Cleaning composition for removing resin masks

Abstract

To provide a detergent composition for resin mask peeling that can suppress copper corrosion without significantly impairing resin mask removability.SOLUTION: In one embodiment, a detergent composition for resin mask peeling contains water-soluble amines (component A), at least one alkali agent selected from quaternary ammonium hydroxides and alkali metal hydroxides (component B), carbonate ions (component C) and water (component D). The component C has a concentration of 0.3 mol / L or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a cleaning composition for stripping a resin mask, a method for cleaning a substrate using the same, and a method for producing an electronic component. [Background technology]

[0002] In recent years, personal computers and various electronic devices have become more energy efficient, faster, and smaller, and the wiring on package substrates mounted on these devices is becoming finer year by year. Until now, the metal mask method has been mainly used to form such fine wiring and connection terminals such as pillars and bumps, but due to its low versatility and the difficulty of responding to the miniaturization of wiring, etc., other new methods are being used.

[0003] As one of the new methods, a method is known in which a dry film resist is used as a thick-film resin mask instead of a metal mask. This resin mask is finally peeled off and removed, and a cleaning agent for peeling off the resin mask, which contains an alkaline agent and water, is known as a cleaning agent used for the peeling off and removal.

[0004] For example, Patent Document 1 describes a resin mask layer cleaning composition that contains a specific quaternary ammonium hydroxide, a water-soluble amine, an acid or its ammonium salt, and water as a cleaning agent that can both promote removal of the resin mask layer after heat treatment of the solder bump and inhibit solder corrosion, thereby improving solder connection reliability. In the examples, it is disclosed that ammonium carbonate is used as the ammonium salt of the acid. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2015-79244 A Summary of the Invention [Problem to be solved by the invention]

[0006] When forming fine wiring on printed circuit boards and the like, a cleaning composition is required to have high cleaning properties in order to reduce not only the residue of a resin mask but also the residue of auxiliary agents contained in solder, plating solution, and the like used in forming the fine wiring and bumps. Here, the resin mask is formed using a resist whose physical properties, such as solubility in a developer, change due to light or an electron beam. Resists are broadly divided into negative and positive types based on the reaction method with light or an electron beam. A negative resist has a property that its solubility in a developer decreases when exposed to light, and the exposed portion of a layer containing a negative resist (hereinafter also referred to as a "negative resist layer") is used as a resin mask after exposure and development processing. A positive resist has a property that its solubility in a developer increases when exposed to light, and the exposed portion of a layer containing a positive resist (hereinafter also referred to as a "positive resist layer") is removed after exposure and development processing, and the unexposed portion is used as a resin mask. By using a resin mask having such properties, fine connections of a circuit board, such as metal wiring, metal pillars, and solder bumps, can be formed.

[0007] However, as wiring becomes finer, it becomes more difficult to remove the resin mask in the fine gap, and therefore the cleaning composition is required to have a high resin mask removability. Furthermore, since the corrosion of copper used in many wirings and connection terminals leads to a decrease in the quality and value of package boards, the cleaning composition is required to have a high corrosion prevention ability. The technology disclosed in Patent Document 1 has a high resin mask removal ability and a solder corrosion inhibition effect, but the copper corrosion inhibition effect is insufficient.

[0008] In view of the above, in one aspect, the present disclosure provides a cleaning composition for stripping a resin mask, which can suppress copper corrosion without significantly impairing the removability (peelability) of the resin mask, and a method for cleaning a substrate. [Means for solving the problem]

[0009] In one aspect, the present disclosure relates to a cleaning composition for stripping a resin mask, comprising a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, carbonate ions (component C), and water (component D), in which the concentration of component C is 0.3 mol / L or more.

[0010] In one aspect, the present disclosure relates to a cleaning composition for stripping a resin mask, comprising a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, a carbonate (component C'), and water (component D), in which the concentration of component C' is 0.3 mol / L or more.

[0011] In one embodiment, the present disclosure relates to a method for cleaning a substrate, the method including a step of peeling off a resin mask from a substrate having a copper-containing metal layer and a resin mask on a surface thereof, by using a cleaning composition containing a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, carbonate ions (component C), and water (component D), wherein the concentration of component C is 0.3 mol / L or more.

[0012] In one embodiment, the present disclosure relates to a method for cleaning a substrate, the method including a step of peeling off a resin mask from a substrate having a copper-containing metal layer and a resin mask on a surface thereof, by using a cleaning composition comprising a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, a carbonate (component C'), and water (component D), wherein the concentration of Component C' is 0.3 mol / L or more.

[0013] In one aspect, the present disclosure relates to a method for cleaning a substrate, the method including a step of peeling off a resin mask from a substrate having a copper-containing metal layer and a resin mask on a surface thereof, by using a cleaning composition containing a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, carbonate ions (component C), and water (component D), in which an amino group of component A is cationized.

[0014] In one aspect, the present disclosure relates to a method for cleaning a substrate, the method comprising the step of peeling off a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface, by using a cleaning composition comprising a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, a carbonate (component C'), and water (component D), in which an amino group of component A is cationized.

[0015] In one aspect, the present disclosure relates to a method for producing an electronic component, comprising a step of cleaning a substrate having a copper-containing metal layer and a resin mask on a surface thereof using the cleaning method of the present disclosure. Effect of the Invention

[0016] According to one embodiment of the present disclosure, a cleaning composition for stripping a resin mask can be provided that can suppress copper corrosion without significantly impairing the removability (peelability) of the resin mask. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present disclosure is based on the finding that a resin mask can be efficiently removed from a substrate surface while suppressing copper corrosion by using a cleaning composition containing a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, a predetermined concentration of carbonate ions (component C), and water (component D), or a cleaning composition for stripping a resin mask comprising a combination of components A, B, a predetermined concentration of a carbonate (component C'), and component D.

[0018] In one aspect, the present disclosure relates to a cleaning composition for stripping resin masks, which contains a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, carbonate ions (component C), and water (component D), in which the concentration of component C is 0.3 mol / L or more; or a cleaning composition for stripping resin masks which comprises a blend of component A, component B, a carbonate (component C'), and component D, in which the concentration of component C' is 0.3 mol / L or more (hereinafter these are also collectively referred to as the "cleaning composition of the present disclosure").

[0019] According to one or more embodiments of the present disclosure, a resin mask stripping cleaning composition capable of suppressing copper corrosion without significantly impairing the removability (stripping ability) of the resin mask can be provided. By using the cleaning composition of the present disclosure, high-quality electronic components can be obtained with high yield. Furthermore, by using the cleaning composition of the present disclosure, electronic components having fine wiring patterns can be efficiently manufactured.

[0020] Although the details of the mechanism of action by which the effects of the present disclosure are expressed are unclear, it is presumed as follows. In the present disclosure, by using a water-soluble amine (component A) in combination with at least one alkaline agent (component B) selected from quaternary ammonium hydroxides and alkali metal hydroxides, it is believed that components A and B penetrate into the resin mask to promote dissociation of the alkali-soluble resin contained in the resin mask, and further promote peeling of the resin mask by causing repulsion of the charges generated by the dissociation. On the other hand, the water-soluble amine (component A) is believed to be involved in etching (corrosion) of copper. Here, a specific concentration of carbonate ions (component C) cationizes the amino group of component A, forming a complex of components A and C, which is believed to suppress etching of copper by component A. However, the present disclosure need not be construed as being limited to this mechanism.

[0021] In the present disclosure, the resin mask to be peeled off and removed is a mask for protecting the surface of a material from treatments such as etching, plating, and heating, i.e., a mask that functions as a protective film. In one or more embodiments, the resin mask may be a resist layer after exposure and development steps, a resist layer that has been subjected to at least one of exposure and development (hereinafter also referred to as "exposed and / or developed"), or a hardened resist layer. In one or more embodiments, the resin material forming the resin mask may be a film-like photosensitive resin, a resist film, or a photoresist. A general-purpose resist film may be used.

[0022] [Water-soluble amine (ingredient A)] The cleaning composition of the present disclosure contains a water-soluble amine (hereinafter, also simply referred to as "component A"). In one or more embodiments, component A may be, for example, an amine represented by the following formula (I), etc. Component A may be one type or a combination of two or more types. In the present disclosure, "water-soluble" refers to having a solubility in water (20°C) of 0.5 g / 100 mL or more, preferably 2 g / 100 mL or more.

[0023] [ka]

[0024] In formula (I), R 1 is a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms; R 2 and R 3 are the same or different and each is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms; R 1 , R 2 and R 3 cannot simultaneously be a hydrogen atom.

[0025] The amine represented by formula (I) may be at least one selected from monoethanolamine, monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N,N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N,N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, ethylenediamine and diethylenetriamine. Among these, from the viewpoint of improving the removability (peelability) of the resin mask, monoethanolamine and diethanolamine are preferred, and monoethanolamine is more preferred.

[0026] As component A, from the viewpoint of inhibiting copper corrosion without significantly impairing the removability (peelability) of the resin mask, at least one selected from monoethanolamine, N,N-diethylethanolamine, N-methylethanolamine, ethylaminoethanol, and propanediamine is mentioned, and among these, monoethanolamine is preferred.

[0027] The content of component A during use of the cleaning composition of the present disclosure is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more from the viewpoint of resin mask removability (peelability), and is preferably 10% by mass or less, more preferably 9% by mass or less, and even more preferably 7% by mass or less from the viewpoint of copper corrosion inhibition. More specifically, the content of component A is preferably 2% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 9% by mass or less, and even more preferably 5% by mass or more and 7% by mass or less. When component A is a combination of two or more kinds, the content of component A refers to the total content thereof.

[0028] In the present disclosure, "the content of each component in the cleaning composition at the time of use" refers to the content of each component at the time of cleaning, i.e., at the time when the use of the cleaning composition for cleaning is started.

[0029] [Alkaline agent (ingredient B)] The cleaning composition of the present disclosure contains at least one alkaline agent selected from a quaternary ammonium hydroxide and an alkali metal hydroxide (hereinafter, also simply referred to as "Component B"). Component B may be one type or a combination of two or more types.

[0030] The quaternary ammonium hydroxide may be one represented by the following formula (II). [ka]

[0031] In the above formula (II), R 4 , R 5 , R 6 and R 7 are each independently at least one selected from a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0032] Examples of the quaternary ammonium hydroxide represented by formula (II) include salts composed of quaternary ammonium cations and hydroxides. Specific examples of the quaternary ammonium hydroxide include at least one selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, 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, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide. Among these, from the viewpoint of improving the removability (peelability) of the resin mask, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred, and tetramethylammonium hydroxide is more preferred.

[0033] In one or a plurality of embodiments, examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.

[0034] The content of Component B when using the cleaning composition of the present disclosure is preferably 0.5 mass% or more, and more preferably 3 mass% or more, from the viewpoint of resin mask removability (peelability). When Component B is a combination of two or more types, the content of Component B refers to the total content thereof. The content of Component B during use of the cleaning composition of the present disclosure is preferably 10 mass % or less, from the viewpoint of saturating the effects of the present invention.

[0035] [Carbonate ion: (Component C)] In one or more embodiments, the cleaning composition of the present disclosure contains carbonate ions (CO 2- ) (hereinafter, also simply referred to as "component C"). In one or more other embodiments, the cleaning composition of the present disclosure is formulated with a carbonate salt (hereinafter, also simply referred to as "component C'") which is a supply source of component C. In the cleaning composition of the present disclosure, it is considered that the etching of copper can be suppressed by the carbonate ion (component C) cationizing the amino group of component A. Therefore, in one or more embodiments, the cleaning composition of the present disclosure is a cleaning composition that contains components A, B, C, and D, and in which the amino group of component A is cationized. In one or more other embodiments, the cleaning composition of the present disclosure is a cleaning composition that contains components A, B, C', and D, and in which the amino group of component A is cationized.

[0036] In one or more embodiments, component C', which is a supply source of component C, is not particularly limited as long as it is a compound capable of supplying carbonate ions, but from the viewpoint of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask, examples of the carbonate salt include alkali metal carbonates, alkaline earth metal carbonates, and quaternary ammonium carbonates. Examples of quaternary ammonium carbonates include tetraalkylammonium carbonates, and specifically, tetramethylammonium carbonate. The supply source of component C may be one type or a combination of two or more types.

[0037] The concentration (mol / L) of component C or component C' during use of the cleaning composition of the present disclosure is 0.3 mol / L or more, preferably 0.8 mol / L or more, from the viewpoint of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask, and from the same viewpoint, is preferably 3 mol / L or less, more preferably 2 mol / L or less. More specifically, the concentration (mol / L) of component C or component C' is preferably 0.3 mol / L or more and 3 mol / L or less, more preferably 0.8 mol / L or more and 2 mol / L or less. In the present disclosure, "the concentration of each component during use of the cleaning composition" refers to the concentration of each component during cleaning, i.e., at the time when the cleaning composition is started to be used for cleaning.

[0038] The molar ratio C / A of component C to component A during use of the cleaning composition of the present disclosure is preferably 0.2 or more, and more preferably 0.6 or more, from the viewpoint of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask. From the same viewpoint, it is preferably 3 or less, and more preferably 2 or less. More specifically, the molar ratio C / A is preferably 0.2 or more and 3 or less, and more preferably 0.6 or more and 2 or less. The molar ratio C' / A of component C' to component A during use of the cleaning composition of the present disclosure can be the same as the molar ratio C / A described above.

[0039] The molar ratio C / B of component C to component B during use of the cleaning composition of the present disclosure is preferably 1 or more, and more preferably 1.5 or more, from the viewpoint of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask. From the same viewpoint, it is preferably 5 or less, and more preferably 3 or less. More specifically, the molar ratio C / B is preferably 1 or more and 5 or less, and more preferably 1.5 or more and 3 or less. The molar ratio C' / B of component C' to component B during use of the cleaning composition of the present disclosure can be the same as the above-mentioned molar ratio C / B.

[0040] [Water (ingredient D)] In one or a plurality of embodiments, examples of water (hereinafter also referred to as "component D") in the cleaning composition of the present disclosure include ion-exchanged water, RO water, distilled water, pure water, and ultrapure water.

[0041] The content of Component D in the cleaning composition of the present disclosure may be the remainder excluding Component A, Component B, Component C, and any optional components described below. Specifically, the content of component D when the cleaning composition of the present disclosure is used is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, from the viewpoints of improving resin mask removability (peelability), inhibiting copper corrosion, reducing the load on wastewater treatment, and reducing the effect on the substrate, and from the viewpoint of improving resin mask removability (peelability), it is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. More specifically, the content of component D when the cleaning composition of the present disclosure is used is preferably 50% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 90% by mass or less, and even more preferably 70% by mass or more and 85% by mass or less.

[0042] The total amount of Components A, B, C and D when using the cleaning composition of the present disclosure is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more, from the viewpoint of suppressing copper corrosion without significantly impairing the removability (peelability) of the resin mask.

[0043] [Organic solvent (component E)] In one or more embodiments, the cleaning composition of the present disclosure may further contain an organic solvent (hereinafter, also simply referred to as "Component E") from the viewpoint of improving removability (peelability) of the resin mask. Component E may be one type or a combination of two or more types. In one or more embodiments, Component E includes at least one solvent selected from glycol ethers and aromatic ketones. From the same viewpoint, examples of glycol ethers include compounds having a structure in which 1 to 3 moles of ethylene glycol are added to an alcohol having a carbon number of 1 to 8. Specific examples of glycol ethers include at least one selected from diethylene glycol monobutyl ether (BDG), ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether. From the same viewpoint, examples of aromatic ketones include acetophenone and the like.

[0044] When the cleaning composition of the present disclosure contains component E, the content of component E during use of the cleaning composition of the present disclosure is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more from the viewpoint of improving the removability (peelability) of the resin mask, and from the same viewpoint, is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 5% by mass or less. More specifically, the content of component E during use is preferably 1% by mass or more and 40% by mass or less, more preferably 1.5% by mass or more and 20% by mass or less, and even more preferably 2% by mass or more and 5% by mass or less. When component E is a combination of two or more types, the content of component E refers to the total content thereof.

[0045] [Chelating agent (ingredient F)] In one or more embodiments, the cleaning composition of the present disclosure may further contain a chelating agent (hereinafter, also simply referred to as "Component F") from the viewpoint of improving removability (peelability) of the resin mask. Component F may be one type or a combination of two or more types. Examples of component F include compounds having two or more acid groups of at least one type selected from carboxy groups and phosphonic acid groups, and from the same viewpoint, compounds having preferably four or less acid groups are preferred. Specific examples of component F in one or more embodiments include aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid (1-hydroxyethane-1,1-diphosphonic acid, HEDP), etc. Among these, from the viewpoint of reducing environmental load, compounds not containing nitrogen atoms such as 2-phosphonobutane-1,2,4-tricarboxylic acid and etidronic acid (HEDP) are preferred.

[0046] When the cleaning composition of the present disclosure contains component F, the content of component F during use of the cleaning composition of the present disclosure is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of improving resin mask removability (peelability), and from the same viewpoint, is preferably 5% by mass or less, more preferably 3% by mass or less. More specifically, the content of component F during use is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less. When component F is a combination of two or more types, the content of component F refers to the total content thereof.

[0047] [Component G: Ammonium salts of organic acids] In one or more embodiments, the cleaning composition of the present disclosure may further contain at least one kind of ammonium salt of an organic acid (hereinafter also referred to as "Component G") from the viewpoint of improving the removability (stripping ability) of the resin mask. 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, more preferably ammonium formate. Component G may be one kind or a combination of two or more kinds.

[0048] When the cleaning composition of the present disclosure contains component G, the content of component G during use of the cleaning composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more from the viewpoint of improving the removability (peelability) of the resin mask, and from the same viewpoint, is preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less. More specifically, the content of component G is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.2% by mass or more and 1.5% by mass or less, and even more preferably 0.3% by mass or more and 1% by mass or less. When component G is a combination of two or more kinds, the content of component G refers to the total content thereof.

[0049] In one or more embodiments, the cleaning composition of the present disclosure preferably further contains Component E, Component F, and Component G from the viewpoint of improving the removability (peelability) of the resin mask.

[0050] [Other ingredients] The cleaning composition of the present disclosure may further contain other components as necessary, in addition to the above-mentioned Components A to G, to the extent that the effects of the present disclosure are not impaired. Examples of other components include components that can be used in ordinary cleaning agents, such as organic solvents other than Component E, surfactants, chelating agents other than Component F, thickeners, dispersants, rust inhibitors, polymeric compounds, solubilizers, antioxidants, preservatives, antifoaming agents, and antibacterial agents. The content of other ingredients in the cleaning composition of the present disclosure during use is preferably 0% by mass or more and 2% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, even more preferably 0% by mass or more and 1.3% by mass or less, and still more preferably 0% by mass or more and 1% by mass or less.

[0051] The total content of organic matter derived from components A, B, C and optional components (component E, component F, component G, other components) during use of the cleaning composition of the present disclosure is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and even more preferably 16% by mass or less from the viewpoint of reducing the wastewater treatment load and reducing the influence on the substrate, and is preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and even more preferably 6% by mass or more from the viewpoint of improving the removability (peelability) of the resin mask. More specifically, the total content of organic matter derived from components A, B, C and optional components (component E, component F, component G, other components) during use of the cleaning composition of the present disclosure 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, even more preferably 4% by mass or more and 20% by mass or less, and even more preferably 6% by mass or more and 16% by mass or less.

[0052] [Method of producing the cleaning composition] The cleaning composition of the present disclosure can be produced by blending a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, a carbonate salt (component C') that is a source of carbonate ions (component C), water (component D), and the above-mentioned optional components (component E, component F, component G, and other components) as necessary by a known method. For example, in one or more embodiments, the cleaning composition of the present disclosure can be a composition comprising component A, component B, component C', and component D blended together. Therefore, the present disclosure relates to a method for producing a cleaning composition, comprising a step of blending at least Component A, Component B, Component C', and Component D. In the present disclosure, "blending" includes mixing Component A, Component B, Component C', Component D, and, as necessary, the above-mentioned optional components simultaneously or in any order. In the method for producing a cleaning composition of the present disclosure, the preferred blending amount of each component may be the same as the preferred content of each component in the cleaning composition of the present disclosure described above.

[0053] The cleaning composition of the present disclosure may be in a form used for cleaning as it is, or may be prepared as a concentrate with the amount of water (component D) reduced to the extent that separation, precipitation, etc. do not occur and storage stability is not impaired. The concentrate of the cleaning composition is preferably a concentrate diluted 3 times or more from the viewpoint of transportation and storage, and is preferably a concentrate diluted 30 times or less from the viewpoint of storage stability. The concentrate of the cleaning composition can be used by diluting with water (component D) so that each component (component A, component B, component C, component D, component E, component F, and other components) has the above-mentioned content or concentration (i.e., content or concentration at the time of cleaning) at the time of use. Furthermore, the concentrate of the cleaning composition can also be used by adding each component separately at the time of use. In the present disclosure, "at the time of use" or "at the time of cleaning" of the concentrated cleaning composition refers to a state in which the concentrate of the cleaning composition is diluted.

[0054] [Item to be cleaned] In one or more embodiments, the cleaning composition of the present disclosure can be used to clean a substrate having a copper-containing metal layer and a resin mask on its surface. In one or more embodiments, the copper-containing metal layer is a copper plating layer. The copper plating layer can be formed, for example, by an electroless copper plating method. In one or more other embodiments, the cleaning composition of the present disclosure may be used to clean an object to which a resin mask is attached. In one or more embodiments, the object to be cleaned may be an object to be cleaned having a copper-containing metal site on the surface, for example, an electronic component and its manufacturing intermediate. The electronic component may be at least one part selected from a printed circuit board, a wafer, and a metal plate such as a copper plate or an aluminum plate. The manufacturing intermediate is an intermediate product in the manufacturing process of an electronic component, and includes an intermediate product after a resin mask treatment. Specific examples of objects to be cleaned with a resin mask attached include electronic components in which wiring, connection terminals, etc. are formed on the surface of a substrate by at least one of soldering and plating (copper plating, aluminum plating, nickel plating, etc.) using a resin mask. In the present disclosure, soldering refers to providing solder in a resin mask-free portion on a substrate and forming a solder bump by heating. In the present disclosure, plating refers to performing at least one plating treatment selected from copper plating, aluminum plating, and nickel plating on a resin mask-free portion on a substrate. The resin mask-free portion refers to a portion of a resist pattern formed by developing a resin mask laminated on a substrate, from which the resin mask has been removed by the development treatment. Thus, in one aspect, the present disclosure relates to the use of the cleaning composition of the present disclosure as a cleaning agent in the manufacture of electronic components. In one or more embodiments, the object to be cleaned is a substrate having a resist pattern formed by developing a resin mask laminated on the substrate, and the substrate has undergone at least one of soldering and plating. For example, the object to be cleaned may be a substrate having a resin mask-present portion on which a cured resist layer is formed, and a solder bump or a plating layer-formed portion on which the resin mask is not present.

[0055] In one or more embodiments, the cleaning composition of the present disclosure can be suitably used for cleaning an object to which a resin mask or a resin mask that has been further plated and / or heated is attached, from the viewpoint of cleaning effect. The resin mask may be, for example, a negative resin mask or a positive resin mask. In the present disclosure, the negative resin mask is formed using a negative resist, and examples of the mask include a negative resist layer that has been exposed and / or developed. In the present disclosure, the positive resin mask is formed using a positive resist, and examples of the mask include a positive resist layer that has been exposed and / or developed.

[0056] [Cleaning method] In one aspect, the present disclosure provides a method for cleaning a substrate, the method comprising 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 its surface, by using a cleaning composition (the cleaning composition of the present disclosure) containing a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide, carbonate ions (component C), and water (component D), and having a concentration of component C of 0.3 mol / L or more; and a method for removing a copper-containing metal layer and a resin mask on its surface, by using a cleaning composition containing component A, component B, a carbonate salt (component C'), and component D, and having a concentration of component C' of 0.3 mol / L or more. The present invention relates to a method for cleaning a substrate, comprising a step of peeling off a resin mask from a substrate having a metal layer and a resin mask; a method for cleaning a substrate, comprising a step (peeling step) of peeling off a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface using a cleaning composition containing components A, B, C, and D, and in which the amino group of component A has been cationized; or a method for cleaning a substrate, comprising a step of peeling off a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface using a cleaning composition containing components A, B, C', and D, and in which the amino group of component A has been cationized (hereinafter, these are also collectively referred to as the "cleaning method of the present disclosure"). Examples of the object to be cleaned include the above-mentioned object to be cleaned. In one or more embodiments, the peeling step includes contacting the object to be cleaned with the cleaning composition of the present disclosure. According to the cleaning method of the present disclosure, in one or more embodiments, the resin mask can be efficiently removed while suppressing copper corrosion. Furthermore, according to the cleaning method of the present disclosure, in one or more embodiments, the residue on the substrate after cleaning can be reduced.

[0057] Examples of the method for peeling off a resin mask from an object to be cleaned using the cleaning composition of the present disclosure, or the method for contacting the object to be cleaned with the cleaning composition of the present disclosure include a method for contacting the object by immersing the object in a cleaning bath containing the cleaning composition, a method for contacting the object by spraying the cleaning composition in a spray form (shower method), and an ultrasonic cleaning method for irradiating the object with ultrasonic waves during immersion. The cleaning composition of the present disclosure can be used for cleaning as it is without dilution. Examples of the object to be cleaned include the above-mentioned objects to be cleaned.

[0058] In one or more embodiments, the cleaning method of the present disclosure may include a step of contacting the object to be cleaned with the cleaning composition, rinsing with water, and drying. In one or more embodiments, the cleaning method of the present disclosure may include a step of contacting the object to be cleaned with the cleaning composition, and rinsing with water.

[0059] In the cleaning method of the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning composition of the present disclosure comes into contact with the object to be cleaned, and it is more preferable that the ultrasonic waves have a relatively high frequency, from the viewpoint of making it easier for the cleaning power of the cleaning composition of the present disclosure to be exerted. From the same viewpoint, the ultrasonic irradiation conditions 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.

[0060] In the cleaning method of the present disclosure, the temperature of the cleaning composition is preferably 40° C. or higher, and more preferably 50° C. or higher, from the viewpoint of allowing the cleaning power of the cleaning composition of the present disclosure to be easily exerted, and is preferably 70° C. or lower, and more preferably 60° C. or lower, from the viewpoint of reducing the effect on the substrate.

[0061] [Electronic component manufacturing method] In one aspect, the present disclosure relates to a method for producing an electronic component (hereinafter also referred to as the "method for producing an electronic component of the present disclosure"), 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 its surface using the cleaning method of the present disclosure. Examples of the object to be cleaned include the above-mentioned objects to be cleaned. In one or more embodiments, the method for producing an electronic component of the present disclosure can include a step of etching the copper-containing metal layer after the cleaning step. According to the manufacturing method of electronic components of the present disclosure, by performing cleaning using the cleaning method of the present disclosure, it is possible to effectively remove the resin mask attached to the electronic components while suppressing copper corrosion, and further to reduce the amount of residue on the substrate after cleaning, thereby enabling the manufacturing of highly reliable electronic components. Furthermore, by performing cleaning using the cleaning method of the present disclosure, it is possible to easily remove the resin mask attached to the electronic components, thereby shortening the cleaning time and improving the manufacturing efficiency of electronic components.

[0062] [kit] In one aspect, the present disclosure relates to a kit for use in any one of the cleaning method of the present disclosure and the method for producing electronic components of the present disclosure (hereinafter, also referred to as the "kit of the present disclosure"). In one or more embodiments, the kit of the present disclosure is a kit for producing the cleaning composition of the present disclosure. According to the kit of the present disclosure, a cleaning composition capable of suppressing copper corrosion can be obtained without significantly impairing the removability (peelability) of a resin mask.

[0063] One embodiment of the kit of the present disclosure includes a kit (three-liquid type cleaning agent composition) that includes a solution (first liquid) containing component A, a solution (second liquid) containing component B, and a solution (third liquid) containing component C or component C' in a mutually unmixed state, and at least one selected from the first liquid, the second liquid, and the third liquid further contains a part or all of water (component D), and the first liquid, the second liquid, and the third liquid are mixed at the time of use. After the first liquid, the second liquid, and the third liquid are mixed, they may be diluted with water (component D) as necessary. Each of the first liquid, the second liquid, and the third liquid may contain the above-mentioned optional components as necessary. Other embodiments of the kit of the present disclosure include a kit (two-liquid type cleaning agent composition) that contains a solution (first liquid) containing component B and a solution (second liquid) containing component A and component C or component C' in a mutually unmixed state, at least one of the first liquid and the second liquid further contains a part or all of water (component D), and the first liquid and the second liquid are mixed at the time of use. After the first liquid and the second liquid are mixed, they may be diluted with water (component D) as necessary. Each of the first liquid and the second liquid may contain the above-mentioned optional components as necessary. EXAMPLES

[0064] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples in any way.

[0065] 1. Preparation of cleaning compositions of Examples 1 to 8 and Comparative Examples 1 and 2 The components shown in Table 1 were blended in the amounts (% by mass, active content) shown in Table 1 and then stirred and mixed to prepare the cleaning compositions of Examples 1 to 8 and Comparative Examples 1 and 2. The concentrations (mol / L) of Components A to C, the molar ratio C / A of carbonate ion / water-soluble amine, and the molar ratio C / B of carbonate ion / alkali agent in each of the prepared cleaning compositions are shown in Table 1.

[0066] The cleaning compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were prepared using the following materials. (Component A) MEA: Monoethanolamine [manufactured by Nippon Shokubai Co., Ltd.] (Component B) TMAH: Tetramethylammonium hydroxide [Showa Denko Co., Ltd., concentration 25%] (Source of Component C (Component C´)) Tetramethylammonium carbonate [pH: 9.3, manufactured by Osaka Chemical Industries, Ltd., concentration 30%] Ammonium carbonate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (Component D) Water [Pure water of 1μS / cm or less produced using the Organo Corporation pure water system G-10DSTSET] (Component E) BDG: Butyl diglycol [Nihon Nyukazai Co., Ltd., diethylene glycol monobutyl ether] (Component F) HEDP: Etidronic acid [Italmatch Japan Co., Ltd., Dequest2010, concentration 60%] (Component G) Ammonium formate [Toyama Pharmaceutical Co., Ltd.]

[0067] 2. Evaluation of cleaning agent compositions The prepared cleaning compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated as follows.

[0068] [Preparation of test pieces] A photosensitive film for forming a PKG (semiconductor package) board circuit was laminated on the surface of the board after electroless plating under the following conditions, and then exposed to light to harden (exposure process) to obtain a board with a resin mask (test piece, 30 mm x 50 mm). (1) Lamination: Using a clean roller (RY-505Z, manufactured by Rayon Kogyo Co., Ltd.) and a vacuum applicator (VA7024 / HP5, manufactured by Rohm and Haas Co.), the roller temperature was 50° C. and the roller pressure was 1.4 Bar. (2) Exposure: A direct imaging device for printed circuit boards (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.) was used, and the exposure dose was 15 mJ / cm 2 The exposure is performed.

[0069] [Cleaning test] 100 g of each of the cleaning compositions of Examples 1 to 8 and Comparative Examples 1 to 2 was added to a tall 200 mL glass beaker, heated to 50° C., and the test piece was immersed for 10 minutes while stirring at 600 rpm using a rotor (fluororesin (PTFE), φ8 mm×25 mm). Then, the test piece was immersed in a rinsing tank containing 100 g of water in a 100 mL glass beaker, rinsed, and then dried by nitrogen blowing.

[0070] [Evaluation of resin mask removability (peelability)] Using an optical microscope "Digital Microscope VHX-6000" (manufactured by Keyence Corporation), the presence or absence of the resin mask remaining on the pattern portion of the test piece after the cleaning test is visually confirmed at 500 times magnification, and evaluated according to the following criteria. <Evaluation criteria> A: No residue is observed even at 5μm / 5μm B: No residue is visible up to 6μm / 6μm C: No residues are visible up to 7μm / 7μm D: Residue is visible even at 7μm / 7μm

[0071] [Evaluation of Cu etching rate (evaluation of copper corrosion)] 2.5 L of each cleaning composition was prepared and heated to 50°C. The composition was circulated using a box-type spray washer equipped with a full-cone nozzle (J020, manufactured by Ikeuchi Co., Ltd.) while plating the surface with copper (area: 25 cm per side). 2 , 50cm on both sides 2 The cleaning composition was diluted and then the amount of copper dissolved was measured using an ICP analysis method (Agilent Technologies Agilent 5110 ICP-OES), and the copper density was calculated to be 8.94 g / cm3 using the following formula. 3 The Cu etching rate (μm / min) was evaluated from the amount of elution as the copper corrosion inhibition effect. The lower the Cu etching rate, the better the copper corrosion inhibition effect. Cu etching rate (μm / min) = amount of copper dissolved (weight) ÷ copper density ÷ plating area ÷ processing time

[0072] [Evaluation of damage to board resin] The above cleaning test is carried out on a board having a solder resist resin, and whether there is any change in color or the like in the resin part of the board before and after the test is visually confirmed and evaluated according to the following evaluation criteria. <Evaluation criteria> A: No change was observed before and after the cleaning test. B: Changes are seen before and after the cleaning test.

[0073] [Table 1]

[0074] As shown in Table 1, the cleaning compositions of Examples 1 to 8 were found to be able to inhibit copper corrosion without significantly impairing the removability (peelability) of the resin mask, compared to Comparative Example 1 which did not contain Component C and Comparative Example 2 which had a concentration of Component C of less than 0.3 mol / L. In addition, when comparing Comparative Example 1 (pH 12), which contains only MEA (component A) and TMAH (component B) other than water, with Example 1 (pH 11), which further contains tetramethylammonium carbonate, it was found that the content of TMAH measured by neutralization titration was the same between the two, even though the pH of Example 1 was reduced by the incorporation of tetramethylammonium carbonate. Therefore, it is considered that the reason for the reduction in pH of Example 1 is the reduction in the content of MEA. From this, it was estimated that in Example 1, tetramethylammonium carbonate cationized the amino group of MEA. Here, the pH is the pH of the cleaning composition at 25°C, and is measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and is the value 3 minutes after immersing the electrode in the cleaning composition. [Industrial Applicability]

[0075] According to the present disclosure, a cleaning composition capable of suppressing copper corrosion without significantly impairing the removability of resin masks can be provided. By using the cleaning composition of the present disclosure, it is possible to shorten the cleaning process for electronic components having resin masks attached thereto and improve the performance and reliability of the manufactured electronic components, thereby improving the productivity of semiconductor devices.

Claims

1. A cleaning composition for stripping a resin mask from a substrate having a copper-containing metal layer and a resin mask on a surface thereof, comprising: The composition contains a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide represented by the following formula (II), a carbonate ion (component C), and water (component D), The concentration of component C is 0.3 mol / L or more, A cleaning composition for stripping a resin mask, wherein a molar ratio C / B of component C to component B during use of the cleaning composition is 1 or more and 5 or less. 【Chemistry 1】 In the above formula (II), R 4 , R 5 , R 6 and R 7 each independently represents at least one selected from a methyl group, an ethyl group, and a propyl group.

2. A cleaning composition for stripping a resin mask from a substrate having a copper-containing metal layer and a resin mask on a surface thereof, comprising: The composition comprises a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide represented by the following formula (II), a carbonate (component C'), and water (component D), The concentration of component C' is 0.3 mol / L or more, A cleaning composition for stripping a resin mask, wherein a molar ratio C' / B of component C' to component B during use of the cleaning composition is 1 or more and 5 or less. 【Chemistry 2】 In the above formula (II), R 4 , R 5 , R 6 and R 7 each independently represents at least one selected from a methyl group, an ethyl group, and a propyl group.

3. 3. The cleaning composition for stripping a resin mask according to claim 1, wherein component A is an amine represented by the following formula (I): 【Chemistry 3】 In formula (I), R 1 is a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms; R 2 and R 3 are the same or different and each is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an aminoalkyl group having 1 to 6 carbon atoms; R 1 , R 2 and R 3 cannot simultaneously be a hydrogen atom.

4. The cleaning composition according to claim 1 , wherein the content of component D is 50% by mass or more and 95% by mass or less.

5. The cleaning composition according to claim 1 , wherein the total amount of component A, component B, component C and component D is 80 mass% or more.

6. A method for cleaning a substrate, the method comprising: removing a resin mask from a substrate having a copper-containing metal layer and a resin mask on a surface thereof, by using a cleaning composition comprising a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide represented by the following formula (II) and an alkali metal hydroxide, carbonate ions (component C) and water (component D), wherein the concentration of component C is 0.3 mol / L or more and a molar ratio C / B of component C to component B during use is 1 or more and 5 or less: 【Chemistry 4】 In the above formula (II), R 4 , R 5 , R 6 and R 7 each independently represents at least one selected from a methyl group, an ethyl group, and a propyl group.

7. A method for cleaning a substrate, comprising: a step of stripping a resin mask from a substrate having a copper-containing metal layer and a resin mask on a surface thereof, using a cleaning composition comprising a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide represented by the following formula (II), a carbonate (component C'), and water (component D), wherein the concentration of component C' is 0.3 mol / L or more and the molar ratio C' / B of component C' to component B during use is 1 or more and 5 or less: 【Chemistry 5】 In the above formula (II), R 4 , R 5 , R 6 and R 7 each independently represents at least one selected from a methyl group, an ethyl group, and a propyl group.

8. The method includes a step of removing a resin mask from a substrate having a copper-containing metal layer and a resin mask on a surface thereof, by using a cleaning composition comprising a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide represented by the following formula (II), carbonate ions (component C) and water (component D), in which an amino group of component A is cationized, The method for cleaning a substrate, wherein a molar ratio C / B of component C to component B during use of the cleaning composition is 1 or more and 5 or less. 【Chemistry 6】 In the above formula (II), R 4 , R 5 , R 6 and R 7 each independently represents at least one selected from a methyl group, an ethyl group, and a propyl group.

9. The method includes a step of removing a resin mask from a substrate having a copper-containing metal layer and a resin mask on a surface thereof, by using a cleaning composition comprising a water-soluble amine (component A), at least one alkaline agent (component B) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide represented by the following formula (II), a carbonate (component C'), and water (component D), in which an amino group of component A is cationized, The method for cleaning a substrate, wherein a molar ratio C' / B of component C' to component B during use of the cleaning composition is 1 or more and 5 or less. 【Chemistry 7】 In the above formula (II), R 4 , R 5 , R 6 and R 7 each independently represents at least one selected from a methyl group, an ethyl group, and a propyl group.

10. The cleaning method according to any one of claims 6 to 9, wherein the copper-containing metal layer is a copper plating layer.

11. 11. The cleaning method according to claim 6, wherein the resin mask is a hardened resist layer.

12. The cleaning method according to any one of claims 6 to 11, wherein the total amount of component A, component B, component C and component D at the time of using the cleaning agent composition is 80 mass% or more.

13. A method for producing an electronic component, comprising the step of cleaning a substrate having a copper-containing metal layer and a resin mask on a surface thereof, by using the cleaning method according to any one of claims 6 to 12.

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