JP2022043812A - Detergent composition for resin mask peeling - Google Patents

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

The present disclosure relates to a cleaning agent composition for removing a resin mask, a method for cleaning a substrate using the same, and a method for manufacturing an electronic component.

In recent years, in personal computers and various electronic devices, power consumption has been reduced, processing speed has been increased, and miniaturization has progressed, and wiring such as package substrates mounted on these has been miniaturized year by year. The metal mask method has been mainly used for the formation of such fine wiring and connection terminals such as pillars and bumps, but its versatility is low and it has become difficult to deal with miniaturization of wiring and the like. Is changing to other new 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. This resin mask is finally peeled off and removed, but as a cleaning agent used for cleaning such as peeling and removal, a cleaning agent for removing a resin mask containing an alkaline agent and water is known.

For example, Patent Document 1 describes a specific quaternary ammonium as a cleaning agent capable of both promoting removal of the resin mask layer after heat treatment of solder bumps and suppressing solder corrosion and improving solder connection reliability. A cleaning agent composition for a resin mask layer containing a hydroxide, a water-soluble amine, an acid or an ammonium salt thereof, and water is described. Then, it is disclosed that ammonium carbonate was used as the ammonium salt of the acid in the examples.

Japanese Unexamined Patent Publication No. 2015-7944

In forming fine wiring on a printed circuit board, etc., not only the residual resin mask, but also the cleaning agent composition to reduce the residual auxiliary agents contained in the solder, plating solution, etc. used for fine wiring and bump formation. High detergency is required for objects.
Here, the resin mask is formed by using a resist whose physical properties such as solubility in a developing solution are changed by light, an electron beam, or the like. Resists are roughly classified into negative type and positive type according to the reaction method with light and electron beam. The negative resist has the property that its solubility in a developing solution decreases when exposed, and the layer containing the negative resist (hereinafter, also referred to as “negative resist layer”) is formed by the exposed portion after exposure and development processing. Used as a resin mask. The positive resist has the property of increasing its solubility in a developing solution when exposed, and the layer containing the positive resist (hereinafter, also referred to as “positive resist layer”) is exposed to the exposed portion after exposure and development processing. It is removed and the unexposed area is used as a resin mask. By using a resin mask having such characteristics, it is possible to form fine connection portions of a circuit board such as metal wiring, metal pillars and solder bumps.

However, as the wiring becomes finer, it becomes difficult to remove the resin mask in the fine gaps, and the detergent composition is required to have high resin mask removing property. Further, since the corrosion of copper used for many wirings and connection terminals causes deterioration of the quality and value of the package substrate, a high corrosion prevention ability is required for the cleaning agent composition. The technique disclosed in Patent Document 1 has a high resin mask removing property and a corrosion suppressing effect of solder, but the corrosion suppressing effect of copper is not sufficient.

Therefore, the present disclosure provides, in one aspect, a cleaning agent composition for removing a resin mask and a method for cleaning a substrate, which can suppress copper corrosion without significantly impairing the removability (removability) of the resin mask.

The present disclosure, in one embodiment, comprises at least one alkaline agent (component B), carbonate ion (component C), selected from a water-soluble amine (component A), a quaternary ammonium hydroxide and an alkali metal hydroxide. The present invention relates to a cleaning agent composition for removing a resin mask, which contains water (component D) and has a concentration of component C of 0.3 mol / L or more.

The present disclosure, in one embodiment, comprises a water-soluble amine (component A), at least one alkaline agent (component B) selected from quaternary ammonium hydroxides and alkali metal hydroxides, and a carbonate (component C). ') And water (component D) are blended, and the concentration of the component C'is 0.3 mol / L or more, and the present invention relates to a cleaning agent composition for removing a resin mask.

The present disclosure, in one embodiment, comprises at least one alkaline agent (component B), carbonate ion (component C), selected from a water-soluble amine (component A), a quaternary ammonium hydroxide and an alkali metal hydroxide. A step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface using a cleaning agent composition containing water (component D) and having a concentration of component C of 0.3 mol / L or more. Including, regarding the method of cleaning the substrate.

The present disclosure, in one embodiment, 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, and a carbonate (component C). A substrate having a copper-containing metal layer and a resin mask on the surface using a cleaning agent composition composed of ´) and water (component D) having a concentration of component C ′ of 0.3 mol / L or more. The present invention relates to a method for cleaning a substrate, which comprises a step of peeling off a resin mask from the metal.

The present disclosure, in one embodiment, comprises at least one alkaline agent (component B), carbonate ion (component C), selected from a water-soluble amine (component A), a quaternary ammonium hydroxide and an alkali metal hydroxide. A substrate comprising a step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface using a cleaning agent composition containing water (component D) and cationizing the amino group of the component A. Regarding the cleaning method of.

The present disclosure, in one embodiment, 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, and a carbonate (component C). A resin mask is obtained from a substrate having a copper-containing metal layer and a resin mask on the surface by using a cleaning agent composition obtained by blending ´) and water (component D) and cationizing the amino group of the component A. The present invention relates to a method for cleaning a substrate, including a step of peeling.

The present disclosure relates to a method for manufacturing an electronic component, which comprises, in one aspect, a step of cleaning a substrate having a copper-containing metal layer and a resin mask on the surface by using the cleaning method of the present disclosure.

According to the present disclosure, in one embodiment, it is possible to provide a detergent composition for removing a resin mask that can suppress copper corrosion without significantly impairing the resin mask removability (peeling property).

The present disclosure comprises at least one alkaline agent (component B) selected from a water-soluble amine (component A), a quaternary ammonium hydroxide and an alkali metal hydroxide, and a carbonate ion (component C) having a predetermined concentration. A cleaning agent composition containing water (component D) or a cleaning agent composition for removing a resin mask, which is a mixture of component A, component B, a carbonate (component C') having a predetermined concentration, and component D, is used. This is based on the finding that the resin mask can be efficiently removed from the substrate surface while suppressing the corrosion of copper.

The present disclosure, in one embodiment, comprises at least one alkaline agent (component B), carbonate ion (component C), selected from water-soluble amines (component A), quaternary ammonium hydroxides and alkali metal hydroxides. A cleaning agent composition for removing a resin mask containing water (component D) and having a concentration of component C of 0.3 mol / L or more, or a component A, a component B, a carbonate (component C'), and a component D. The present invention relates to a resin mask stripping cleaning agent composition having a concentration of component C'of 0.3 mol / L or more (hereinafter, these are collectively referred to as "the cleaning agent composition of the present disclosure").

According to the present disclosure, it is possible to provide a resin mask peeling detergent composition capable of suppressing copper corrosion without significantly impairing the resin mask removability (peeling property) in one or a plurality of embodiments. Then, by using the detergent composition of the present disclosure, high quality electronic components can be obtained in high yield. Further, by using the cleaning agent composition of the present disclosure, it is possible to efficiently manufacture an electronic component having a fine wiring pattern.

The details of the mechanism of action of the effect manifestation of the present disclosure are unclear, but 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 a quaternary ammonium hydroxide and an alkali metal hydroxide, the components A and B are used in combination. Is considered to permeate into the resin mask and promote the dissociation of the alkali-soluble resin contained in the resin mask, and further promote the peeling of the resin mask by causing the repulsion of the charge generated by the dissociation. On the other hand, the water-soluble amine (component A) is considered to be involved in the etching (corrosion) of copper. Here, it is considered that the carbonate ion (component C) having a specific concentration cationizes the amino group of the component A to form a complex of the component A and the component C, and the etching of copper by the component A can be suppressed.
However, the present disclosure may not be construed as being limited to this mechanism.

The resin mask to be peeled off / removed in the present disclosure is a mask for protecting the surface of a substance from treatments such as etching, plating, and heating, that is, a mask that functions as a protective film. In one or more embodiments, the resin mask is subjected to at least one of the resist layer after the exposure and development steps, and the exposure and development (hereinafter, also referred to as “exposure and / or development treatment”). Examples thereof include a resist layer and a cured resist layer. Examples of the resin material forming the resin mask include a film-shaped photosensitive resin, a resist film, or a photoresist in one or more embodiments. A general-purpose resist film can be used.

[Water-soluble amine (component A)]
The detergent composition of the present disclosure contains a water-soluble amine (hereinafter, also simply referred to as "component A"). Examples of the component A include amines represented by the following formula (I) in one or more embodiments. The component A may be one kind or a combination of two or more kinds. In the present disclosure, "water-soluble" means having a solubility of 0.5 g / 100 mL or more, preferably 2 g / 100 mL or more, in water (20 ° C.).

In the 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, and R ² And R ³ are the same or different, respectively, and are 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, and are R ¹ and R. ² and R ³ do not become hydrogen atoms at the same time.

Examples of the amine represented by the formula (I) include monoethanolamine, monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine and diisopropanol. Amine, 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) diisopropanol At least one selected from amines, ethylenediamines and diethylenetriamines may be mentioned. Among these, monoethanolamine and diethanolamine are preferable, and monoethanolamine is more preferable, from the viewpoint of improving the resin mask removability (peeling property).

As the component A, monoethanolamine, N, N-diethylethanolamine, N-methylethanolamine, ethylaminoethanol, and At least one selected from propanediamine is mentioned, and among these, monoethanolamine is preferable.

The content of the component A at the time of use of the cleaning agent composition of the present disclosure is preferably 2% by mass or more, more preferably 3% by mass or more, and 5% by mass or more from the viewpoint of resin mask removability (peeling property). Further, from the viewpoint of suppressing copper corrosion, 10% by mass or less is preferable, 9% by mass or less is more preferable, and 7% by mass or less is further preferable. More specifically, the content of the 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 further preferably 5% by mass or more and 7% by mass or less. When the component A is a combination of two or more kinds, the content of the component A means the total content thereof.

In the present disclosure, the "content of each component at the time of use of the detergent composition" means the content of each component at the time of cleaning, that is, at the time when the use of the detergent composition for cleaning is started.

[Alkaline agent (component B)]
The cleaning agent composition of the present disclosure contains at least one alkaline agent (hereinafter, also simply referred to as “component B”) selected from a quaternary ammonium hydroxide and an alkali metal hydroxide. The component B may be one kind or a combination of two or more kinds.

Examples of the quaternary ammonium hydroxide include a quaternary ammonium hydroxide represented by the following formula (II).

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

Examples of the quaternary ammonium hydroxide represented by the formula (II) include a salt composed of a quaternary ammonium cation and a hydroxide. Specific examples of the quaternary ammonium hydroxide are tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), and 2-hydroxyethyltriethyl. Ammonium Hydroxide, 2-Hydroxyethyl Tripropylammonium 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, Included are at least one selected from tris (2-hydroxyethyl) propylammonium hydroxides, tetrakis (2-hydroxyethyl) ammonium hydroxides, and tetrakis (2-hydroxypropyl) ammonium hydroxides. Among these, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferable, and tetramethylammonium hydroxide is more preferable, from the viewpoint of improving the resin mask removability (peeling property).

Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and the like in one or more embodiments.

The content of component B at the time of use of the detergent composition of the present disclosure is preferably 0.5% by mass or more, more preferably 3% by mass or more, from the viewpoint of resin mask removability (peeling property). When the component B is a combination of two or more kinds, the content of the component B means the total content thereof.
The content of component B at the time of use of the detergent composition of the present disclosure is preferably 10% by mass or less from the viewpoint of saturated the effect of the present invention.

[Carbonate ion: (component C)]
The detergent composition of the present disclosure contains carbonate ions ( ^{CO 32-} ₎ (hereinafter, also simply referred to as "component C") in one or more embodiments. The detergent composition of the present disclosure comprises, in one or more other embodiments, a carbonate (hereinafter, also simply referred to as "component C'") which is a source of component C. In the detergent composition of the present disclosure, it is considered that the etching of copper can be suppressed by cationizing the amino group of the component A by the carbonate ion (component C). Therefore, the detergent composition of the present disclosure is, in one or more embodiments, a detergent composition containing component A, component B, component C and component D, in which the amino group of component A is cationized. .. In one or more other embodiments, the detergent composition of the present disclosure is a detergent in which component A, component B, component C'and component D are blended, and the amino group of component A is cationized. It is a composition.

The component C'which is the source of the component C is not particularly limited as long as it is a compound capable of supplying carbonate ions in one or a plurality of embodiments, but copper is not significantly impaired in the resin mask removability (peeling property). From the viewpoint of suppressing corrosion, carbonates of alkali metals, carbonates of alkaline earth metals, carbonates of quaternary ammonium and the like can be mentioned. Examples of the carbonate of the quaternary ammonium include tetraalkylammonium carbonate, and specific examples thereof include tetramethylammonium carbonate and the like. The source of the component C may be one kind or a combination of two or more kinds.

The concentration (mol / L) of the component C or the component C'when using the cleaning agent composition of the present disclosure is 0. It is preferably 3 mol / L or more, preferably 0.8 mol / L or more, and from the same viewpoint, 3 mol / L or less is preferable, and 2 mol / L or less is more preferable. More specifically, the concentration (mol / L) of the component C or the component C'is preferably 0.3 mol / L or more and 3 mol / L or less, and more preferably 0.8 mol / L or more and 2 mol / L or less. In the present disclosure, the "concentration of each component at the time of using the detergent composition" means the concentration of each component at the time of cleaning, that is, at the time when the use of the detergent composition for cleaning is started.

The molar ratio C / A of component C to component A during use of the detergent composition of the present disclosure is 0.2 or more from the viewpoint of suppressing copper corrosion without significantly impairing the resin mask removability (peeling property). Is preferable, and 0.6 or more is more preferable. From the same viewpoint, 3 or less is preferable, and 2 or less is more preferable. 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 the component C ′ to the component A at the time of using the detergent composition of the present disclosure can be the same as the above-mentioned molar ratio C / A.

The molar ratio C / B of component C to component B during use of the detergent composition of the present disclosure is preferably 1 or more from the viewpoint of suppressing copper corrosion without significantly impairing the resin mask removability (peeling property). , 1.5 or more is more preferable. From the same viewpoint, 5 or less is preferable, and 3 or less is more preferable. 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 the component C ′ to the component B at the time of using the detergent composition of the present disclosure can be the same as the above-mentioned molar ratio C / B.

[Water (component D)]
Examples of the water (hereinafter, also referred to as “component D”) in the cleaning agent composition of the present disclosure include ion-exchanged water, RO water, distilled water, pure water, ultrapure water, and the like in one or more embodiments. ..

The content of component D in the detergent composition of the present disclosure can be a residue excluding component A, component B, component C and optional components described later.
Specifically, the content of the component D at the time of use of the cleaning agent composition of the present disclosure is from the viewpoint of improving the resin mask removability (peeling property), suppressing copper corrosion, reducing the wastewater treatment load, and reducing the influence on the substrate. , 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and from the viewpoint of improving the resin mask removability (peeling property), 95% by mass or less is preferable, and 90% by mass or less. Is more preferable, and 85% by mass or less is further preferable. More specifically, the content of the component D at the time of use of the detergent composition of the present disclosure 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 more preferably 70% by mass. It is more preferably 85% by mass or less.

The total amount of the component A, the component B, the component C, and the component D at the time of using the cleaning agent composition of the present disclosure is 50 from the viewpoint of suppressing copper corrosion without significantly impairing the resin mask removability (peeling property). By mass or more is preferable, 60% by mass or more is more preferable, 70% by mass or more is further preferable, 80% by mass or more is further preferable, and 90% by mass or more is further preferable.

[Organic solvent (component E)]
In one or more embodiments, the detergent composition of the present disclosure may further contain an organic solvent (hereinafter, also simply referred to as "component E") from the viewpoint of improving the resin mask removability (peeling property). .. The component E may be one kind or a combination of two or more kinds.
The component E includes at least one solvent selected from glycol ethers and aromatic ketones in one or more embodiments.
From the same viewpoint, examples of the glycol ether include compounds having a structure in which 1 or more and 3 mol or less of ethylene glycol is added to an alcohol having 1 or more and 8 or less carbon atoms. Specific examples of the glycol ether 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.
Examples of the aromatic ketone include acetophenone and the like from the same viewpoint.

When the detergent composition of the present disclosure contains the component E, the content of the component E at the time of using the cleaning agent composition of the present disclosure is 1% by mass or more from the viewpoint of improving the resin mask removability (peeling property). Is preferable, 1.5% by mass or more is more preferable, 2% by mass or more is further preferable, and from the same viewpoint, 40% by mass or less is preferable, 20% by mass or less is more preferable, and 5% by mass or less is further preferable. .. More specifically, the content of the component E at the time of 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 2% by mass or more and 5% by mass or less. More preferred. When the component E is a combination of two or more kinds, the content of the component E means the total content thereof.

[Chelating agent (component F)]
In one or more embodiments, the detergent composition of the present disclosure may further contain a chelating agent (hereinafter, also simply referred to as "component F") from the viewpoint of improving the resin mask removability (peeling property). .. The component F may be one kind or a combination of two or more kinds.
Examples of the component F include a compound having two or more at least one acid group selected from a carboxy group and a phosphonic acid group, and from the same viewpoint, the compound preferably having four or less of the acid groups. preferable. Specific examples of the component F include aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid (1-hydroxyethane-1,1-diphosphonic acid,) in one or more embodiments. HEDP) and the like. Among these, 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid (HEDP) and the like, which are compounds containing no nitrogen atom, are preferable from the viewpoint of reducing the environmental load.

When the cleaning agent composition of the present disclosure contains the component F, the content of the component F at the time of using the cleaning agent composition of the present disclosure is 0.5 mass by mass from the viewpoint of improving the resin mask removability (peeling property). % Or more is preferable, 1% by mass or more is more preferable, and from the same viewpoint, 5% by mass or less is preferable, and 3% by mass or less is more preferable. More specifically, the content of the component F at the time of use is preferably 0.5% by mass or more and 5% by mass or less, and more preferably 1% by mass or more and 3% by mass or less. When the component F is a combination of two or more kinds, the content of the component F means the total content thereof.

[Component G: Ammonium salt of organic acid]
In one or more embodiments, the detergent composition of the present disclosure contains at least one ammonium salt of an organic acid (hereinafter, also referred to as "component G") from the viewpoint of improving the resin mask removability (peeling property). It can be further contained. From the same viewpoint, the ammonium salt of the organic acid is preferably an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms, and more preferably ammonium formate. The component G may be one kind or a combination of two or more kinds.

When the cleaning agent composition of the present disclosure contains the component G, the content of the component G at the time of use of the cleaning agent composition of the present disclosure is 0.1 mass by mass from the viewpoint of improving the resin mask removability (peeling property). % Or more is preferable, 0.2% by mass or more is more preferable, 0.3% by mass or more is further preferable, and from the same viewpoint, 2% by mass or less is preferable, 1.5% by mass or less is more preferable, and 1 More preferably, it is by mass or less. More specifically, the content of the 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 0.3% by mass or more and 1% by mass. % Or less is more preferable. When the component G is a combination of two or more kinds, the content of the component G means the total content thereof.

In one or more embodiments, the detergent composition of the present disclosure preferably further contains component E, component F, and component G from the viewpoint of improving the resin mask removability (peeling property).

[Other ingredients]
The detergent composition of the present disclosure may further contain other components, if necessary, in addition to the above-mentioned components A to G, as long as the effects of the present disclosure are not impaired. Examples of other components include components that can be used in ordinary detergents, for example, organic solvents other than component E, surfactants, chelating agents other than component F, thickeners, dispersants, and rust preventives. Examples thereof include agents, polymer compounds, solubilizers, antioxidants, preservatives, antifoaming agents, antibacterial agents and the like.
The other content of the cleaning agent composition of the present disclosure at the time of 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, and 0% by mass or more and 1.3% by mass. % Or less is more preferable, and 0% by mass or more and 1% by mass or less is even more preferable.

The total content of organic substances derived from component A, component B, component C and optional components (component E, component F, component G, and other components) when the cleaning agent composition of the present disclosure is used is such that the wastewater treatment load is reduced. From the viewpoint of reducing the influence on the substrate, 30% by mass or less is preferable, 25% by mass or less is more preferable, 20% by mass or less is further preferable, 16% by mass or less is further preferable, and resin mask removability (peeling property). ) From the viewpoint of improvement, 2% by mass or more is preferable, 3% by mass or more is more preferable, 4% by mass or more is further preferable, and 6% by mass or more is further preferable. More specifically, the total content of organic substances derived from component A, component B, component C and optional components (component E, component F, component G, and other components) when the cleaning composition of the present disclosure is used is It is preferably 2% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, further preferably 4% by mass or more and 20% by mass or less, and further preferably 6% by mass or more and 16% by mass or less.

[Manufacturing method of detergent composition]
The cleaning agent composition of the present disclosure comprises at least one alkaline agent (component B) selected from a water-soluble amine (component A), a quaternary ammonium hydroxide and an alkali metal hydroxide, and a carbonate ion (component C). By blending a carbonate (component C'), water (component D), which is a source of the above-mentioned optional components (component E, component F, component G, and other components) as required, by a known method. Can be manufactured. For example, the detergent composition of the present disclosure may be made by blending component A, component B, component C'and component D in one or more embodiments.
Therefore, the present disclosure relates to a method for producing a detergent composition, which comprises at least a step of blending 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 optionally, any of the above-mentioned components at the same time or in any order. In the method for producing the detergent composition of the present disclosure, the preferable blending amount of each component can be the same as the preferable content of each component of the detergent composition of the present disclosure described above.

The detergent composition of the present disclosure may be used as it is for cleaning, and is prepared as a concentrate in which the amount of water (component D) is reduced within a range that does not cause separation, precipitation, etc. and impair storage stability. You may. The concentrate of the detergent composition is preferably a concentrate having a dilution ratio of 3 times or more from the viewpoint of transportation and storage, and preferably a concentrate having a dilution ratio of 30 times or less from the viewpoint of storage stability. .. The concentrate of the detergent composition has the above-mentioned content or concentration (that is, at the time of cleaning) of each component (component A, component B, component C, component D, component E, component F, and other components) at the time of use. It can be used by diluting it with water (component D) so as to have the content or concentration of. Further, the concentrate of the detergent composition can 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 detergent composition of the concentrate means a state in which the concentrate of the detergent composition is diluted.

[Item to be washed]
The detergent composition of the present disclosure may be used in one or more embodiments to clean a substrate having a copper-containing metal layer and a resin mask on its 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 cleaning agent composition of the present disclosure can be used in one or more other embodiments for cleaning an object to be cleaned to which a resin mask is attached. Examples of the object to be cleaned include, in one or more embodiments, an object to be cleaned having a copper-containing metal moiety on the surface, and examples thereof include electronic parts and their manufacturing intermediates. Examples of the electronic component include at least one component selected from a metal plate such as a printed circuit board, a wafer, a copper plate, and an aluminum plate. The manufacturing intermediate product is an intermediate product in the manufacturing process of the electronic component, and includes an intermediate product after the resin mask treatment.
As a specific example of the object to be cleaned to which the resin mask is attached, for example, by going through at least one of the soldering and plating treatments (copper plating, aluminum plating, nickel plating, etc.) using the resin mask. Examples thereof include electronic components in which wiring, connection terminals, and the like are formed on the surface of a substrate. In the present disclosure, soldering means that solder is present in a portion of a substrate in which a resin mask does not exist, and solder bumps are formed by heating. In the present disclosure, the plating treatment means to perform at least one type of plating treatment selected from copper plating, aluminum plating and nickel plating on the non-existent portion of the resin mask on the substrate. The non-existent portion of the resin mask is a portion of the resist pattern formed by developing the resin mask laminated on the substrate, from which the resin mask has been removed by the developing treatment. Accordingly, the present disclosure relates, in one aspect, to the use of the cleaning agent 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 step of performing at least one of soldering and plating treatment on a substrate having a resist pattern formed by developing a resin mask laminated on the substrate. It has passed. For example, examples of the substrate to be cleaned include a substrate having a portion where a cured resist layer is formed on a substrate and a resin mask is present, and a portion where a solder bump or a plating layer is formed on a portion where the resin mask is not present. Be done.

In one or more embodiments, the detergent composition of the present disclosure is suitable for cleaning a resin mask or an object to be cleaned to which a plating-treated and / or heat-treated resin mask is attached, from the viewpoint of cleaning effect. Can be used for. The resin mask may be, for example, a negative type resin mask or a positive type resin mask. In the present disclosure, the negative resin mask is formed by using a negative resist, and examples thereof include an exposed and / or developed negative resist layer. In the present disclosure, the positive resin mask is formed by using a positive resist, and examples thereof include an exposed and / or developed positive resist layer.

[Washing method]
The present disclosure, in one embodiment, comprises at least one alkaline agent (component B), carbonate ion (component C), selected from a water-soluble amine (component A), a quaternary ammonium hydroxide and an alkali metal hydroxide. Using a cleaning agent composition (cleaning agent composition of the present disclosure) containing water (component D) and having a concentration of component C of 0.3 mol / L or more, a copper-containing metal layer and a resin mask are provided on the surface. A method for cleaning a substrate, including a step of peeling a resin mask from a substrate (object to be cleaned) (hereinafter, also simply referred to as a "peeling step"), a component A, a component B, a carbonate (component C'), and a component D. A substrate comprising a step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface using a cleaning agent composition which is blended and has a concentration of component C'of 0.3 mol / L or more. From a substrate having a copper-containing metal layer and a resin mask on the surface, using a cleaning agent composition containing the components A, B, C and D and cationizing the amino group of the component A. A method for cleaning a substrate, which includes a step of peeling off a resin mask (peeling step), or a cleaning method in which component A, component B, component C', and component D are blended and the amino group of component A is cationized. A method for cleaning a substrate, which comprises a step of peeling the resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface using the agent composition (hereinafter, these are collectively referred to as “the cleaning method of the present disclosure”). Regarding. Examples of the object to be cleaned include the above-mentioned object to be cleaned. The peeling step, in one or more embodiments, comprises 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 the corrosion of copper. Further, according to the cleaning method of the present disclosure, in one or more embodiments, the residue on the substrate after cleaning can be reduced.

As a method of peeling the resin mask from the object to be cleaned using the cleaning agent composition of the present disclosure, or a method of contacting the cleaning agent composition of the present disclosure with the object to be cleaned, for example, a cleaning agent composition is added. Examples thereof include a method of contacting by immersing in a washing tub, a method of injecting a cleaning agent composition into contact by spraying it (shower method), and an ultrasonic cleaning method of irradiating ultrasonic waves during immersion. The detergent composition of the present disclosure can be used as it is for cleaning without being diluted. Examples of the object to be cleaned include the above-mentioned object to be cleaned.

The cleaning method of the present disclosure may include, in one or more embodiments, a step of contacting the cleaning agent composition with the object to be cleaned, rinsing with water, and drying. The cleaning method of the present disclosure may include, in one or more embodiments, a step of contacting the cleaning agent composition with the object to be cleaned and then rinsing with water.

In the cleaning method of the present disclosure, it is preferable to irradiate ultrasonic waves at the time of contact between the cleaning agent composition of the present disclosure and the object to be cleaned, because the cleaning power of the cleaning agent composition of the present disclosure is easily exerted. It is more preferable that the sound wave has a relatively high frequency. From the same viewpoint, the ultrasonic irradiation conditions are preferably, for example, 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

In the cleaning method of the present disclosure, the temperature of the cleaning agent composition is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and the influence on the substrate is reduced, from the viewpoint that the cleaning power of the cleaning agent composition of the present disclosure is easily exhibited. From the viewpoint of the above, 70 ° C. or lower is preferable, and 60 ° C. or lower is more preferable.

[Manufacturing method of electronic parts]
The present disclosure is, in one aspect, a method for manufacturing an electronic component, comprising a step (cleaning step) of cleaning a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on the surface by using the cleaning method of the present disclosure. (Hereinafter, also referred to as "the manufacturing method of the electronic parts of the present disclosure"). Examples of the object to be cleaned include the above-mentioned object to be cleaned. The method for manufacturing electronic components of the present disclosure may include, in one or more embodiments, a step of etching a metal layer containing copper after the cleaning step.
According to the method for manufacturing 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 adhering to the electronic components while suppressing the corrosion of copper, and further cleaning. Since the residue on the substrate can be reduced later, it becomes possible to manufacture highly reliable electronic components. Further, by performing cleaning using the cleaning method of the present disclosure, 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.

[kit]
The present disclosure relates, in one aspect, to a kit for use in any of the cleaning methods of the present disclosure and the method of manufacturing electronic components of the present disclosure (hereinafter, also referred to as "kit of the present disclosure"). The kit of the present disclosure is a kit for producing the detergent composition of the present disclosure in one or more embodiments. According to the kit of the present disclosure, it is possible to obtain a detergent composition capable of suppressing copper corrosion without significantly impairing the resin mask removability (peeling property).

As one embodiment of the kit of the present disclosure, a solution containing component A (first solution), a solution containing component B (second solution), and a solution containing component C or component C'(third solution). Liquid) is contained in a state where it is not mixed with each other, and at least one selected from the first liquid, the second liquid and the third liquid further contains a part or all of water (component D) and is the first liquid. A kit (three-component cleaning agent composition) in which the second liquid and the third liquid are mixed at the time of use can be mentioned. After the first liquid, the second liquid and the third liquid are mixed, they may be diluted with water (component D) if necessary. Each of the first liquid, the second liquid, and the third liquid may contain the above-mentioned optional components, if necessary.
As another embodiment of the kit of the present disclosure, a solution containing component B (liquid 1) and a solution containing component A and component C or component C'(liquid 2) are mixed with each other. Kit (2), which is contained in an undisturbed state, in which at least one of the first solution and the second solution further contains a part or all of water (component D), and the first solution and the second solution are mixed at the time of use. Liquid type detergent composition). After the first liquid and the second liquid are mixed, they may be diluted with water (component D) if necessary. Each of the first liquid and the second liquid may contain the above-mentioned optional components, if necessary.

Hereinafter, the present disclosure will be specifically described with reference to Examples, but the present disclosure is not limited to these Examples.

1. 1. Preparation of Detergent Compositions of Examples 1 to 8 and Comparative Examples 1 to 2 Each component shown in Table 1 is blended in the blending amount (mass%, effective content) shown in Table 1, and the mixture is stirred and mixed. Thereby, the detergent compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were prepared. Tables show the concentrations (mol / L) of components A to C in each of the prepared cleaning agent compositions, the molar ratio C / A of carbonate ion / water-soluble amine, and the molar ratio C / B of carbonate ion / alkaline agent. Shown in 1.

The following were used to prepare the detergent compositions of Examples 1 to 8 and Comparative Examples 1 and 2.
(Component A)
MEA: Monoethanolamine [manufactured by Nippon Shokubai Co., Ltd.]
(Component B)
TMAH: Tetramethylammonium hydroxide [manufactured by Showa Denko KK, concentration 25%]
(Source of component C (component C'))
Tetramethylammonium carbonate [pH: 9.3, manufactured by Osaka Chemical Co., Ltd., concentration 30%]
Ammonium carbonate [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.]
(Component D)
Water [Pure water of 1 μS / cm or less manufactured by Organo Corporation's pure water device G-10DSTSET]
(Component E)
BDG: Butyl diglycol [manufactured by Nippon Embroidery Co., Ltd., diethylene glycol monobutyl ether]
(Ingredient F) HEDP: etidronic acid [Italmatch Japan Co., Ltd., Dequest2010, concentration 60%]
(Component G)
Ammonium formate [manufactured by Tomiyama Pure Chemical Industries, Ltd.]

2. 2. Evaluation of Detergent Composition The following evaluations were performed on the prepared detergent compositions of Examples 1 to 8 and Comparative Examples 1 and 2.

[Making test pieces]
A substrate having a resin mask (test piece, 30 mm ×) is obtained by laminating a photosensitive film for forming a PKG (semiconductor package) substrate circuit on the surface of the substrate after electroless plating under the following conditions, exposing it to an exposure process, and then curing it (exposure step). 50 mm) was obtained.
(1) Lamination: Using a clean roller (RY-505Z, manufactured by Leyon Industries, Ltd.) and a vacuum applicator (VA7024 / HP5, manufactured by ROHM & Haas), the roller temperature is 50 ° C. and the roller pressure is 1.4 Bar.
(2) Exposure: Using a direct drawing device for a printed circuit board (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.), exposure is performed at an exposure amount of 15 mJ / cm ² .

[Washing test]
To a tall type 200 mL glass beaker, 100 g of each cleaning agent composition of Examples 1 to 8 and Comparative Examples 1 and 2 was added and heated to 50 ° C., and the rotor (fluororesin (PTFE), φ8 mm × 25 mm) was heated. The test piece is immersed for 10 minutes while being stirred at a rotation speed of 600 rpm. Then, it is immersed in a rinsing tank containing 100 g of water in a 100 mL glass beaker for rinsing, and then dried with a nitrogen blow.

[Evaluation of resin mask removability (peeling property)]
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 was visually confirmed by magnifying it 500 times. , Evaluate according to the following criteria.
<Evaluation criteria>
A: No residue is seen even at 5 μm / 5 μm B: No residue is seen up to 6 μm / 6 μm C: No residue is seen up to 7 μm / 7 μm D: Residue is seen even at 7 μm / 7 μm

[Evaluation of Cu etching rate (evaluation of copper corrosion)]
Adjust 2.5 L of each cleaning agent composition, heat it to 50 ° C, and circulate it in a box-type spray washing machine equipped with a filled cone nozzle (J020, manufactured by Ikeuchi Co., Ltd.) as a spray nozzle, and copper on the surface. Spray for 4 minutes (pressure: 0.05 MPa, spray distance: 80 mm) on the plated test piece (area is 25 cm ² per side, 50 cm ² on both sides). After diluting the cleaning agent composition, the elution amount of copper was measured by ICP analysis method (Agilent 5110 ICP-OES manufactured by Agilent Technologies), and the copper density was set to 8.94 g / cm ³ by the following formula, and the Cu etching rate was determined from the elution amount. (Μm / min) was evaluated. It can be judged that the lower the value of the Cu etching rate, the better the copper corrosion suppressing effect.
Cu etching rate (μm / min) = copper elution amount (weight) ÷ copper density ÷ plating area ÷ processing time

[Evaluation of damage to substrate resin]
The above-mentioned cleaning test is performed on a substrate having a solder resist resin, and it is visually confirmed whether or not a change in color or the like occurs in the resin portion of the substrate before and after the substrate, and the evaluation is made according to the following evaluation criteria.
<Evaluation criteria>
A: No change is seen before and after the cleaning test.
B: Changes are seen before and after the cleaning test.

As shown in Table 1, the detergent compositions of Examples 1 to 8 have a resin mask as compared with Comparative Example 1 containing no component C and Comparative Example 2 having a concentration of component C of less than 0.3 mol / L. It was found that copper corrosion could be suppressed without significantly impairing the removability (peeling property).
Comparing Comparative Example 1 (pH 12) containing only MEA (component A) and TMAH (component B) in addition to water with Example 1 (pH 11) containing tetramethylammonium carbonate, tetramethylammonium carbonate It was found that there was no difference in the content of TMAH measured by neutralization titration between the two, although the pH of Example 1 was lowered by the compounding. Therefore, it is considered that the reason why the pH of Example 1 decreased is that the content of MEA decreased. From this, it was presumed that in Example 1, tetramethylammonium carbonate cationized the amino group of MEA. Here, the pH is the pH of the cleaning agent composition at 25 ° C., measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and 3 minutes after the electrode is immersed in the cleaning agent composition. It is a numerical value of.

According to the present disclosure, it is possible to provide a detergent composition capable of suppressing copper corrosion without significantly impairing the resin mask removability. By using the cleaning agent composition of the present disclosure, it is possible to shorten the cleaning process of electronic parts to which a resin mask is attached, improve the performance and reliability of manufactured electronic parts, and improve the productivity of semiconductor devices. ..

Claims (11)

Contains at least one alkaline agent (component B), carbonate ion (component C) and water (component D) selected from water-soluble amines (component A), quaternary ammonium hydroxides and alkali metal hydroxides. ,
A detergent composition for removing a resin mask, wherein the concentration of the component C is 0.3 mol / L or more. 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). ) And
A detergent composition for removing a resin mask, wherein the concentration of the component C'is 0.3 mol / L or more. The detergent composition for a resin mask layer according to claim 1 or 2, wherein the component A is an amine represented by the following formula (I).

In the 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, and R ² And R ³ are the same or different, respectively, and are 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, and are R ¹ and R. ² and R ³ do not become hydrogen atoms at the same time. The detergent composition according to any one of claims 1 to 3, wherein the content of the component D is 50% by mass or more and 95% by mass or less. Contains at least one alkaline agent (component B) selected from water-soluble amine (component A), quaternary ammonium hydroxide and alkali metal hydroxide, carbonate ion (component C) and water (component D). A method for cleaning a substrate, comprising a step of peeling the resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface using a cleaning agent composition having a concentration of component C of 0.3 mol / L or more. 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). ), And the resin mask is peeled off from the substrate having the copper-containing metal layer and the resin mask on the surface by using the cleaning agent composition having the concentration of the component C'of 0.3 mol / L or more. How to clean the substrate, including. Contains at least one alkaline agent (component B) selected from water-soluble amine (component A), quaternary ammonium hydroxide and alkali metal hydroxide, carbonate ion (component C) and water (component D). , A method for cleaning a substrate, comprising a step of peeling the resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface, using a cleaning agent composition obtained by cationizing the amino group of the component A. 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). ), And the resin mask is peeled off from the substrate having the copper-containing metal layer and the resin mask on the surface by using the cleaning agent composition obtained by cationizing the amino group of the component A. Cleaning method. The cleaning method according to any one of claims 5 to 8, wherein the copper-containing metal layer is a copper-plated layer. The cleaning method according to any one of claims 5 to 9, wherein the resin mask is a cured resist layer. A method for manufacturing an electronic component, comprising a step of cleaning a substrate having a copper-containing metal layer and a resin mask on the surface by using the cleaning method according to any one of claims 5 to 10.