TW202214831A - Method for cleaning substrate - Google Patents

Abstract

One embodiment of the present disclosure provides a method for cleaning a substrate, said method being capable of inhibiting copper corrosion without greatly deteriorating removability (separability) of a resin mask and without greatly increasing residues on the substrate after the cleaning. One embodiment of the present disclosure relates to a method for cleaning a substrate, said method comprising a step wherein a resin mask is separated from a substrate, which has a copper-containing metal layer and the resin mask on the surface, with use of a cleaning agent composition that contains the component A, the component B and the component C described below. Component A: a quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II) Component B: a reducing agent Component C: water.

Description

Cleaning method of substrate

The present invention relates to a cleaning composition for resin mask peeling, a method for cleaning a substrate using the same, and a method for producing electronic parts.

In recent years, in personal computers and various electronic devices, lower power consumption, higher processing speed, and miniaturization are progressing, and wiring such as package substrates mounted in these devices is being miniaturized year by year. The metal mask method has been mainly used for the formation of such fine wiring and connection terminals such as posts and bumps. However, since the versatility is low, or it is difficult to cope with the miniaturization of wiring and the like, it is changing to other novel methods.

As one of the new methods, a method of using a dry film resist as a thick film resin mask instead of a metal mask is known. The resin mask is eventually peeled off and removed, and as a cleaning agent used for cleaning such as peeling and removal, a resin mask peeling cleaning agent containing an alkali agent and water is known. For example, in Japanese Patent Laid-Open No. 2019-112498 (Patent Document 1), in order to provide a resin mask peeling and cleaning method excellent in resin mask removability and continuous operation stability, the following resin mask peeling and cleaning is disclosed A method using a detergent composition containing a specified quaternary ammonium hydroxide, a specified amine, and water.

In addition, technology to suppress corrosion of metal films after cleaning is also being developed. For example, in Japanese Patent Laid-Open No. 2007-256955 (Patent Document 2), in order to provide a chemical cleaning composition for cleaning a resist stripping solution, which is excellent in no corrosion to metal films after cleaning and excellent cleaning effect, it is disclosed that The following chemical cleaning composition for resist stripping liquid cleaning, which contains selected from organic amine-based compounds, organic solvents, triazole-based anticorrosion agents, hydroxyphenols, gallic acid alkyl esters, and reducing agents Corrosion inhibitor and water in the group.

於上述式(I)中，R ¹、R ²、R ³及R ⁴分別獨立為選自甲基、乙基、丙基、羥甲基、羥乙基及羥丙基之至少1種。 [化2]

於上述式(II)中，R ⁵表示選自氫原子、甲基、乙基及胺基乙基之至少1種，R ⁶表示選自氫原子、羥乙基、羥丙基、甲基及乙基之至少1種，R ⁷表示選自胺基乙基、羥乙基及羥丙基之至少1種。 In one aspect, the present invention relates to a method for cleaning a substrate, comprising the steps of: using a detergent composition containing the following component A, the following component B, and the following component C, from the surface of the cleaning agent composition containing copper The metal layer and the substrate of the resin mask peel off the resin mask. Component A: A quaternary ammonium hydroxide represented by the following formula (I) and an amine represented by the following formula (II) Component B: Reducing agent Component C: Water

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. [hua 2]

In the above formula (II), R ⁵ represents at least one selected from a hydrogen atom, methyl, ethyl and aminoethyl, and R ⁶ represents a hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and At least one kind of ethyl group, and R ⁷ represents at least one kind selected from aminoethyl group, hydroxyethyl group and hydroxypropyl group.

In one aspect, the present invention relates to a method for manufacturing an electronic component, comprising the steps of: using the cleaning method of the present invention, peeling off the resin mask from the substrate having the copper-containing metal layer and the resin mask on the surface.

於上述式(I)中，R ¹、R ²、R ³及R ⁴分別獨立為選自甲基、乙基、丙基、羥甲基、羥乙基及羥丙基之至少1種。 [化4]

於上述式(II)中，R ⁵表示選自氫原子、甲基、乙基及胺基乙基之至少1種，R ⁶表示選自氫原子、羥乙基、羥丙基、甲基及乙基之至少1種，R ⁷表示選自胺基乙基、羥乙基及羥丙基之至少1種。 In one aspect, the present invention relates to a detergent composition for peeling off a resin mask, which contains the following component A, the following component B, and the following component C. Component A: A quaternary ammonium hydroxide represented by the following formula (I) and an amine represented by the following formula (II) Component B: Reducing agent Component C: Water

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. [hua 4]

In the above formula (II), R ⁵ represents at least one selected from a hydrogen atom, methyl, ethyl and aminoethyl, and R ⁶ represents a hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and At least one kind of ethyl group, and R ⁷ represents at least one kind selected from aminoethyl group, hydroxyethyl group and hydroxypropyl group.

於上述式(I)中，R ¹、R ²、R ³及R ⁴分別獨立為選自甲基、乙基、丙基、羥甲基、羥乙基及羥丙基之至少1種。 [化6]

於上述式(II)中，R ⁵表示選自氫原子、甲基、乙基及胺基乙基之至少1種，R ⁶表示選自氫原子、羥乙基、羥丙基、甲基及乙基之至少1種，R ⁷表示選自胺基乙基、羥乙基及羥丙基之至少1種。 In one aspect, the present invention relates to the use of a cleaning composition for resin mask peeling, which is used as a cleaning agent in the manufacture of electronic parts, wherein the above-mentioned resin mask peeling cleaning composition contains the following Component A, component B described below, and component C described below. Component A: A quaternary ammonium hydroxide represented by the following formula (I) and an amine represented by the following formula (II) Component B: Reducing agent Component C: Water

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. [hua 6]

In the above formula (II), R ⁵ represents at least one selected from a hydrogen atom, methyl, ethyl and aminoethyl, and R ⁶ represents a hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and At least one kind of ethyl group, and R ⁷ represents at least one kind selected from aminoethyl group, hydroxyethyl group and hydroxypropyl group.

Regarding the formation of fine wiring on a printed circuit board, etc., in order to reduce the residue of the resin mask, and to reduce the residue of the solder used for the formation of the fine wiring or the bump, or the auxiliary agent contained in the plating solution, etc., cleaning is performed. Agent compositions require higher detergency. Here, the resin mask refers to a resist formed by using a resist whose physical properties, such as solubility in a developer, are changed by light, electron beam, or the like. According to the reaction method with light or electron beam, resists can be roughly classified into negative type and positive type. The negative-type resist has the property that the solubility to the developing solution decreases when exposed to light, and the layer containing the negative-type resist (hereinafter also referred to as "negative-type resist layer") is exposed and developed. Used as a resin mask. The positive resist has the property of increasing its solubility in the developing solution when exposed to light. is removed, and the unexposed portion is used as a resin mask. By using the resin mask having such characteristics, it is possible to form a fine connection portion of a circuit board such as metal wiring and metal pillars and solder bumps.

However, with the miniaturization of wiring, it becomes difficult to remove the resin mask existing in the fine gaps, and high resin mask removability is required for the detergent composition. In addition, since the corrosion of copper used in many wirings and connection terminals leads to a decrease in the quality and value of the package substrate, high corrosion resistance is required for the cleaning composition. In addition, the residue on the cleaned substrate may hinder the etching of the subsequent steps, and thus a cleaning agent composition capable of reducing the residue is required.

Therefore, the present invention provides a method for cleaning a substrate and a method for manufacturing an electronic component, which can suppress copper corrosion without significantly impairing the removability (peelability) of the resin mask, and without significantly increasing the residue on the substrate after cleaning. , and a cleaning composition for resin mask peeling.

The present invention is based on the finding that by using a specific organic nitrogen-containing compound (component A) and a reducing agent (component B), corrosion of copper can be suppressed, and resin mask can be efficiently removed from the surface of the substrate, in addition , which can reduce the residue on the substrate after cleaning.

In one aspect, the present invention relates to a method for cleaning a substrate (hereinafter also referred to as "the cleaning method of the present invention"), which comprises the steps of: using the following components A, the following components B, and the following The detergent composition of component C peels the resin mask from the substrate having the copper-containing metal layer and the resin mask on the surface. Component A: the quaternary ammonium hydroxide represented by the above formula (I) and the amine represented by the above formula (II) Ingredient B: reducing agent Ingredient C: Water

According to the present invention, it is possible to provide a cleaning method capable of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask and without significantly increasing the residue on the substrate after cleaning. Furthermore, by using the cleaning method of the present invention, high-quality electronic parts can be obtained with high yield. Furthermore, by using the cleaning method of this invention, the electronic component which has a fine wiring pattern can be manufactured efficiently.

Although the details of the action mechanism of the effect of the present invention are not clear, the following assumptions are made. In the present invention, it is considered that a specific organic nitrogen-containing compound (ingredient A) penetrates into the resin mask to promote the dissociation of the alkali-soluble resin formulated into the resin mask, thereby causing the repulsion of the charges generated by the dissociation, thereby promoting the The peeling of the resin mask. On the other hand, it is considered that a specific organic nitrogen-containing compound (component A) also participates in the etching (corrosion) of copper. However, it is considered that in the present invention, by using a specific organic nitrogen-containing compound (component A) and a reducing agent (ingredient B), the action of the reducing agent (ingredient B) is used to suppress the positive charging of the copper surface, thereby suppressing the Etching (corrosion) of copper caused by the coordination of a specific organic nitrogen-containing compound (ingredient A). As a result, it is considered that in the presence of the specific organic nitrogen-containing compound (component A), copper etching (corrosion) is suppressed, and good peeling performance (resin mask removability) is exhibited. Furthermore, since the reducing agent (component B) is not a film type but a non-film type, it is considered that the etching (corrosion) of copper can be suppressed, and the residue on the substrate after cleaning can be reduced. However, the present invention may be explained without being limited to this mechanism.

In the present invention, the peeled and removed resin mask refers to a mask used to protect the surface of a substance from etching, plating, heating and other treatments, that is, a mask that functions as a protective film. As the resin mask, in one or more embodiments, there may be exemplified: a resist layer after exposure and development steps, at least one treatment of exposure and development (hereinafter also referred to as "exposure and/or development treatment") ”) resist layer, or hardened resist layer. As a resin material which forms a resin mask, in one or a plurality of embodiments, a film-like photosensitive resin, a resist film, or a photoresist can be mentioned. A general-purpose resist film can be used. In one or more embodiments, the resin mask is a mask for copper or tin plating for copper or tin plating.

[detergent composition] The detergent composition of this invention is the detergent composition for resin mask peeling which contains the component A, the component B, and the component C mentioned later in one or more embodiment.

[Organic nitrogen-containing compound (ingredient A)] The detergent composition of the present invention contains a combination of two components (hereinafter also abbreviated as "" Ingredient A"). Component A1 may be one type or a combination of two or more types. Component A2 may be one type or a combination of two or more types.

[hua 7]

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.

[hua 8]

In the above formula (II), R ⁵ represents at least one selected from a hydrogen atom, methyl, ethyl and aminoethyl, and R ⁶ represents a hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and At least one kind of ethyl group, and R ⁷ represents at least one kind selected from aminoethyl group, hydroxyethyl group and hydroxypropyl group.

As the quaternary ammonium hydroxide (component A1) represented by the formula (I), for example, a salt containing a quaternary ammonium cation and a hydroxide can be mentioned. Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and 2-hydroxyethyltrimethylammonium hydroxide. ammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2 -Hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl) base) ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydrogen At least one of oxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide. Among them, from the viewpoint of improving the removability of the resin mask, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred, and tetramethylammonium hydroxide (TMAH) is more preferred. .

As an amine (component A2) represented by Formula (II), an alkanolamine, a primary-tertiary amine, a heterocyclic compound, etc. are mentioned, for example. Specific examples of the amine include monoethanolamine (MEA), monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethyl Isopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N- (β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, 1-methylpiperazine, 1 At least one of -(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperidine, ethylenediamine, and dipethylenetriamine. Among these, from the viewpoint of improving the removability of the resin mask, monoethanolamine (MEA) and diethanolamine are preferable, and monoethanolamine (MEA) is more preferable.

Regarding the content of the component A (the total content of the content of the component A1 and the content of the component A2) at the time of use of the detergent composition of the present invention, the removability (peelability) of the resin mask is not greatly impaired, and the cleaning From the viewpoint that the residue on the cleaned substrate is greatly increased to suppress copper corrosion, it is preferably 5 mass % or more, more preferably 6 mass % or more, and still more preferably 7 mass % or more, and from the same viewpoint More preferably, it is 15 mass % or less, More preferably, it is 13 mass % or less, More preferably, it is 12 mass % or less. More specifically, the content of the component A at the time of use of the detergent composition of the present invention is preferably 5 mass % or more and 15 mass % or less, more preferably 6 mass % or more and 13 mass % or less, and still more preferably 7 mass % or less. Mass % or more and 12 mass % or less. When the component A1 is a combination of two or more types, the content of the component A1 refers to the total content of the components. When component A2 is a combination of two or more types, the content of component A2 refers to the total content of these components.

Regarding the ratio (mass ratio A1/A2) of the content of the component A1 to the content of the component A2 in the detergent composition of the present invention, the removability (peelability) of the resin mask is not greatly impaired, and the cleaning From the viewpoint that the residue on the substrate is greatly increased after that and suppresses copper corrosion, it is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.6 or more, and, from the same viewpoint, preferably 2 Below, it is more preferable that it is 1.5 or less, and it is still more preferable that it is 1 or less. More specifically, the mass ratio A1/A2 is preferably 0.1 or more and 2 or less, more preferably 0.3 or more and 1.5 or less, and still more preferably 0.6 or more and 1 or less.

In the present invention, "the content of each component at the time of use of the detergent composition" refers to the content of each component at the time of washing, that is, the point in time when the detergent composition starts to be used for washing.

[Reducing agent (ingredient B)] The detergent composition of the present invention contains a reducing agent (hereinafter also simply referred to as "component B"). As the component B, from the viewpoint of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask, and without significantly increasing the residue on the substrate after cleaning, ascorbic acid (hereinafter also referred to as Component B) can be selected from the group consisting of ascorbic acid referred to as "component B1"), and at least 1 of an N-oxide compound containing a nitrogen-containing heteroaromatic ring in which at least one hydrogen atom of a nitrogen-containing heteroaromatic ring is substituted with a hydroxyl group (hereinafter also referred to as "component B2") kind. Among these, from the viewpoint of the stability of the detergent composition, ingredient B2 is preferred. As said salt, an alkali metal salt, an alkaline earth metal salt, an organic amine salt, an ammonium salt, etc. are mentioned. Component B may be used alone or in combination of two or more.

As the component B1, one or more kinds selected from L-ascorbic acid, D-ascorbic acid, erythorbic acid, and salts thereof may, for example, be mentioned. At least one nitrogen atom contained in the nitrogen-containing heteroaromatic ring skeleton of component B2 forms an N-oxide. As the nitrogen-containing heteroaromatic ring contained in the component B2, in one or more embodiments, a monocyclic or bicyclic condensed ring can be exemplified. The number of nitrogen atoms of the nitrogen-containing heteroaromatic ring contained in the component B2 is from the viewpoint of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask and without significantly increasing the residue on the substrate after cleaning. Specifically, 1 to 3 are preferable, 1 or 2 are more preferable, and 1 is still more preferable. As the nitrogen-containing heteroaromatic ring skeleton contained in the component B2, in one or more embodiments, a pyridine-N-oxide skeleton can be exemplified. In the present invention, the pyridine-N-oxide skeleton refers to a structure in which a nitrogen atom contained in a pyridine ring forms an N-oxide. As the component B2, at least one kind selected from the group consisting of N-oxide compounds having a pyridine ring in which at least one hydrogen atom is substituted with a hydroxyl group, and salts thereof can be exemplified. As a specific example of component B2, 2-hydroxypyridine-N-oxide etc. are mentioned.

In the present invention, the N-oxide compound represents a compound having an N-oxide group (N→O group) in one or more embodiments. The N-oxide compound may have one or two or more N→O groups, and the number of N→O groups is preferably one from the viewpoint of availability.

Component B is preferably ascorbic acid and 2-hydroxypyridine-N from the viewpoint of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask and without significantly increasing the residue on the substrate after cleaning. - at least one of the oxides.

The content of the component B when the detergent composition of the present invention is used does not greatly impair the removability (peelability) of the resin mask, and suppresses copper corrosion without greatly increasing the residue on the substrate after cleaning. From a viewpoint, it is preferably 0.05 mass % or more, more preferably 0.1 mass % or more, and still more preferably 0.2 mass % or more, and from the same viewpoint, preferably 5 mass % or less, more preferably 3 mass % or less, more preferably 1 mass % or less. More specifically, the content of component B is preferably 0.05 mass % or more and 5 mass % or less, more preferably 0.1 mass % or more and 3 mass % or less, and still more preferably 0.2 mass % or more and 1 mass % or less. When component B is a combination of two or more types, the content of component B refers to the total content of these components.

Regarding the ratio of the content of component A to the content of component B in the detergent composition of the present invention (mass ratio A/B), the resin mask removability (peelability) is not greatly impaired, and cleaning From the viewpoint that the residue on the substrate is greatly increased afterward to suppress copper corrosion, it is preferably 8 or more, more preferably 14 or more, more preferably 18 or more, and still more preferably 20 or more, and from the same viewpoint Specifically, it is preferably 50 or less, more preferably 45 or less, and still more preferably 40 or less. More specifically, the mass ratio A/B is preferably 8 or more and 50 or less, more preferably 14 or more and 45 or less, still more preferably 18 or more and 45 or less, and still more preferably 20 or more and 40 or less.

[Water (ingredient C)] In one or more embodiments, ion-exchanged water, reverse osmosis water, distilled water, pure water, and Ultrapure water, etc.

The content of the component C in the detergent composition of the present invention can be set as the residue after removing the component A, the component B, and the optional components described later. Specifically, the content of component C when the detergent composition of the present invention is used does not greatly impair the removability (peelability) of the resin mask and does not significantly increase the residue on the substrate after cleaning From the viewpoint of suppressing copper corrosion, reducing the load of drainage treatment, and reducing the influence on the substrate, it is preferably 50 mass % or more, more preferably 60 mass % or more, and still more preferably 70 mass % or more. More preferably, it is 80 mass % or more, and from the same viewpoint, it is preferably 99 mass % or less, more preferably 98 mass % or less, and still more preferably 97 mass % or less. More specifically, the content of the component C in use of the detergent composition of the present invention is preferably 50% by mass or more and 99% by mass or less, more preferably 60% by mass or more and 99% by mass or less, and still more preferably 70% by mass. The mass % or more is 98 mass % or less, more preferably 80 mass % or more and 97 mass % or less.

The total amount of Component A, Component B, and Component C when using the detergent composition of the present invention does not greatly impair the removability (peelability) of the resin mask and does not leave residues on the substrate after cleaning From the viewpoint of suppressing copper corrosion due to a large increase in the amount of copper, the content is preferably 60% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

[Organic solvent (ingredient D)] In one or more embodiments, the detergent composition of the present invention does not greatly impair the removability (peelability) of the resin mask, and suppresses copper corrosion without greatly increasing the residue on the substrate after cleaning. From a viewpoint, an organic solvent (henceforth also abbreviated as "component D") may be further contained. Component D may be one type or a combination of two or more types. As component D, in one or a plurality of embodiments, at least one solvent selected from glycol ethers and aromatic ketones may, for example, be mentioned. From the same viewpoint, the glycol ether includes a compound having a structure obtained by adding 1 to 3 mol or less of ethylene glycol to an alcohol having 1 to 8 carbon atoms. Specific examples of glycol ethers include diethylene glycol monobutyl ether (BDG), ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol. At least one kind of alcohol diethyl ether. As an aromatic ketone, acetophenone etc. are mentioned from the same viewpoint.

When the detergent composition of the present invention contains the component D, the content of the component D at the time of use of the detergent composition of the present invention does not greatly impair the removability (peelability) of the resin mask, and does not From the viewpoint of significantly increasing the residue on the cleaned substrate and suppressing copper corrosion, it is preferably 1 mass % or more, more preferably 1.5 mass % or more, still more preferably 2 mass % or more, and the same From a viewpoint, 40 mass % or less is preferable, 20 mass % or less is more preferable, and 5 mass % or less is still more preferable. More specifically, the content of component D at the time of use is preferably 1 mass % or more and 40 mass % or less, more preferably 1.5 mass % or more and 20 mass % or less, and still more preferably 2 mass % or more and 5 mass % or less. When component D is a combination of two or more types, the content of component D refers to the total content of these components.

[chelating agent (ingredient E)] In one or more embodiments, the detergent composition of the present invention does not greatly impair the removability (peelability) of the resin mask, and suppresses copper corrosion without greatly increasing the residue on the substrate after cleaning. From the viewpoint, a chelating agent (hereinafter also simply referred to as "component E") may be further contained. Component E may be one type or a combination of two or more types. As the component E, for example, a compound having at least one acid group selected from a carboxyl group and a phosphonic acid group can be mentioned, and from the same viewpoint, the following compounds are preferred, and the compound having at least four acid groups is preferred. the above acid group. As a specific example of component E, in one or a plurality of embodiments, aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and etidronate may, for example, be mentioned. acid (1-hydroxyethane-1,1-diphosphonic acid, HEDP), etc. Among them, from the viewpoint of reducing environmental load, compounds containing no nitrogen atom such as 2-phosphonobutane-1,2,4-tricarboxylic acid and etidronic acid (HEDP) are preferred. .

When the detergent composition of the present invention contains the component E, the content of the component E at the time of use of the detergent composition of the present invention does not greatly impair the removability (peelability) of the resin mask, and the From the viewpoint that the residue on the substrate after cleaning is greatly increased to suppress copper corrosion, it is preferably 0.5 mass % or more, more preferably 1 mass % or more, and from the same viewpoint, 5 mass % is preferable % or less, more preferably 3 mass % or less. More specifically, the content of the component E in use 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 E is a combination of two or more types, the content of component E refers to the total content of these components.

[Ingredient F: Ammonium salt of organic acid] In one or more embodiments, the detergent composition of the present invention does not greatly impair the removability (peelability) of the resin mask, and suppresses copper corrosion without greatly increasing the residue on the substrate after cleaning. From a viewpoint, at least one type of ammonium salt of an organic acid (hereinafter also referred to as "component F") may be further contained. From the same viewpoint, the ammonium salt of an organic acid is preferably an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms, and more preferably ammonium formate. Component F may be one type or a combination of two or more types.

When the detergent composition of the present invention contains the component F, the content of the component F at the time of use of the detergent composition of the present invention does not greatly impair the removability (peelability) of the resin mask, and the From the viewpoint of significantly increasing the residue on the substrate after cleaning and suppressing copper corrosion, it is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, still more preferably 0.3 mass % or more, and the same From a viewpoint, 2 mass % or less is preferable, 1.5 mass % or less is more preferable, and 1 mass % or less is still more preferable. More specifically, the content of component F is preferably 0.1 mass % or more and 2 mass % or less, more preferably 0.2 mass % or more and 1.5 mass % or less, and still more preferably 0.3 mass % or more and 1 mass % or less. When component F is a combination of two or more types, the content of component F refers to the total content of these components.

In one or a plurality of embodiments, the detergent composition of the present invention preferably further contains Component D, Component E, and Component F from the viewpoint of improving the removability of the resin mask.

[other ingredients] The detergent composition of the present invention may further contain other components as necessary in addition to the above-mentioned components A to F within the range that does not impair the effects of the present invention. As other components, components that can be used in ordinary detergents can be exemplified, for example, alkali agents other than component A, organic solvents other than component D, surfactants, chelating agents other than component E, thickeners Agents, dispersants, rust inhibitors, polymer compounds, cosolvents, antioxidants, preservatives, defoaming agents, and antibacterial agents, etc. The content of other components at the time of use of the detergent composition of the present invention is preferably 0 mass % or more and 2 mass % or less, more preferably 0 mass % or more and 1.5 mass % or less, still more preferably 0 mass % or more and 1.3 mass % % or less, more preferably 0 mass % or more and 1 mass % or less.

In one or more embodiments, the detergent composition of the present invention preferably does not contain a triazole-based anticorrosion agent. For example, in one or more embodiments, the content of the triazole-based anticorrosion agent at the time of use of the cleaning composition of the present invention is less than 0.005 mass %.

When the detergent composition of the present invention is used, the total content of organic substances derived from component A, component B and optional components (component D, component E, component F, and other components) reduces the waste water treatment load and reduces the load on the substrate. From the viewpoint of influence, it is preferably 30 mass % or less, more preferably 25 mass % or less, more preferably 20 mass % or less, and still more preferably 16 mass % or less, and in terms of improving the removability of the resin mask. From a viewpoint, 2 mass % or more is preferable, 3 mass % or more is more preferable, 4 mass % or more is still more preferable, and 6 mass % or more is more preferable. More specifically, the total content of organic substances derived from component A, component B, component C and optional components (component D, component E, component F, other components) when the detergent composition of the present invention is used is preferably 2 mass % or more and 30 mass % or less, more preferably 3 mass % or more and 25 mass % or less, more preferably 4 mass % or more and 20 mass % or less, still more preferably 6 mass % or more and 16 mass % or less.

[Manufacturing method of detergent composition] The detergent composition of the present invention can be produced by preparing the component A, component B, component C, and optionally the above-mentioned optional components (component D, component E, component F, and other components) by a known method. For example, in one or a plurality of embodiments, the detergent composition of the present invention may be prepared by blending at least Component A, Component B, and Component C. Therefore, the present invention relates to a method for producing a detergent composition, which includes at least the step of preparing the component A, the component B, and the component C. In the present invention, "mixing" includes mixing Component A, Component B, Component C, and optionally the above-mentioned optional components (Component D, Component E, Component F, and other components) at the same time or in any order. In the manufacturing method of the detergent composition of the present invention, the preferable compounding amount of each component can be set to be the same as the preferable content of each component of the above-mentioned detergent composition of the present invention.

The detergent composition of the present invention may be directly used for cleaning, or may be prepared as a concentrate in which the amount of water (ingredient C) is reduced within a range where separation or precipitation does not impair storage stability. . From the viewpoint of transportation and storage, the concentrate of the detergent composition is preferably made into a concentrate with a dilution ratio of 3 times or more, and from the viewpoint of storage stability, it is preferably made into a dilution ratio of 30 times or less. of the concentrate. The concentrate of the detergent composition can be used by water (ingredient C) with each ingredient (ingredient A, ingredient B, ingredient C, ingredient D, ingredient E, ingredient F, and other ingredients) into the above-mentioned content (ie, ingredient C). , the content when washing) is diluted and used. Furthermore, the concentrate of a detergent composition can also be used by adding each component separately at the time of use. In the present invention, "at the time of use" or "at the time of washing" of the detergent composition of the concentrate refers to a state in which the concentrate of the detergent composition is diluted.

[to be washed] In one or more embodiments, the object to be cleaned is a substrate with a copper-containing metal layer and a resin mask on the surface. As said board|substrate, the board of an insulator, a film, etc. are mentioned, for example. Therefore, in one or more embodiments, the detergent composition of the present invention can be used to clean a substrate having a copper-containing metal layer and a resin mask on the surface. The copper-containing metal layer is, in one or more embodiments, a copper-plated layer. The copper plating layer can be formed by, for example, an electroless copper plating method. The copper-containing metal layer is used as metal wiring in one or more embodiments. In one or more embodiments, the substrate having the copper-containing metal layer and the resin mask on the surface undergoes the step of at least one of soldering and plating using the resin mask. In one or more embodiments, the above-mentioned substrate has a copper-containing metal layer or a tin-containing metal layer with a thickness of 15 μm or more. The thickness of the copper-containing metal layer or the tin-containing metal layer having a thickness of 15 μm or more is preferably 15 μm or more and 85 μm or less, more preferably 20 μm or more and 80 μm or less, from the viewpoint of electrical properties and manufacturability, and more preferably Preferably, it is 30 μm or more and 70 μm or less. A copper-containing metal layer or a tin-containing metal layer having a thickness of 15 μm or more is used as a metal wiring or a wiring connection in one or more embodiments.

In one or more embodiments, the object to be cleaned is an object to be cleaned to which a resin mask is attached. Therefore, in one or more embodiments, the detergent composition of the present invention can be used for cleaning the object to be cleaned to which the resin mask is attached. As the object to be cleaned to which the resin mask is attached, in one or more embodiments, an electronic component having a copper-containing metal portion and a resin mask on the surface, and an intermediate product thereof can be exemplified. As an electronic component, at least 1 component chosen from metal plates, such as a printed circuit board, a wafer, and a copper plate and an aluminum plate, is mentioned, for example. The above-mentioned manufacturing intermediate is an intermediate manufactured in the manufacturing steps of electronic parts, including the intermediate manufactured after resin mask treatment. As a specific example of the object to be cleaned to which the resin mask is attached, for example, electronic parts, etc., which are processed by welding and plating (copper plating, aluminum plating, nickel plating, A step of at least one treatment of tin, etc.), thereby forming wirings or connecting terminals, etc. on the surface of the substrate. In the present invention, soldering refers to the formation of solder bumps by heating the solder in the resin mask-free portion on the substrate. In the present invention, the plating treatment means that at least one kind of plating treatment selected from copper plating, aluminum plating, nickel plating and tin plating is performed on the resin mask-free portion on the substrate. The resin mask-absent portion means that in the resist pattern (pattern-shaped resin mask) formed by subjecting the resin mask laminated to the substrate to the development process, the resin mask is removed by the development process part of. Accordingly, the present invention in one aspect relates to the use of a detergent composition of the present invention as a detergent in the manufacture of electronic parts.

In one or more embodiments, the object to be cleaned is subjected to a substrate having a resist pattern (pattern-shaped resin mask) formed by developing a resin mask laminated to the substrate. Steps of at least one of soldering and plating treatments. For example, as the object to be cleaned, there may be mentioned a substrate having a portion as a resin mask existing portion formed with a hardened resist layer on the substrate, and a solder bump or plated portion formed on the resin mask nonexistent portion. The part of the coating.

In one or more embodiments, the object to be cleaned is a substrate having a resin mask existing in a fine gap. In the present invention, the gap refers to the distance between patterns (the distance between adjacent wirings) in one or more embodiments, and is also referred to as space (S). Moreover, the width|variety of a pattern (wiring) is also called a line (L). In one or more embodiments, the resin mask existing in the fine gap refers to the resin mask existing in a space with a space width of 10 μm or less. As a resin mask which exists in a fine gap, the resin mask which exists in the space whose space width is 4-7 micrometers is mentioned, for example.

In one or a plurality of embodiments, the detergent composition of the present invention can be favorably used for cleaning a resin mask attached, or further subjected to a plating treatment and/or a heat treatment from the viewpoint of the cleaning effect. The object to be cleaned of the resin cover. The resin mask may be, for example, a negative resin mask or a positive resin mask. In the present invention, the so-called negative-type resin mask refers to what is formed using a negative-type resist, for example, a negative-type resist layer that has been exposed and/or developed. In the present invention, the positive-type resin mask refers to what is formed using a positive-type resist, for example, a positive-type resist layer that has been exposed and/or developed.

[Washing method] In one or more embodiments, the cleaning method of the present invention includes the following steps (hereinafter also referred to as "peeling step"): using the cleaning composition of the present invention to have a copper-containing metal layer and a resin mask from the surface The substrate (object to be cleaned) peels off the resin mask. In one or more embodiments, the above-mentioned peeling step includes contacting the object to be cleaned with the cleaning composition of the present invention. In one or more embodiments, the above-mentioned peeling step includes removing the resin mask existing in the fine gap. The resin mask existing in the fine gap is, as described above, a resin mask existing in a space with a space width of 10 μm or less. According to the cleaning method of the present invention, copper corrosion can be suppressed without significantly impairing the removability (peelability) of the resin mask, and without significantly increasing the residue on the substrate after cleaning.

As a method of peeling off the resin mask from the object to be cleaned using the detergent composition of the present invention, or a method of contacting the object to be cleaned with the detergent composition of the present invention, for example, by dipping to The method of contacting in a cleaning bath containing the detergent composition, the method of contacting by spraying the detergent composition in the form of a spray (spray method), and the ultrasonic cleaning method of irradiating ultrasonic waves during immersion Wait. The detergent composition of the present invention can be directly used for cleaning without dilution. As the object to be washed, the aforementioned object to be washed can be exemplified.

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

In the cleaning method of the present invention, from the viewpoint of easily exerting the cleaning power of the detergent composition of the present invention, it is preferable to irradiate ultrasonic waves when the detergent composition of the present invention is in contact with the object to be cleaned, More preferably, the ultrasound is of a higher frequency. From the same viewpoint, the irradiation conditions of the above-mentioned ultrasonic waves are, for example, preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

In the cleaning method of the present invention, the temperature of the detergent composition is preferably 40°C or higher, more preferably 50°C or higher, from the viewpoint of easily exerting the cleaning power of the detergent composition of the present invention. Moreover, from a viewpoint of reducing the influence on a board|substrate, 70 degrees C or less is preferable, and 60 degrees C or less is more preferable.

[Manufacturing method of electronic parts] In one aspect, the present invention 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 comprises using the cleaning method of the present invention to provide a surface with a copper-containing metal layer and the step of cleaning the substrate (object to be cleaned) of the resin mask (cleaning step). As the object to be washed, the above-mentioned object to be washed may, for example, be mentioned. In one or more embodiments, the method for manufacturing an electronic component of the present invention may include, prior to the cleaning step, at least one electronic component selected from a printed circuit board, a wafer, and a metal plate using a resin mask. Steps of at least one of soldering and plating treatments. In one or more embodiments, the method for manufacturing an electronic component of the present invention may include a step of etching the copper-containing metal layer after the cleaning step. The manufacturing method of the electronic component of the present invention can be cleaned by using the cleaning method of the present invention, without greatly impairing the removability (peelability) of the resin mask, and without greatly increasing the residue on the substrate after cleaning. Corrosion of copper is inhibited, so it is possible to manufacture electronic parts with high reliability. Furthermore, by carrying out the cleaning method of the present invention, the resin mask adhering to the electronic component can be easily removed, so that the cleaning time can be shortened, and the manufacturing efficiency of the electronic component can be improved.

[set] In one aspect, the present invention relates to a kit (hereinafter also referred to as "the kit of the present invention") for use in any one of the cleaning method of the present invention and the manufacturing method of an electronic component of the present invention. The kit of the present invention, in one or more embodiments, is a kit for making the detergent composition of the present invention. According to the kit of the present invention, it is possible to obtain a cleaning composition capable of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask and without significantly increasing the residue on the substrate after cleaning.

As one embodiment of the kit of the present invention, a kit (two-component detergent composition) comprising a solution containing component A (first solution) and component B in a state that they are not mixed with each other can be exemplified The solution (second liquid), at least one of the first liquid and the second liquid further contains a part or all of water (component C), and the first liquid and the second liquid are mixed at the time of use. After mixing the 1st liquid and the 2nd liquid, you may dilute with water (component C) as needed. Each of the first liquid and the second liquid may contain any of the above-mentioned components as necessary. Example

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by these examples at all.

1. Preparation of detergent compositions of Examples 1 to 13, Comparative Example 1 and Reference Examples 1 to 2 Examples 1 to 13, Comparative Example 1, and Reference Examples 1 to 2 were prepared by blending, stirring and mixing the components shown in Table 1 according to the blending amounts (mass %, effective fraction) described in Table 1. detergent composition.

The following components were used for the preparation of the detergent compositions of Examples 1 to 13, Comparative Example 1 and Reference Examples 1 to 2. (ingredient A) TMAH: Tetramethylammonium hydroxide [manufactured by Showa Denko Co., Ltd., concentration 25%] MEA: Monoethanolamine [manufactured by Nippon Shokubai Co., Ltd.] (ingredient B) Ascorbic acid [Fujifilm Wako Pure Chemical Industries Ltd.] HOPO: 2-hydroxypyridine-N-oxide [manufactured by Suzhou Haofan Biological Co., Ltd.] (ingredient C) Water [Pure water below 1 μS/cm produced by Organo Co., Ltd. Purified Water Device G-10DSTSET] (ingredient D) BDG: Diethylene glycol butyl ether [manufactured by Nippon Emulsifier Co., Ltd., diethylene glycol monobutyl ether] (ingredient E) HEDP: etidronic acid [manufactured by Italmatch Japan Co., Ltd., Dequest2010, concentration 60%] (ingredient F) Ammonium formate [manufactured by Toyama Pharmaceutical Co., Ltd.] (other ingredients) Benzotriazole [Mitsui Fine Chemicals Co., Ltd.] (coating type etching inhibitor) Thioacetamide [Fujifilm Wako Pure Chemical Industries, Ltd.] (coated etching inhibitor)

2. Evaluation of detergent compositions The following evaluations were performed on the prepared detergent compositions of Examples 1 to 13, Comparative Example 1, and Reference Examples 1 to 2.

[Preparation of Test Piece I] A photosensitive film for forming a PKG (semiconductor package) substrate circuit was laminated on the surface of the substrate after electroless plating under the following conditions, and the exposed portion was selectively cured by exposure treatment (exposure step ), the unexposed portion is removed by developing treatment (developing step) to obtain a substrate with a resist pattern (negative resin mask in the shape of a pattern). Furthermore, copper plating (thickness 10 μm) was performed on the region where the unexposed portion was removed by the above-mentioned development treatment, thereby obtaining a resin mask comprising a copper-containing metal layer (copper wiring) and a hardened resist layer on the surface. Test piece I of the substrate (50 mm × 50 mm). (1) Lamination: using a cleaning roller (manufactured by RAYON INDUSTRIAL Co., Ltd., RY-505Z) and a vacuum applicator (manufactured by Rohm and Haas, VA7024/HP5), at a roller temperature of 50° C. and a roller pressure of 1.4 Bar. (2) Exposure: Using a direct drawing device for printed circuit boards (manufactured by SCREEN Graphic and Precision Solutions Co., Ltd., Mercurex LI-9500), exposure was performed at an exposure amount of 15 mJ/cm ² . (3) Pattern shape: L/S=5 μm/5 μm, 6 μm/6 μm, 7 μm/7 μm stripe pattern. In addition, L/S shows: the line (L) which shows the width|variety of a pattern (copper wiring), and the space (S) which shows the distance (width of an insulating part) between adjacent patterns. (4) Development: Using a substrate developing device (manufactured by Yangbo Technology Co., Ltd., LT-980366), a 1% sodium carbonate aqueous solution at 30°C, and a spray pressure of 0.2 MPa, the resin mask of the unexposed part was removed.

[Cleaning test] The test piece I was washed with each detergent composition, and the resin mask was peeled off from the substrate. Add 3 kg of detergent composition to a 5 L stainless steel beaker, heat it to 50°C, and use a box-type spray washing machine equipped with a single-fluid nozzle (dense cone) J020 (manufactured by H.IKEUCHI Co., Ltd.) as a spray nozzle. While circulating in the cleaning machine, the test piece I was sprayed (pressure: 0.1 MPa, spray distance: 8 cm) for 1 minute (peeling step or washing step). Then, it was immersed in a 1 L glass beaker in a rinse tank in which 1 kg of water was added, rinsed, and then blown dry with nitrogen.

[Evaluation of Removability I of Resin Mask] Using an optical microscope "Digital Microscope VHX-6000" (manufactured by Keyence Corporation), magnify 500 times and visually confirm whether there is any residual resin mask in the pattern portion of the test piece I after the above cleaning test. standard for evaluation. The results are shown in Table 1. ＜Evaluation Criteria＞ A: No residue was found even at 5 μm/5 μm B: No residue found up to 6 μm/6 μm C: No residue found up to 7 μm/7 μm D: Residue can still be found at 7 μm/7 μm

[Evaluation of Cu etching rate (Evaluation of copper corrosion)] Each detergent composition was adjusted to 2.5 L, heated to 50°C, and installed with a dense cone nozzle (manufactured by H.IKEUCHI Co., Ltd., J020) In the box-type spray cleaning machine used as a spray nozzle, one side was circulated, and the other side was sprayed on the test piece I whose surface was copper-plated (25 cm ² per one side, 50 cm ² on both sides) (pressure: 0.05 MPa, spraying Distance: 80 mm) 4 minutes. After diluting the detergent composition, the eluted amount of copper was measured by ICP (Inductively coupled plasma) analysis (manufactured by Agilent Technologies, Agilent5110 ICP-OES). The density of copper was set by the following formula. It was 8.94 g/cm ³ , and the Cu etching rate (μm/min) was evaluated according to the dissolution amount. The results are shown in Table 1. The lower the numerical value of the Cu etching rate, the more excellent the copper corrosion inhibition effect can be judged. Cu etching rate (μm/min) = copper dissolution amount (weight) ÷ copper density ÷ plating area ÷ treatment time

[Residual properties of ingredients] The copper-plated portion of the substrate sample subjected to the above-mentioned cleaning test was analyzed by X-ray photoelectron spectroscopy, and the residue was evaluated according to the following criteria based on the signal intensities of carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. The results are shown in Table 1. If obvious signals of carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms are detected, it is determined that components derived from the detergent composition remain on the cleaned substrate. ＜Evaluation Criteria＞ A: No signal detected, or only weak signal detected B: Obvious signal detected

[stability] The change in color or turbidity of the appearance of the detergent composition before and after the above-mentioned cleaning test was visually observed, and evaluated according to the following criteria. The results are shown in Table 1. ＜Evaluation Criteria＞ A: No change was found before and after the cleaning test B: Changes were found before and after the cleaning test

[Table 1] Table 1 Comparative example Example Reference example 1 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 Compounding amount (mass %) Ingredient A TMAH 4.0 4.0 4.0 4.0 1.0 7.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 MEA 6.0 6.0 2.0 8.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Ingredient B ascorbic acid 0.5 0.5 0.5 0.5 0.5 0.2 1.0 0.5 HOPO 0.5 0.5 0.5 0.5 0.5 Ingredient C water 90.0 89.5 93.5 87.5 92.5 86.5 89.8 89.0 89.5 86.5 87.7 89.0 84.2 84.2 84.2 84.2 Ingredient D BDG 3.0 3.0 3.0 3.0 3.0 Ingredient E HEDP 1.8 1.8 1.8 1.8 1.8 Ingredient F Ammonium formate 0.5 0.5 0.5 0.5 0.5 other ingredients benzotriazole 0.5 Thioacetamide 0.5 Total (mass %) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Mass ratio A/B - 20 12 twenty four 14 26 50 10 20 20 20 20 20 20 - - peel I B B C B B B B B B B B B A A B B Corrosivity: Cu etch rate (µm/min) 0.05 0.02 0.02 0.03 0.03 0.02 0.03 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.00 Residue of ingredients A A A A A A A A A A A A A A B B Stability of detergent compositions A B B B B B B B A A A A A B A A

As shown in Table 1, it can be seen that the detergent compositions of Examples 1 to 13 can not significantly impair the removability of the resin mask as compared with Comparative Example 1 and Reference Examples 1 to 2 that do not contain Component B The residue on the cleaned substrate is greatly increased to inhibit copper corrosion.

The prepared detergent compositions of Example 1 and Comparative Example 1 were further evaluated as follows.

[Test Piece II] The photosensitive film for forming a PKG (semiconductor package) board circuit was laminated on the surface of the substrate after electroless plating under the following conditions, and after selectively exposure treatment was performed to harden the exposed portion (exposure step), The unexposed portion is removed by developing treatment (developing step) to obtain a substrate having a resist pattern (negative resin mask of pattern shape). In addition, copper plating (50 μm in thickness) was performed on the region where the unexposed portion was removed by the above-mentioned development treatment, thereby obtaining a resin mask including a copper-containing metal layer (copper wiring) and a hardened resist layer on the surface. Test piece II of the substrate (50 mm x 50 mm). (1) Lamination: using a cleaning roller (manufactured by RAYON INDUSTRIAL Co., Ltd., RY-505Z) and a vacuum applicator (manufactured by Rohm and Haas, VA7024/HP5), at a roller temperature of 50° C. and a roller pressure of 1.4 Bar. (2) Exposure: Using a direct drawing device for printed circuit boards (manufactured by SCREEN Graphic and Precision Solutions Co., Ltd., Mercurex LI-9500), exposure was performed at an exposure amount of 15 mJ/cm ² . (3) Pattern shape: stripe pattern with L/S=20 μm/20 μm. In addition, L/S shows: the line (L) which shows the width|variety of a pattern (copper wiring), and the space (S) which shows the distance (width of an insulating part) between adjacent patterns. (4) Development: Using a substrate developing device (manufactured by Yangbo Technology Co., Ltd., LT-980366), a 1% sodium carbonate aqueous solution at 30°C, and a spray pressure of 0.2 MPa, the resin mask of the unexposed part was removed.

[Cleaning test] The test piece II was washed with each detergent composition, and the resin mask was peeled off from the substrate. Add 3 kg of detergent composition to a 5 L stainless steel beaker, heat it to 50°C, and use a box-type spray washing machine equipped with a single-fluid nozzle (dense cone) J020 (manufactured by H.IKEUCHI Co., Ltd.) as a spray nozzle. While circulating in the cleaning machine, the test piece II was sprayed (pressure: 0.1 MPa, spray distance: 8 cm) for 10 minutes (peeling step or washing step). Then, it was immersed in a 1 L glass beaker in a rinse tank in which 1 kg of water was added, rinsed, and then blown dry with nitrogen.

[Evaluation of Removability II of Resin Mask] Using an optical microscope "Digital Microscope VHX-6000" (manufactured by Keyence Corporation), magnify 500 times and visually confirm whether there is any residual resin mask in the pattern portion of the test piece II after the above cleaning test. standard for evaluation. The results are shown in Table 2. ＜Evaluation Criteria＞ A: The residue per chip is 2 or less B: The residue per wafer is 3 or more and 9 or less C: 10 or more and 20 or less residues per wafer D: 21 or more residues per wafer

[Evaluation of Cu etching rate (Evaluation of copper corrosion)] The evaluation of the copper corrosion of the test piece II was performed in the same manner as the evaluation of the copper corrosion of the test piece I. The results are shown in Table 2.

[Table 2] Table 2 Comparative example Example 1 1 Compounding amount (mass %) Ingredient A TMAH 4.0 4.0 MEA 6.0 6.0 Ingredient B ascorbic acid 0.5 Ingredient C water 90.0 89.5 Total (mass %) 100.0 100.0 Mass ratio A/B - 20 Stripping II C A Corrosivity: Cu etch rate (µm/min) 0.05 0.02

As shown in Table 2, it can be seen that the detergent composition of Example 1 can improve the resin mask removability and suppress copper corrosion as compared with Comparative Example 1 which does not contain component B. [Industrial Availability]

According to the present invention, it is possible to provide a cleaning method capable of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask and without significantly increasing the residue on the substrate after cleaning. The cleaning method of the present invention can shorten the cleaning steps of the electronic parts to which the resin mask is attached, and can improve the performance and reliability of the manufactured electronic parts, and can improve the productivity of the semiconductor device.

Claims (16)

A method for cleaning a substrate, comprising the steps of: using a detergent composition containing the following component A, the following component B and the following component C, peeling off resin from a substrate having a copper-containing metal layer and a resin mask on the surface Mask; Component A: quaternary ammonium hydroxide represented by the following formula (I) and amine represented by the following formula (II) Component B: reducing agent Component C: water

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

In the above formula (II), R ⁵ represents at least one selected from a hydrogen atom, methyl, ethyl and aminoethyl, and R ⁶ represents a hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and At least one kind of ethyl group, and R ⁷ represents at least one kind selected from aminoethyl group, hydroxyethyl group and hydroxypropyl group. The cleaning method of claim 1, wherein the copper-containing metal layer is a copper-plated layer. The cleaning method of claim 1, wherein the resin mask is a hardened resist layer. The cleaning method according to claim 1, wherein the component B is one or more selected from ascorbic acid and N-oxide compounds containing nitrogen-containing heteroaromatic rings in which at least one hydrogen atom of the nitrogen-containing heteroaromatic ring is substituted with a hydroxyl group. The cleaning method of claim 1, wherein the content of component B is 0.05 mass % or more and 5 mass % or less. The cleaning method of claim 1, wherein the substrate has a copper-containing metal layer with a thickness of 15 μm or more. The cleaning method of claim 1, wherein the step of peeling off the resin mask includes removing the resin mask existing in the fine gaps. The cleaning method of any one of claims 1 to 7, wherein the substrate having the copper-containing metal layer and the resin mask on the surface is subjected to at least one of soldering and plating using the resin mask. A method for manufacturing an electronic component, comprising the steps of: using the cleaning method according to any one of claims 1 to 8, cleaning a substrate having a copper-containing metal layer and a resin mask on the surface. A detergent composition for peeling off a resin mask, comprising the following component A, the following component B, and the following component C: Component A: a quaternary ammonium hydroxide represented by the following formula (I) and the following Amine Component B represented by Formula (II): Reducing Agent Component C: Water

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

In the above formula (II), R ⁵ represents at least one selected from a hydrogen atom, methyl, ethyl and aminoethyl, and R ⁶ represents a hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and At least one kind of ethyl group, and R ⁷ represents at least one kind selected from aminoethyl group, hydroxyethyl group and hydroxypropyl group. The detergent composition of claim 10, wherein component B is at least one of ascorbic acid and 2-hydroxypyridine-N-oxide. The detergent composition of claim 10, wherein the content of component A is 5 mass % or more and 15 mass % or less, and the content of component B is 0.05 mass % or more and 5 mass % or less. The detergent composition of claim 10, wherein the total amount of component A, component B and component C is 90% by mass or more. The detergent composition of claim 10, wherein the content of component C is 60% by mass or more. The cleaning composition for resin mask peeling according to any one of claims 10 to 14, wherein the resin mask is a mask for copper plating or tin plating. A use of a cleaning composition for peeling off a resin mask, which is used as a cleaning agent in the manufacture of electronic parts, the above-mentioned cleaning composition for peeling off a resin mask contains the following component A, the following component B and the following Component C; Component A: quaternary ammonium hydroxide represented by the following formula (I) and amine represented by the following formula (II) Component B: reducing agent Component C: water

In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently at least one selected from methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl; [ 6]

In the above formula (II), R ⁵ represents at least one selected from a hydrogen atom, methyl, ethyl and aminoethyl, and R ⁶ represents a hydrogen atom, hydroxyethyl, hydroxypropyl, methyl and At least one kind of ethyl group, and R ⁷ represents at least one kind selected from aminoethyl group, hydroxyethyl group and hydroxypropyl group.