Co., Ltd., Dequest 2010, concentration 60%] (Component F)

[0101] Ammonium formate [Fuji Photo Film Co., Ltd. and Otsuka Pharmaceutical Co., Ltd.]

[0102] Dimethyl sulfoxide [Fuji Photo Film Co., Ltd. and Otsuka Pharmaceutical Co., Ltd.]

[0103] 2. Evaluation of the cleaning agent composition (Examples 1 to 9 and Comparative Examples 1 to 2)

[0104] The cleaning agent compositions of Examples 1 to 9 and Comparative Examples 1 to 2 prepared were subjected to the following evaluations.

[0105] [Manufacture of Test Sheet 1]

[0106] A photosensitive film for forming a circuit of a PKG (package) substrate was laminated on the surface of a substrate after electrolytic plating under the following conditions, and subjected to an exposure process to cure it (exposure step), thereby obtaining a substrate having a resin mask (cured resist layer) (Test Sheet 1, 30 mm x 50 mm).

[0107] (1) Lamination: using a cleaning roller (manufactured by RAYON Co., Ltd., RY-505Z) and a vacuum applicator (manufactured by Rohm & Haas Co., Ltd., VA7024 / HP5), it was performed at a roller temperature of 50°C and a roll pressure of 1.4 Bar.

[0108] (2) Exposure: using a direct writing device for a printed substrate (manufactured by SCREEN Graphic and Precision Solutions Co., Ltd., Mercurex LI-9500), it was performed at an exposure amount of 15 mJ / cm 2 .

[0109] [Cleaning Test]

[0110] In a 200 mL glass beaker of high form, 100 g of each of the cleaning agent compositions of Examples 1 to 9 and Comparative Examples 1 to 2 was added, warmed to 50°C, and stirred at a rotation speed of 600 rpm using a rotor (fluororesin (PTFE), φ 8 mm x 25 mm). In this state, Test Piece 1 was immersed for 10 minutes. Then, after rinsing in a rinse tank in which 100 g of water was added to a 100 mL glass beaker, drying was performed by a nitrogen blower.

[0111] [Peeling time of resin mask (evaluation of peelability (removability))}

[0112] In the above cleaning test, the time (minutes) until the resin mask was completely removed was measured by visual observation.

[0113] [Evaluation of Cu etching rate (evaluation of corrosion of copper (corrosivity))}

[0114] Each of 2.5 L of the cleaning agent compositions was prepared, warmed to 50°C, and while being circulated using a box-type spray cleaning machine equipped with a dense conical nozzle (J020, manufactured by Iuchi Corporation) as a spray nozzle, Test Piece 2 (substrate having a copper-plated layer on the surface) on which copper plating was performed (with respect to the area, 25 cm 2 on each single side, and 50 cm 2 on both sides) was sprayed for 4 minutes (pressure: 0.05 MPa; spray distance: 80 mm). After diluting the cleaning agent composition, the elution amount of copper was measured by ICP analysis (Agilent 5110 ICP-OES manufactured by Agilent Technologies), the density of copper was taken as 8.94 g / cm 3 , and the Cu etching rate (μm / min) was evaluated from the elution amount. The lower the value of the Cu etching rate, the more excellent the copper corrosion inhibiting effect can be judged to be.

[0115] Cu etching rate (μm / min) = elution amount of copper (weight) ÷ density of copper ÷ plated area ÷ treatment time

[0116] [Appearance of copper on substrate (evaluation of discoloration of copper)}

[0117] In the above evaluation of etching rate, discoloration of the copper portion was observed by visual observation.

[0118] [Evaluation of damage to substrate resin]

[0119] The above cleaning test was performed on a substrate (Test Piece 3) having a solder resist resin, and whether or not a change in color or the like occurred in the resin portion of the substrate before and after the above cleaning test was confirmed by visual observation, and evaluation was performed according to the following evaluation criteria.

[0120] [Evaluation Criteria]

[0121] A: No change before and after the cleaning test.

[0122] B: Change before and after the cleaning test.

[0123] [Table 1]

[0124]

[0125] As shown in Table 1, it was found that the cleaning agent compositions of Examples 1 to 9 could inhibit corrosion and discoloration of copper and had excellent resin mask removal properties, as compared with Comparative Example 1 in which the molar ratio B / C was not within the prescribed range and Comparative Example 2 which did not contain component C.

[0126] In addition, in the case where thio-glycerin was used instead of ammonium mercaptoacetate for the cleaning agent composition of Example 3, a result of poor resin mask removal properties and poor copper discoloration inhibition effect was obtained as compared with Example 3 (data not shown).

[0127] 3. Evaluation of the cleaning agent composition (Example 8 and Comparative Example 3)

[0128] The cleaning agent compositions of Example 8 and Comparative Example 3 prepared were used to perform the following evaluations.

[0129] [Production of Test Sheet 4 with Thick Film DF]

[0130] A photosensitive thick film (thickness: 140 μm) for PKG substrate circuit formation was laminated on the surface of the substrate after electrolytic plating under the following conditions, and exposure treatment was performed to cure it (exposure step), thereby obtaining a substrate (test sheet 4, 30 mm x 50 mm) having a resin mask (cured resist layer).

[0131] (1) Lamination: A clean roller (manufactured by RAYON Co., Ltd., RY-505Z) and a vacuum applicator (manufactured by Rohm & Haas, VA7024 / HP5) were used at a roller temperature of 50°C and a roll pressure of 1.4 Bar.

[0132] (2) Exposure: A direct writing device for printed boards (manufactured by SCREEN Graphic and Precision Solutions Co., Ltd., Mercurex LI-9500) was used at an exposure amount of 15 mJ / cm 2 .

[0133] [Production of Test Sheet 5 with Fine Line Circuit Pattern]

[0134] The photosensitive film for PKG substrate circuit formation was laminated on the surface of the substrate after electrolytic plating under the following conditions, and after exposure treatment to cure it (exposure step), electrolytic plating was performed, thereby obtaining a substrate (test piece 5, 30 mm x 50 mm) having a resin mask (cured resist layer) and a fine line circuit pattern with a line / gap of 5 μm / 5 μm.

[0135] (1) Lamination: Using a clean roller (Clean Roller, manufactured by RAYON Co., Ltd., RY-505Z) and a vacuum applicator (manufactured by Rohm & Haas, VA7024 / HP5), it was performed at a roller temperature of 50°C and a roll pressure of 1.4 Bar.

[0136] (2) Exposure: Using a direct writing device for printed boards (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.), it was performed at an exposure amount of 15 mJ / cm 2

[0137] [Cleaning Test]

[0138] In a 200 mL glass beaker, 100 g of each of the cleaning agent compositions of Example 8 and Comparative Example 3 was added, warmed to 50°C, and stirred at a rotation speed of 600 rpm using a rotor (fluororesin (PTFE), φ 8 mm x 25 mm), and in this state, test piece 4 or 5 was immersed for 10 minutes. Then, after rinsing by immersion in a rinse tank in which 100 g of water was added to a 100 mL glass beaker, drying was performed by a nitrogen blower.

[0139] [Resin mask peeling time (evaluation of removability)]

[0140] In the above cleaning test of test piece 4, the time (minutes) until the resin mask was completely removed was measured by visual observation.

[0141] [Peeling property of fine line circuit pattern (evaluation of removability)]

[0142] Using an optical microscope "Digital Microscope VHX-2000" (manufactured by Keyence Corporation), the presence or absence of the resin mask remaining in the fine line circuit pattern of test piece 5 after the above cleaning test was visually confirmed at a magnification of 1000 times.

[0143] [Table 2]

[0144]

[0145] As shown in Table 2, it was found that the resin mask removability of the cleaning agent composition of Example 8 was excellent compared to Comparative Example 3 which did not contain component C.​

[0146] Industrial applicability

[0147] According to the present application, a cleaning method can be provided which is excellent in resin mask removal, can suppress corrosion and discoloration of copper, can shorten a cleaning process of an electronic component to which a resin mask is attached, and can improve performance and reliability of the manufactured electronic component, and can improve productivity of a semiconductor device.

Claims

1. A cleaning method of a substrate, comprising a step of stripping a resin mask from a substrate having a copper-containing metal layer and the resin mask on a surface using a cleaning agent composition, The cleaning agent composition contains: an alkali agent, i.e., component A; an ammonium ion, i.e., NH4 + , component B; a mercaptoacetic acid, i.e., component C; and water, i.e., component D, component A contains tetraalkylammonium hydroxide, and the molar ratio of component B to component C, i.e., B / C, is 1.5 or more, the content of the component A is 0.5 mass% or more and 8 mass% or less, the content of the component B is 0.02 mol / 100 g or more and 0.08 mol / 100 g or less, and the content of the component C is 0.4 mass% or more and 4 mass% or less.

2. The cleaning method according to claim 1, wherein, the copper-containing metal layer is a copper plating layer.

3. The cleaning method according to claim 1 or 2, wherein, the resin mask is a cured resist layer.

4. The cleaning method according to claim 1 or 2, wherein, the content of the component D is 60 mass% or more when the cleaning agent composition is used.

5. The cleaning method according to claim 1 or 2, wherein, the component A is tetraalkylammonium hydroxide.

6. The cleaning method according to claim 1 or 2, wherein, the substrate has a copper wiring, and the minimum value of the interval of the wiring is 1 μm or more and 10 μm or less.

7. The cleaning method according to claim 1 or 2, wherein, the substrate is a solder resist resin substrate.

8. A manufacturing method of an electronic component, comprising a step of cleaning a substrate having a copper-containing metal layer and a resin mask on a surface using the cleaning method according to any one of claims 1 to 7.

9. A cleaning agent composition for resin mask stripping, comprising: an alkali agent, i.e., component A; an ammonium ion, i.e., NH4 + , component B; mercaptoacetic acid, i.e., component C; and water, i.e., component D. the component A contains tetraalkylammonium hydroxide, and the molar ratio of the component B to the component C (B / C) is 1.5 or more, the content of the component A is 0.5 mass% or more and 8 mass% or less, the content of the component B is 0.02 mol / 100 g or more and 0.08 mol / 100 g or less, the content of the component C is 0.4 mass% or more and 4 mass% or less.

10. The cleaning agent composition according to claim 9, wherein, the component A is tetraalkylammonium hydroxide.

11. The cleaning agent composition according to claim 9 or 10, wherein, the total amount of the component A, the component B, the component C, and the component D is 90 mass% or more.

12. The cleaning agent composition according to claim 9 or 10, wherein, the content of the component D is 60 mass% or more.

13. Use of a cleaning agent composition for cleaning a substrate having a copper-containing metal layer and a resin mask on a surface, The cleaning agent composition contains: an alkali agent, i.e., component A; ammonium ions, i.e., NH4 + , component B; mercaptoacetic acid, i.e., component C; and water, i.e., component D, component A contains tetraalkylammonium hydroxide, and the molar ratio of component B to component C, i.e., B / C, is 1.5 or more, the content of the component A is 0.5 mass% or more and 8 mass% or less, the content of the component B is 0.02 mol / 100 g or more and 0.08 mol / 100 g or less, and the content of the component C is 0.4 mass% or more and 4 mass% or less.

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