TWI647303B - Detergent composition for resin mask layer and manufacturing method of circuit board - Google Patents

Abstract

The present invention provides a detergent composition for a resin masking layer with reduced residue of a resin masking layer (resin film) and suppression of solder corrosion, and a method for manufacturing a circuit board using the same. In one aspect, 100 parts by mass of the detergent composition for a resin masking layer used in the manufacture of a circuit board contains 0.5 part by mass or more of quaternary ammonium hydroxide (component A) and 3.0 parts by mass or less, containing 3.0 parts by mass or more and 14.0 parts by mass of water-soluble amine (component B), 0.3 parts by mass or more and 2.5 parts by mass or less of acid or its ammonium salt (component C), and 50.0 parts of water (component D) Part by mass or more and 95.0 parts by mass or less.

Description

Detergent composition for resin mask layer and manufacturing method of circuit board

The present invention relates to a cleaning composition for a resin masking layer and a method for manufacturing a circuit board.

In recent years, regarding mounting of electronic components on printed circuit wiring boards or ceramic substrates, the demand for higher density has been increasing year by year. As a method to meet this requirement, bare chip mounting methods have attracted attention. In the bare chip mounting method, there is a tendency to widely use face-down mounting by metal bumps instead of the previous face-up mounting to realize the electrical connection between the chip and the substrate wiring by wire bonding. According to the so-called metal bump method of face-down mounting by a metal bump, a low-resistance connection between electronic components can be expected.

Patent Document 1 discloses a stripping solution made of an aqueous solution containing a specific quaternary ammonium hydroxide, a water-soluble amine, and a hydroxylamine as a stripping solution for a photoresist.

Patent Document 2 discloses a dual-purpose cleaner capable of simultaneously cleaning a solder auxiliary agent containing benzyl alcohol, an amine compound, and water and a dry film resist.

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2002-62668

Patent Document 2: Japanese Patent Laid-Open No. 2007-224165

In the metal bump method, it is desirable to improve the removal rate of a resin masking layer (resin film) such as a dry film used for bump formation. The reason is that if a resin masking layer (resin film) remains on the substrate surface, it is difficult to implement good electronic component mounting.

When a circuit board having a resin shielding layer is heated for the formation of bumps, the resin shielding layer has a high molecular weight due to heat. The cleaning agent of the photoresist (resin masking layer) of Patent Document 1 may be insufficient for the cleaning performance of the resin masking layer after the high molecular weight. In addition, it is insufficient for the corrosion prevention of solder. In Patent Document 2, it is desired to further improve the detergency of the solder auxiliary agent and the dry film resist.

Therefore, in one aspect of the present invention, there is provided a detergent composition for a resin masking layer in which the residue of the resin masking layer (resin film) after heat treatment is reduced and the suppression of solder corrosion is improved.

One aspect of the present invention relates to a detergent composition for a resin masking layer. The detergent composition for a resin masking layer contains 100 parts by mass of the detergent composition and contains the following formula (I): The quaternary ammonium hydroxide (component A) represented by 0.5 parts by mass or more and 3.0 parts by mass or less, containing 3.0 parts by mass or more and 10.0 parts by mass or less of water-soluble amine (component B), and containing an acid or its ammonium salt (component C) 0.3 Part by mass or more and 2.5 parts by mass or less, and containing 50.0 parts by mass or more and 95.0 parts by mass or less of water (component D).

(In the formula, R ₁ , R ₂ , and R ₃ are the same or different, and are alkyl groups having 1 to 4 carbons; R ₄ is alkyl groups having 1 to 4 carbons or hydroxy-substituted alkyl groups having 1 to 4 carbons)

Another aspect of the present invention relates to a circuit board including the following steps (1) to (5) Of manufacturing method.

Step (1): a step of forming a resin masking layer on the surface of the substrate provided with the soldering portion.

Step (2): A step of forming an opening portion in the resin mask layer so that the welding portion is exposed.

Step (3): A step of filling the above-mentioned opening with a solder bump forming material.

Step (4): a step of melting the solder bump forming material by heating to fix the solder bump to the soldered portion.

Step (5): A step of cleaning the substrate obtained in step (4) using the detergent composition for a resin masking layer of the present invention.

According to the detergent composition for a resin masking layer and the method for manufacturing a circuit board of the present invention, a solder masking layer (resin film) such as a dry film is used to fix a solder bump to a soldering portion (such as an electrode) of a circuit board. At the same time, the removal of the resin masking layer (resin film) after the heating treatment (reflow) of the solder bump can be achieved at the same time, and the solder corrosion can be suppressed, and the effect of improving the reliability of solder connection can be achieved.

1‧‧‧ substrate

2‧‧‧ electrode

3‧‧‧solder mask

4‧‧‧ resin masking layer

5‧‧‧Solder bump forming material

6‧‧‧solder bump

7‧‧‧ opening

1 (a) to (e) are explanatory diagrams showing the outline steps of one or more embodiments of the method for manufacturing a circuit board of the present invention.

FIG. 2 is an example of the presence or absence of corrosion observed on the solder surface before and after immersion at 50 ° C. for 20 minutes in the detergent composition of Example 10 and Comparative Example 1 using the FE-SEM.

One aspect of the present invention is based on the insight that when a solder bump is formed on a soldered portion by a resin masking method, the resin masking layer subjected to heat treatment is peeled off by using a solution containing tetrahydroxide. Detergent composition of grade ammonium (component A), water-soluble amine (component B), acid or its ammonium salt (component C), and water (component D) can effectively remove The hard-to-peel resin masking layer can suppress solder corrosion, thereby improving solder connection reliability.

That is, one aspect of the present invention relates to a detergent composition for a resin masking layer (hereinafter also referred to as a "detergent composition of the present invention"). 100 parts by mass of the detergent composition contains 0.5 to 3 parts by mass of quaternary ammonium hydroxide (component A) represented by the following formula (I) and 3 to parts by mass of water-soluble amine (component B) 10 mass parts or less, containing an acid or its ammonium salt (component C) of 0.3 mass parts or more and 2.5 mass parts or less, and containing water (component D) of 50 mass parts or more and 95 mass parts or less.

(In the formula, R ₁ , R ₂ , and R ₃ are the same or different, and are alkyl groups having 1 to 4 carbons; R ₄ is alkyl groups having 1 to 4 carbons or hydroxy-substituted alkyl groups having 1 to 4 carbons)

In the detergent composition of the present invention, although the action mechanism for improving the removability of the resin masking layer is not clear, it is presumed to be the following mechanism. It can be considered that, with regard to quaternary ammonium hydroxide (component A) and water-soluble amine (component B), the use of an alkali component to cut off the acid component contained in the solder paste and the flux auxiliary component, or the occurrence of high heating occurs. Reducing the molecular weight of the resin mask (resist film). In addition, it is considered that the water-soluble amine (component B) and water (component D) are impregnated into the resist film after being reduced in molecular weight and can be dissolved and removed. In addition, it is inferred that although tin (Sn), which is a main component of solder, is dissolved in a strong alkaline aqueous solution, the dissolution reaction is suppressed by the acid or its ammonium salt (component C).

[Ingredient A]

In one or more embodiments, as the component A of the detergent composition of the present invention, that is, quaternary ammonium hydroxide, a salt formed from a cation and a hydroxide can be exemplified. In one or more embodiments, examples of the cation include tetramethylamine, tetraethylammonium, tetra (n- or iso) propylammonium, tetra (n- or iso) butylammonium, and tetrapentyl. Tetraalkylammonium cations such as ammonium, tetrahexylammonium, and trimethylethylammonium (carbon number of the alkyl group is 1 to 6), and examples include trimethyl (2-hydroxyethyl) ammonium and triethyl Alkyl ammonium cations having a hydroxyalkyl group such as (2-hydroxyethyl) ammonium (carbon number of the alkyl group is 1 to 6). Among these, tetramethylammonium is preferred from the viewpoints of improving the removability of the resin mask layer and suppressing corrosion of the solder. Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, and Hexyl ammonium hydroxide, trimethyl ethyl ammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydroxide, and the like. Among these, tetramethylammonium hydroxide is preferred from the viewpoint of improving the removability of the resin mask layer and suppressing solder corrosion. In one or more embodiments, the detergent composition of the present invention contains one or more ingredients A.

Regarding the content of the component A in the detergent composition of the present invention, that is, the content of quaternary ammonium hydroxide, it is 0.5 parts by mass or more in 100 parts by mass of the detergent composition, thereby improving the removal ability of the resin mask layer and suppressing solder From the viewpoint of corrosion, it is preferably 0.7 parts by mass or more. From the same viewpoint, the content of quaternary ammonium hydroxide as component A in 100 parts by mass of the detergent composition is 3.0 parts by mass or less, preferably 2.0 parts by mass or less, and more preferably 1.5 parts by mass. The following.

[Ingredient B]

In one or more embodiments, as the component B of the detergent composition of the present invention, that is, the water-soluble amine, alkyl amines, alkanolamines, polyamines, and cyclic amines can be used to improve the resin mask. From the viewpoint of layer removability and suppression of solder corrosion, an alkanolamine is preferred. In one or more embodiments, examples of the alkanolamine include monoethanolamine, N-ethylethanolamine, N-n-butylethanolamine, N, N-diethylethanolamine, and N, N-dibutylethanolamine. , N-third butylethanolamine, N-methylethanolamine and the like. Among these, monoethanolamine is preferred from the viewpoint of improving the removability of the resin mask layer and suppressing corrosion of the solder. In one or more In several embodiments, the detergent composition of the present invention contains one or a plurality of components B.

In one or more embodiments, the water-soluble amine as the component B is preferably an amine compound represented by the following formula (II).

(Wherein R ₅ is a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxy alkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms, and R ₆ and R ₇ are each the same or The difference is that it is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms. R ₅ , R ₆ , and R ₇ are not hydrogen atoms at the same time. )

R _{5 in} the formula (II) is preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms.

As a specific example of the amine compound represented by the above formula (II), an amine compound having an acid dissociation constant pKa of 9.0 or higher in an aqueous solution at 25 ° C is preferred, and examples include monoethanolamine (pKa = 9.55), N, N -Diethylethanolamine (pKa = 9.87), N-methylethanolamine (pKa = 9.95), ethylaminoethanol (pKa = 9.9), amines having hydroxyalkyl groups, propylene diamine (pKa = 10.6), etc. Aminoalkylamines. Among these, from the viewpoints of improving the removal ability of the resin mask layer and suppressing the corrosion of the solder, N-methylethanolamine and propylenediamine are preferred, and N-methylethanolamine is more preferred.

The content of the water-soluble amine, which is the component B of the detergent composition of the present invention, is 3.0 parts by mass or more in 100 parts by mass of the detergent composition, from the viewpoints of improving the removal ability of the resin mask layer and suppressing solder corrosion In particular, it is preferably 4.0 parts by mass or more. The content of the water-soluble amine as the component B is 14.0 parts by mass or less in 100 parts by mass of the detergent composition. From the same viewpoint, it is preferably 12.0 parts by mass or less, and more preferably 10.0 parts by mass. Hereinafter, it is more preferably 8.0 parts by mass or less, and still more preferably 7.0 parts by mass or less.

[Ingredient C]

As the component C in the detergent composition of the present invention, that is, the acid or its ammonium salt, organic acids and inorganic acids or their ammonium salts can be cited. As the organic acid, formic acid, acetic acid, oxalic acid, succinic acid, and citric acid can be cited. Examples of the inorganic acid include carbonic acid, sulfuric acid, nitric acid, and phosphoric acid. The ammonium salt of an acid may be an acid salt of ammonia. In one or more embodiments, the detergent composition of the present invention contains one or more ingredients C. As component C, specifically, one or more members selected from the group consisting of ammonium formate, ammonium acetate, ammonium oxalate, ammonium succinate, ammonium citrate, ammonium carbonate, ammonium sulfate, ammonium nitrate, and ammonium phosphate are preferable. Of compounds.

The content of the component C, that is, the acid or its ammonium salt, in the detergent composition of the present invention is preferably 0.3 parts by mass or more in 100 parts by mass of the detergent composition, from the viewpoint of suppressing the corrosion of solder. It is preferably 0.6 parts by mass or more, more preferably 0.8 parts by mass or more, and still more preferably 0.9 parts by mass or more. The content of the acid or its ammonium salt is 2.5 parts by mass or less in 100 parts by mass of the detergent composition, and from the viewpoint of sufficiently cleaning the resin masking layer, it is preferably 1.5 parts by mass or less.

[Ingredient D]

Examples of water as the component D in the detergent composition of the present invention include water that suppresses ionic substances such as ion-exchanged water and ultrapure water. The content of water in the detergent composition is 50.0 parts by mass or more in 100 parts by mass of the detergent composition, and from the viewpoint of sufficiently cleaning the resin masking layer, it is preferably 70.0 parts by mass or more, The content of water in the detergent composition is more preferably 75.0 parts by mass or more, and still more preferably 80.0 parts by mass or more. In 100 parts by mass of the detergent composition, the content is 95.0 parts by mass or less. From the viewpoint of solder corrosion, it is preferably 93.0 parts by mass or less.

[pH value]

In one or more embodiments, from the viewpoint of sufficiently cleaning the resin masking layer, the pH value of the detergent composition of the present invention is preferably 10.0 or more, and more preferably 10.5 or more. From a viewpoint, 14 or less is preferable, 13.5 or less is more preferable, and 13.0 or less is more preferable. The pH can be adjusted, for example, by the content of (A) ~ (C) components whole.

[Other ingredients: organic solvents]

In one or more embodiments, from the viewpoint of the solubility of the resin mask, the detergent composition of the present invention may contain an organic solvent. In one or more embodiments, examples of the organic solvent include diethylene glycol methyl ether, diethylene glycol butyl ether, and dimethyl sulfene. From the standpoint of improving the removal ability of the resin mask layer and suppressing the corrosion of the solder, the organic solvent in the detergent composition of the present invention is preferably 0 parts by mass or more in 100 parts by mass of the detergent composition, more preferably It is preferably 0.4 parts by mass or more, and more preferably 0.8 parts by mass or more. From the same viewpoint, it is preferably 35.0 parts by mass or less, more preferably 20.0 parts by mass or less, and still more preferably 10.0 parts by mass or less.

[Other ingredients: nitrogen-containing heterocyclic aromatic compound]

In one or more embodiments, the detergent composition of the present invention may contain a nitrogen-containing heterocyclic aromatic compound from the viewpoint of suppressing solder corrosion. In one or more embodiments, examples of the nitrogen-containing heterocyclic aromatic compound include 1H-benzotriazole, 1-methyl-1H-benzotriazole, and 1,2,3-triazole. From the viewpoint of improving the removal ability of the resin mask layer and suppressing the corrosion of the solder, the nitrogen-containing heterocyclic aromatic compound in the detergent composition of the present invention is preferably 0.01 in 100 parts by mass of the detergent composition. At least 0.02 parts by mass, more preferably at least 0.02 parts by mass, more preferably at least 0.03 parts by mass, and from the same viewpoint, it is preferably at most 1 part by mass, more preferably at most 0.8 part by mass, and even more preferably at least 0.5 part by mass The following.

[Preparation method of detergent composition]

That is, in one or more embodiments, the detergent composition of the present invention can be prepared in 100 parts by mass of the detergent composition, and a quaternary ammonium hydroxide (component) represented by the following formula (I) can be formulated A) 0.5 parts by mass or more and 3 parts by mass or less, 3 parts by mass or more and 10 parts by mass or less of water-soluble amine (component B), 0.3 parts by mass or more and 2.5 parts by mass or less of acid or its ammonium salt (component C), water ( Component D) A resin masking layer made of 50 parts by mass or more and 95 parts by mass or less Use the detergent composition.

(In the formula, R ₁ , R ₂ , and R ₃ are the same or different, and are alkyl groups having 1 to 4 carbons; R ₄ is alkyl groups having 1 to 4 carbons or hydroxy-substituted alkyl groups having 1 to 4 carbons)

In one or more embodiments without limitation, the detergent composition of the present invention can be prepared by blending the above-mentioned components A to D within the above-mentioned content range and uniformly mixing them. It should be noted that the detergent composition of the present invention can be prepared as a concentrate in which the amount of water of component D is reduced. From the viewpoint of transportation and storage, the concentrate of the detergent composition is preferably concentrated to 3 times or more, and from the viewpoint of stable production and storage, it is preferably concentrated to 10 times or less. The detergent composition made into a concentrate can be diluted at the time of use to any concentration within the scope of the present invention.

[Manufacturing method of circuit board]

In one or more embodiments, the detergent composition of the present invention can be used in the manufacture of circuit substrates forming solder bumps. That is, one aspect of the present invention relates to a method for manufacturing a circuit board (hereinafter, also referred to as a "manufacturing method of the present invention") including a step of cleaning using the detergent composition of the present invention.

Based on Fig. 1, one or more embodiments of the manufacturing method of the present invention will be described. FIG. 1 is an explanatory diagram showing the outline steps of one or more embodiments of the manufacturing method of the present invention. As shown in FIG. 1 (a), a solder resist film 3 (insulating layer) is formed on the surface of the substrate 1 and is firmly fixed. A surface of the substrate 1 on which the electrode 2 is exposed from the opening portion 7 formed in the solder resist film 3 is used to remove a part of the electrode 2 by exposure to form a resin masking layer 4 using a resist film. Then, as shown in FIG. 1 (b), the surface of the substrate 1 is coated with a solder bump forming material 5. Alternatively, instead of the solder bump forming material, a solder ball may be arranged in the opening portion 7. Then, as shown in FIG. 1 (c), heating is performed to deposit solder on the surface of the electrode 2 to form a solder bump 6. Moreover, as shown in FIG.1 (d), the resin masking layer 4 is peeled by the detergent composition of this invention, and the circuit board 1 in which the solder bump 6 was formed was obtained. It should be noted that, in one or more embodiments, as shown in FIG. 1 (e), the planarization of the solder bumps 6 is performed.

Therefore, in one or more embodiments, the manufacturing method of the present invention is a manufacturing method of a circuit board including the following steps (1) to (5).

Step (1): a step of forming a resin masking layer on the surface of the substrate provided with the soldering portion.

Step (2): A step of forming an opening portion in the resin mask layer so that the welding portion is exposed.

Step (3): A step of filling the above-mentioned opening with a solder bump forming material.

Step (4): a step of melting the solder bump forming material by heating to fix the solder bump to the soldered portion.

Step (5): A step of cleaning the substrate obtained in step (4) using the detergent composition of the present invention.

[step 1)]

Step (1) is a step of forming a resin mask layer on the surface of the substrate provided with the soldering portion. In one or more embodiments, for a substrate provided with a soldering portion, a circuit board provided with a soldering portion that should form a solder bump can be listed. In one or more embodiments, the soldering portion is an electrode. unit. In one or more embodiments, as shown in FIG. 1 (a), the above substrate may be exemplified by a surface in which the surface of the substrate 1 is covered by the solder resist film 3 and the electrode portion 2 is exposed on the surface, and the solder resist film 3 It is firmly fixed to the surface of the substrate 1. In one or more embodiments without limitation, as the solder resist film 3, an epoxy-based, acrylic-based, polyimide-based resin, or the like can be used. In addition, for the solder resist film 3, in order to expose the electrode portion 2, an opening portion may be formed before step (2), or may be the same as step (2). An opening is formed at some time or thereafter to expose the electrode portion 2.

In one or more embodiments, as the resin material forming the resin masking layer, from the viewpoint of forming a uniform thick film, it is preferable to use a film-like photosensitive resin, and more preferably a resist film. As the resist film, a general substance can be used.

In one or more embodiments, the thickness of the resin masking layer is preferably 10 μm or more, and more preferably 30 μm or more, from the viewpoint of the amount of solder precipitation required to form bumps by depositing solder. In addition, in one or more embodiments, the thickness of the resin masking layer is preferably 300 μm or less, and more preferably 150 μm or less, from the viewpoint of curing the resin masking layer to the bottom.

[Step (2)]

Step (2) is a step of forming an opening portion in the resin mask layer formed in step (1) so that the welding portion is exposed. In one or more embodiments, the openings can be formed by exposure and development processes. Furthermore, in one or more embodiments, the step (2) may form opening portions of the solder resist film simultaneously or sequentially by exposure and development processes. As shown in one or more embodiments shown in FIG. 1 (a), a solder resist film 3 and a resin masking layer 4 are formed on the surface of the circuit substrate 1 by using step (2), and can be obtained from the solder resist films formed thereon. 3 and the opening portion 7 of the resin mask layer 4 expose the substrate of the electrode portion 2.

[Step (3)]

Step (3) is a step of filling the solder bump forming material in the opening formed in step (2). In one or more embodiments, the solder bump forming material is a solder paste, which can be filled by a paste printing method, for example. Furthermore, in one or more embodiments, the solder bump forming material is a solder ball, and for example, it can be filled by a ball mounting method.

In one or more embodiments, as the solder paste, (a) a solder paste containing tin powder and a metal salt such as lead, copper, silver, or the like, or (b) containing tin powder, and selected from silver A solder paste in which at least one of ions and copper ions is complexed with at least one selected from the group consisting of arylphosphines, alkylphosphines and azoles. The fault between the metal salt of (a) and (b) above Mixtures are used in combination. In addition, the so-called tin powder includes, in addition to metal tin powder, for example, silver-containing tin-silver-based tin alloy powder or copper-containing tin-copper-based tin alloy powder. Examples of the metal salt include organic carboxylate and organic sulfonate.

The solder alloy contained in the solder bump forming material is typically a tin-based solder alloy, but a non-tin-based solder alloy such as an indium-based alloy can also be used in the present invention. Although particles of a conventional tin-lead eutectic solder alloy can also be used, particles of a lead-free solder alloy are preferably used. Preferred lead-free solder alloys include tin-silver-based, tin-copper-based, tin-silver-copper-based, and the like. If a representative composition example is listed, it is as follows (% is mass%):

Sn: balance, Ag: 0.3%, Cu: 0.5%

Sn: balance, Ag: 3.5%, Cu: 0.7%

Sn: balance, Ag: 3.5%

Sn: balance, Cu: 0.7%.

In the solder paste, a flux auxiliary component and a solvent may be further mixed. As the flux auxiliary component, generally used can be used for solder materials such as tin-lead, tin-silver, tin-copper, etc. As a solvent, as long as it is a component that can dissolve other components in the composition, adjust the viscosity and concentration. The substance is not particularly limited as long as it is a substance. As shown in one or more embodiments shown in FIG. 1 (b), a solder resist film 3 and a resin masking layer 4 are formed on the surface of the circuit substrate 1 by using step (3). The opening portion of the electrode portion 2 on the front surface is filled or arranged with a circuit board 1 having a solder forming material 5.

[Step (4)]

Step (4) is a step of heating the solder bump forming material filled in step (3) and melting it, thereby fixing the solder bump to the soldering portion. In one or more embodiments, the heating temperature is 200 ° C or higher, and in consideration of the heat resistance of the circuit board, 200 ° C to 260 ° C can be cited. The liquidus temperature of the solder bump forming material is usually 200 ° C or higher. In one or more other embodiments, the heating temperature is the above solder bump forming material. Above the liquidus temperature, and considering the heat resistance of the circuit board, the above liquidus temperature is 260 ° C or lower. The heating time is determined according to the composition of the solder bump forming material and the like. In one or more embodiments, it is preferably about 30 seconds to 10 minutes, and more preferably about 1 minute to 5 minutes. From the viewpoint of the productivity of the circuit board, it is preferable to fix the bumps by a single heat treatment. As shown in one or more embodiments shown in FIG. 1 (c), a solder resist film 3 and a resin masking layer 4 are formed on the surface of the circuit substrate 1 in step (4), and can also be obtained in the circuit substrate 1. A substrate of the solder bump 6 is formed on the surface electrode portion 2.

[Step (5)]

Step (5) is a step of cleaning the substrate obtained in step (4) using the detergent composition of the present invention. In one or more embodiments, as a method for cleaning the substrate with the detergent composition, various cleaning methods including an ultrasonic cleaning method, a spray method, a dipping shaking method, a dipping method, and a wiping method can be cited. Adapted to the type of circuit substrate, these methods can be combined individually or appropriately. From a viewpoint of suppressing an influence on a circuit board and a viewpoint of detergency, a spray method, a dipping shaking method, or a dipping method is preferable.

From the viewpoint of sufficiently cleaning the resin masking layer, the temperature at the time of cleaning in step (5) is preferably 25 ° C or higher, and more preferably 40 ° C or higher. From the viewpoint of suppressing evaporation of water, the temperature is preferably 90 ° C or lower, and more preferably 80 ° C or lower. From the viewpoint of sufficiently cleaning the resin masking layer, the pH value during the washing in step (5) is preferably 10.0 or more, more preferably 11.0 or more, even more preferably 12.0 or more, and more preferably 14.0 or less, more preferably 13.5 or less, and even more preferably 13.0 or less.

From the viewpoint of sufficiently cleaning the resin masking layer, the cleaning time in step (5) is preferably 1 minute or more, more preferably 3 minutes or more, and further preferably 5 minutes or more, which shortens the manufacturing of the circuit board. From the viewpoint of time, it is preferably 30 minutes or less, and more preferably 20 minutes or less.

Soluble in detergent combinations remaining on the circuit board are removed from the circuit board From the viewpoint of the dirt and / or the composition of the detergent composition, in the step (5), it is also preferable to perform a rinsing treatment (hereinafter also referred to as step (5a)) after the completion of the washing treatment. )). In the rinsing treatment, water or alcohol is preferably used. The pH value in the rinsing treatment is preferably performed near neutrality (for example, a pH value of 6.0 to 8.0 or a pH value of 6.5 to 7.5). Furthermore, after the washing process or the rinsing process is completed, it is preferable to perform a drying process (hereinafter also referred to as step (5b)) in order to remove moisture remaining on the surface of the circuit board.

Examples of the rinsing method include various methods such as a dipping method, an ultrasonic cleaning method, a dipping shaking method, and a spray method. From the viewpoint of rinsability, a spray method and a dipping method are preferred, and a spray method and a dipping method are more preferably used in combination. From the viewpoint of rinsing properties, the temperature of the rinsing treatment is preferably 25 ° C or higher, more preferably 40 ° C or higher, and from the viewpoint of suppressing evaporation of water, 90 ° C or lower, more preferably 80 ° C. the following. From the viewpoint of rinsing property, the time of the rinsing treatment is preferably 3 minutes or more, more preferably 5 minutes or more, and from the viewpoint of shortening the manufacturing time of the circuit board, 30 minutes or less is more preferable, and 20 minutes is more preferable. the following.

In addition, as a drying method in the drying process, for example, a method using an oven or a blower dryer for drying is preferable. From the viewpoint of drying property, the drying temperature is preferably 80 ° C or higher to suppress the influence on the circuit board. From the viewpoint, heating to 120 ° C or lower is preferred, and 100 ° C or lower is more preferred.

[Step (6)]

In one or more embodiments, from the viewpoint of obtaining a circuit board on which solder bumps are formed after the resin masking layer is removed at a higher removal rate, the manufacturing method of the present invention preferably includes the following steps (6 ).

Step (6): Use amine and / or tetrahydroxide containing dimethylsulfinium (DMSO) (component S), glycol ether (component T), and acid dissociation constant pKa of 9.0 or higher in an aqueous solution at 25 ° C A cleaning agent composition of grade ammonium (component U) and water (component V), a step of cleaning the substrate obtained in step (5).

By performing step (6), a circuit board having solder bumps formed after the resin masking layer is removed at a high removal rate can be obtained. That is, as shown in one or more embodiments shown in FIG. 1 (d), solder bumps 6 are formed on the electrode portion 2 on the surface of the circuit substrate 1 by using step (6), and obtained from the surface of the circuit substrate 1. The substrate after the resin mask layer is removed from the solder resist film 3 at a high removal rate.

In the step (6), as the method for cleaning the substrate obtained in the step (5) by using the detergent composition, there can be mentioned various cleaning methods including ultrasonic cleaning method, spray method, dipping shaking method, dipping method, and wiping method. method. Adapted to the type of circuit board, these methods can be used alone or in appropriate combinations to clean the resin barrier layer. From a viewpoint of suppressing an influence on a circuit board and a viewpoint of detergency, a spray method, a dipping shaking method, or a dipping method is preferable.

From the viewpoint of sufficiently cleaning the resin masking layer, the temperature at the time of washing in step (6) is preferably 25 ° C or higher, more preferably 40 ° C or higher, and from the viewpoint of suppressing evaporation of water, The temperature is preferably 90 ° C or lower, and more preferably 80 ° C or lower. In addition, in one or more embodiments, from the viewpoint of sufficiently cleaning the resin masking layer, the pH at the time of washing in step (6) is preferably 11 or more, and more preferably 12 or more.

From the viewpoint of sufficiently cleaning the resin masking layer, the cleaning time in step (6) is preferably 1 minute or more, more preferably 3 minutes or more, and further preferably 5 minutes or more, which shortens the manufacturing of the circuit board. From the viewpoint of time, it is preferably 30 minutes or less, and more preferably 20 minutes or less.

[Detergent composition of step (6)]

The detergent composition used in step (6) contains dimethylsulfinium (DMSO) (component S), a glycol ether (component T), and an amine having an acid dissociation constant pKa of 9.0 or higher in an aqueous solution at 25 ° C. And / or quaternary ammonium hydroxide (component U) and water (component V). The detergent composition can be obtained by mixing dimethylsulfinium (component S), glycol ether (component T), the above-mentioned amine and / or quaternary ammonium hydroxide (component U), and water (component V), for example Prepared by mixing at 25 ° C. In addition, dimethylsulfinium (component S), glycol ether (component T), and the above-mentioned amine and / or quaternary ammonium hydroxide may be prepared in advance. The concentrated solution of (ingredient U) is diluted with water (ingredient V) to prepare the detergent composition of step (6) and used.

[Ingredient S]

Ingredient S is dimethylsulfinium (DMSO). From the viewpoint of sufficiently cleaning the resin masking layer, the content of dimethylmethylene in the detergent composition is 100 parts by mass of the detergent composition, preferably 10.0 parts by mass or more, and more preferably 30.0 parts by mass or more, more preferably 35.0 parts by mass or more, and even more preferably 39.0 parts by mass or more. In addition, from the same viewpoint, it is preferably 50.0 parts by mass or less, and more preferably 43.0 parts by mass or less, out of 100 parts by mass of the detergent composition.

[Ingredient T]

Component T is a glycol ether. In one or more embodiments, the component T is preferably a glycol ether represented by the following formula (III).

R ₈ O (AO) _n R ₉ (III)

(Wherein R ₈ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, R ₉ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and AO is an alkylene group having 2 or 3 carbon atoms (Oxy group, n is the average addition mole number and is 1 to 4)

In one or more embodiments, the component T is an alkyl ether or an aryl ether of a (poly) alkylene glycol. Examples of the (poly) alkylene glycol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol. Examples of the alkyl ether include monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monoisobutyl ether, monohexyl ether, dimethyl ether, diethyl ether, butyl methyl ether, ethyl propyl ether, and butyl ether. , Dipropyl ether, dibutyl ether. Examples of the aryl ether include monophenyl ether and monobenzyl ether. From the viewpoint of sufficiently cleaning the resin masking layer, the component T is preferably monomethyl ether, monoethyl ether, monobutyl ether, monoisobutyl ether, monobenzyl glycol, diethylene glycol, or triethylene glycol. Ether, specifically, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and ethylene glycol monobenzyl ether are preferable, and diethylene glycol monobutyl ether is more preferable. The component T may be a single compound represented by the above formula (III), or may be composed of a plurality of compounds. to make.

From the viewpoint of sufficiently cleaning the resin masking layer, the content of the component T in the detergent composition is 100 parts by mass of the detergent composition, preferably 30.0 parts by mass or more, and more preferably 35.0 parts by mass or more . From the same viewpoint, the content of the component T in 100 parts by mass of the detergent composition is preferably 70.0 parts by mass or less, more preferably 50.0 parts by mass or less, and even more preferably 43.0 parts by mass or less.

From the viewpoint of the removability of the resin masking layer, the mass ratio [(S) / (T)] of the component S to the component T is preferably 0.15 or more, more preferably 0.30 or more, and even more preferably 0.50 or more, and It is preferably 2.00 or less, more preferably 1.50 or less, and even more preferably 1.20 or less.

[Ingredient U]

Component U is an amine and / or quaternary ammonium hydroxide having an acid dissociation constant pKa of 9.0 or more in an aqueous solution at 25 ° C. From the viewpoint of suppressing solder corrosion, component U is preferably amine, and from the viewpoint of sufficiently cleaning the resin masking layer, quaternary ammonium hydroxide is preferred. In one or more embodiments, component U is an amine represented by the following formula (IV) and having an acid dissociation constant pKa of 9.0 or higher in an aqueous solution at 25 ° C and / or hydrogen represented by the following formula (V) Quaternary ammonium oxide. The pKa is described in, for example, "Basics of Chemistry (Basic Chemistry)" (Maruzen Co., Ltd., Japan Chemical Society) Maruzen Co., Ltd., Japan Chemical Society). The pKa is preferably 9.5 or more, more preferably 9.8 or more, and more preferably 12.0 or less, more preferably 11.5 or less, and even more preferably 11.0 or less.

(R ₁₀ ) ₃ N (IV)

(Wherein R _{10 is the} same or different, and is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms, and three R ₁₀ (Not both hydrogen atoms)

_{[(R 11) 3 -NR 12} ] + OH - (V)

(Wherein, R ₁₁ represents an alkyl group having 1 to 3 carbon atoms, and R ₁₂ represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms)

Specific examples of the amine compound having an acid dissociation constant pKa of 9.0 or higher in an aqueous solution at 25 ° C. represented by the above formula (IV) include monoethanolamine (pKa = 9.55), N, N-diethylethanolamine ( pKa = 9.87), N-methylethanolamine (pKa = 9.95), ethylaminoethanol (pKa = 9.9), amines having hydroxyalkyl groups, propylenediamine (pKa = 10.6), amines having amine alkyl groups . Among these, from the viewpoint of removing the resin mask, N-methylethanolamine and propylene diamine are preferred, and N-methylethanolamine is more preferred. It is considered that by using an amine having a pKa of 9.0 or higher, it is considered that the use of an alkali to reduce the molecular weight of the resin masking layer.

Examples of the quaternary ammonium hydroxide represented by the formula (V) include salts formed from the following cations and hydroxides. Examples of the cation include tetramethylammonium cation (tetraalkylammonium cation (carbon number of 1 to 6), tetramethylammonium, tetraethylammonium, tetra (n- or iso) propylammonium, tetrakis ( N- or iso) butylammonium, tetrapentylammonium, tetrahexylammonium, trimethylethylammonium, and an alkylammonium cation having a hydroxyalkyl group (carbon number of the alkyl group is 1 to 6) Trimethyl (2-hydroxyethyl) ammonium and triethyl (2-hydroxyethyl) ammonium. Among them, tetramethylammonium is preferred. Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, and tetramethylammonium hydroxide. Hexyl ammonium hydroxide, trimethyl ethyl ammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydroxide, and the like. Among these, from the viewpoint of removing the resin mask, tetramethylammonium hydroxide is preferred.

From the viewpoint of the removability of the resin masking layer, the content of the component U in the detergent composition is 100 parts by mass of the detergent composition, preferably 0.5 parts by mass or more, and more preferably 1.0 parts by mass or more Furthermore, it is more preferably 3.0 parts by mass or more, and in 100 parts by mass of the detergent composition, it is preferably 20.0 parts by mass or less, and more preferably 15.0 parts by mass or less.

[Ingredient V]

The component V is water, and is preferably water that suppresses ionic substances such as ion-exchanged water and ultrapure water. From the viewpoint of the removability of the resin masking layer, the content of the component V in the detergent composition is 100 parts by mass of the detergent composition, preferably 3.0 parts by mass or more, and more preferably 8.0 It is preferably 12.0 parts by mass or more, and more preferably 20.0 parts by mass or less, and more preferably 18.0 parts by mass or less, out of 100 parts by mass of the detergent composition.

From the viewpoint of the removability of the resin mask layer, the mass ratio [(U) / (V)] of the component U to the component V is preferably 0.1 or more, more preferably 0.2 or more, and more preferably 1.5 or less, more It is preferably 0.9 or less, and more preferably 0.6 or less.

From the viewpoint of the removability of the resin masking layer, the mass ratio of the total amount of components S and T to the total amount of components U and V [[(S) + (T)] / [(U) + ( V)]] is preferably 1.0 or more, more preferably 2.0 or more, and preferably 10.0 or less, and more preferably 5.0 or less.

[pH value]

In one or more embodiments, from the viewpoint of sufficiently cleaning the resin masking layer, the pH of the detergent composition is preferably 11 or more, more preferably 12 or more. The pH value can be adjusted by the content of the amine and / or quaternary ammonium hydroxide of the component U.

From the viewpoint of removing from the circuit board the dirt and / or the components of the detergent composition that are soluble in the detergent composition remaining on the circuit board, step (6) after the cleaning process is completed, It is also preferable to perform a rinsing treatment [hereinafter also referred to as step (6a)]. In the rinsing treatment, water or alcohol is preferably used. The pH value in the rinsing treatment is preferably performed near neutrality (for example, a pH value of 6.0 to 8.0 or a pH value of 6.5 to 7.5). Furthermore, after the washing process or the rinsing process is completed, it is preferable to perform a drying process [hereinafter also referred to as step (6b)] in order to remove moisture remaining on the surface of the circuit board.

Examples of the rinsing method include various methods such as a dipping method, an ultrasonic cleaning method, a dipping shaking method, and a spray method. From the viewpoint of rinsability, a spray method and a dipping method are preferred, and a spray method and a dipping method are more preferably used in combination. From the viewpoint of rinsing property, the temperature of the rinsing treatment is preferably 25 ° C or higher, more preferably 40 ° C or higher, and from the viewpoint of suppressing evaporation of water, preferably 90 ° C or lower, and more preferably 80 ° C. the following. From the viewpoint of rinsing property, the time of rinsing treatment is preferably 3 minutes or more, more preferably 5 minutes or more, and from the viewpoint of shortening the manufacturing time of the circuit board, 30 minutes or less is more preferable, and 20 minutes is more preferable To under.

In addition, as a drying method in the drying process, for example, a method using an oven or a blower dryer for drying is preferable. From the viewpoint of drying property, the drying temperature is preferably 80 ° C or higher to suppress the influence on the circuit board. From the viewpoint, heating to 120 ° C or lower is preferred, and 100 ° C or lower is more preferred.

[Joining of electronic components]

In one or more embodiments, the method for manufacturing a circuit board of the present invention further includes the steps of placing an electronic component on the substrate obtained in the step (5), and heating the electronic component to the liquidus temperature of the solder bump. At a temperature of 260 ° C. or less, the soldered portion of the electronic component is bonded to the soldered portion of the substrate, thereby obtaining a substrate to which the electronic component is bonded. According to this embodiment, a circuit board to which electronic components are bonded can be manufactured.

[Removal method of resin mask layer]

In another aspect, the present invention is a method for removing a resin masking layer from a circuit substrate on which the resin masking layer is formed, that is, a method including a step of cleaning the substrate using the detergent composition of the present invention. . The specific constitution of the release agent composition and the detergent composition, and the cleaning method using these may be as described above.

[Kit]

Another aspect of the present invention is a method for manufacturing a circuit board of the present invention and / or a kit for use in a method for removing a resin masking layer of the present invention, wherein the kit contains the washing method of the present invention in a state before preparation. A kit of at least one of the components A to D of the detergent composition. The specific constitution of the detergent composition of the present invention and the cleaning method using these can be as described above.

Regarding the above-mentioned embodiments, the present invention further discloses one or more of the following embodiments, the above-mentioned composition, production method, or use.

<1> A method for manufacturing a circuit board including the following steps (1) to (5).

Step (1): a step of forming a resin masking layer on the surface of the substrate provided with the soldering portion.

Step (2): A step of forming an opening portion in the resin mask layer so that the welding portion is exposed.

Step (3): A step of filling the above-mentioned opening with a solder bump forming material.

Step (4): A step of fixing the solder bump to the soldered portion by heating to melt the solder bump forming material.

Step (5): A step of cleaning the substrate obtained in step (4) by using a detergent composition, wherein the detergent composition contains 100% by mass of the detergent composition and contains the following formula ( I) The quaternary ammonium hydroxide (component A) represented by 0.5 parts by mass or more and 3.0 parts by mass or less, containing 3.0 parts by mass or more and 14.0 parts by mass or less of a water-soluble amine (component B), and containing an acid or its ammonium salt C) 0.3 mass part or more and 2.5 mass parts or less, and containing 50.0 mass parts or more and 95.0 mass parts or less of water (component D).

(In the formula, R ₁ , R ₂ , and R ₃ are the same or different, and are alkyl groups having 1 to 4 carbons; R ₄ is alkyl groups having 1 to 4 carbons or hydroxy-substituted alkyl groups having 1 to 4 carbons)

<2> The method for manufacturing a circuit board according to <1>, wherein the quaternary ammonium hydroxide as the component A is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and Butyl ammonium hydroxide, tetrapentyl ammonium hydroxide, tetrahexyl ammonium hydroxide, trimethyl ethyl ammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxy Ethyl) ammonium hydroxide and combinations thereof.

<3> The method for manufacturing a circuit board according to <1> or <2>, wherein the content of the quaternary ammonium hydroxide as the above component A is 100 parts by mass of the detergent composition, and is preferably 0.5 parts by mass or more, preferably It is 0.7 parts by mass or more and / or 3.0 parts by mass or less, preferably 2.0 parts by mass or less, and more preferably 1.5 parts by mass or less.

<4> The method for manufacturing a circuit board according to any one of <1> to <3>, wherein the water-soluble amine as the component B is selected from the group consisting of an alkylamine, an alkanolamine, a polyamine, a cyclic amine, and The group composed of these combinations is preferably an alkanolamine. The alkanolamine is selected from the group consisting of monoethanolamine, N-ethylethanolamine, N-n-butylethanolamine, N, N-diethylethanolamine, N, The group consisting of N-dibutylethanolamine, N-thirdbutylethanolamine, N-methylethanolamine, and combinations thereof is preferably monoethanolamine.

<5> The method for producing a circuit board according to any one of <1> to <4>, wherein the water-soluble amine as the component B is an amine represented by the following formula (II).

<6> The method for producing a circuit board according to any one of <1> to <5>, wherein the content of the water-soluble amine as the component B is 3.0 parts by mass or more in 100 parts by mass of the detergent composition, It is preferably 4.0 parts by mass or more and / or 14.0 parts by mass, more preferably 12.0 parts by mass or less, more preferably 10.0 parts by mass or less, still more preferably 8.0 parts by mass or less, and even more preferably 7.0 parts by mass or less.

<7> The method for producing a circuit board according to any one of <1> to <6>, wherein the content of the acid or its ammonium salt as the component C is 0.3 parts by mass in 100 parts by mass of the detergent composition. The above is preferably 0.6 parts by mass or more, more preferably 0.8 parts by mass or more, still more preferably 0.9 parts by mass or more, and 2.5 parts by mass or less, and preferably 1.5 parts by mass or less.

<8> The method for manufacturing a circuit board according to any one of <1> to <7>, wherein the content of water as the component D is 100 parts by mass of the detergent composition, and is preferably 50.0 parts by mass or more, preferably It is 70.0 parts by mass or more, more preferably 75.0 parts by mass or more, still more preferably 80.0 parts by mass or more and / or 95.0 parts by mass or less, and more preferably 93.0 parts by mass or less.

<9> The method for manufacturing a circuit board according to any one of <1> to <8>, wherein the heating temperature in the above step (4) is preferably 200 ° C or higher and / or preferably 260 ° C or higher under.

<10> The method for manufacturing a circuit board according to any one of <1> to <9>, wherein the heating temperature in the step (4) is preferably equal to or higher than the liquidus temperature of the solder bump forming material and 260 ° C. The following temperature.

<11> The method for manufacturing a circuit board according to any one of <1> to <10>, wherein the pH value during the cleaning in the step (5) is preferably 10.0 or more, more preferably 11.0 or more, and It is preferably 12.0 or more and / or 14.0 or less, more preferably 13.5 or less, and even more preferably 13.0 or less.

<12> The method for manufacturing a circuit board according to any one of <1> to <11>, wherein the temperature during cleaning in the above step (5) is preferably 25 ° C or higher, more preferably 40 ° C or higher and / Or it is preferably 90 ° C or lower, more preferably 80 ° C or lower.

<13> The method for manufacturing a circuit board according to any one of <1> to <12>, wherein step (5) further includes performing a rinsing process (step (5a)) and / or a drying process ( Step (5b)).

<14> The method for manufacturing a circuit board according to any one of <1> to <13>, further including the following step (6).

Step (6): Use amine and / or tetrahydroxide containing dimethylsulfinium (DMSO) (component S), glycol ether (component T), and acid dissociation constant pKa of 9.0 or higher in an aqueous solution at 25 ° C A cleaning agent composition of grade ammonium (component U) and water (component V), a step of cleaning the substrate obtained in step (5).

<15> The method for producing a circuit board according to <14>, wherein the glycol ether (ingredient T) in the detergent composition in step (6) is a glycol ether represented by the following formula (III).

R ₈ O (AO) _n R ₉ (III)

(Wherein R ₈ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, R ₉ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and AO is an alkylene group having 2 or 3 carbon atoms (Oxy group, n is the average addition mole number and is 1 ~ 4)

<16> The method for manufacturing a circuit board according to <14> or <15>, wherein the amine and / or quaternary ammonium hydroxide (component U) in the detergent composition of the above step (6) is the following formula ( The amine represented by IV) and / or the quaternary ammonium hydroxide represented by the following formula (V).

(R ₁₀ ) ₃ N (IV)

(Wherein, R ₁₀ are each the same or different, is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, the carbon atoms of the hydroxyalkyl group having 1 to 6, carbon atoms, or an alkyl group of 1 to 6, R ₁₀ and 3 (Not a hydrogen atom at the same time)

_{[(R 11) 3 -NR 12} ] + OH - (V)

(Wherein R _{11 is the} same or different and is an alkyl group having 1 to 3 carbon atoms, R ₁₂ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms)

<17> The method for manufacturing a circuit board according to any one of <14> to <16>, wherein the detergent composition of the above step (6) contains 100 parts by mass of the detergent composition and contains dimethyl 10.0 parts by mass or more, preferably 30.0 parts by mass or more, more preferably 35.0 parts by mass or more, more preferably 39.0 parts by mass or more and / or 50.0 parts by mass or less, and preferably 43.0 parts by mass or less 30.0 parts by mass or more, preferably 35.0 parts by mass or more and / or 70.0 parts by mass or less, preferably 50.0 parts by mass or less, more preferably 43.0 parts by mass or less, containing an amine and / or Tetraammonium hydroxide (component U) is 0.5 parts by mass or more, preferably 1.0 part by mass or more, more preferably 3.0 parts by mass or more and / or 20.0 parts by mass or less, preferably 15.0 parts by mass or less, and contains water (ingredient V ) 3.0 parts by mass or more, preferably 8.0 parts by mass or more, more preferably 12.0 parts by mass or more and / or 20.0 parts by mass or less, and more preferably 18.0 parts by mass or less.

<18> The method for manufacturing a circuit board according to any one of <14> to <17>, wherein the dimethylsulfinium (component S) and the glycol ether (component S) in the detergent composition of the above step (6) The mass ratio [(S) / (T)] of component T) is 0.15 or more, preferably 0.30 or more, more preferably 0.50 or more and / or 2.00 or less, preferably 1.50 or less, and more preferably 1.20 or less.

<19> The method for manufacturing a circuit board according to any one of <14> to <18>, which The acid dissociation constant pKa of the amine and / or quaternary ammonium hydroxide (component U) in the detergent composition of the above step (6) in an aqueous solution at 25 ° C is preferably 9.5 or more, more preferably 9.8 or more and It is preferably 12.0 or less, more preferably 11.5 or less, and even more preferably 11.0 or less.

<20> The method for manufacturing a circuit board according to any one of <14> to <19>, wherein the amine and / or quaternary ammonium hydroxide (ingredient U) in the detergent composition of the above step (6) Content is 0.5 mass part or more in 100 mass parts of a detergent composition, Preferably it is 1.0 mass part or more, More preferably, it is 3.0 mass part or more and / or 20.0 mass part or less, More preferably, it is 15.0 mass part or less.

<21> The method for manufacturing a circuit board according to any one of <14> to <20>, wherein the content of water (ingredient V) in the detergent composition of the above step (6) is 3.0 parts by mass or more, It is preferably 8.0 parts by mass or more, more preferably 12.0 parts by mass or more and / or 20.0 parts by mass or less, and more preferably 18.0 parts by mass or less.

<22> The method for manufacturing a circuit board according to any one of <14> to <21>, wherein the mass ratio [(U) / (V)] of the component U to the component V is preferably 0.1 or more, and more preferably 0.2 The above and / or is preferably 1.5 or less, more preferably 0.9 or less, and still more preferably 0.6 or less.

<23> The method for manufacturing a circuit board according to any one of <14> to <22>, wherein the mass ratio of the total amount of the components S and T to the total amount of the components U and V [[(S) + ( T)] / [(U) + (V)]] is preferably 1.0 or more, more preferably 2.0 or more, and / or 10.0 or less, and more preferably 5.0 or less.

<24> The manufacturing method according to any one of <14> to <23>, wherein the pH value of the detergent composition in the step (6) is preferably 11 or more, and more preferably 12 or more.

<25> The method for manufacturing a circuit board according to any one of <14> to <24>, wherein a step of rinsing treatment is included between the above step (5) and the above step (6).

<26> A detergent composition containing, in 100 parts by mass of the detergent composition, 0.5 parts by mass or more and 3.0 parts by mass or less of quaternary ammonium hydroxide (component A) represented by the following formula (I) , Contains 3.0 parts by mass or more and 14.0 parts by mass or less of water-soluble amine (component B), 0.3 parts by mass or more and 2.5 parts by mass or less of acid or its ammonium salt (component C), and 50.0 parts by mass or more and 95.0 parts of water (component D) Mass parts or less.

(In the formula, R ₁ , R ₂ , and R ₃ are the same or different, and are alkyl groups having 1 to 4 carbons; R ₄ is alkyl groups having 1 to 4 carbons or hydroxy-substituted alkyl groups having 1 to 4 carbons)

<27> An application of the detergent composition as described in <26> as the detergent composition in step (5) of the method for manufacturing a circuit board according to any one of <1> to <25>.

<28> A detergent composition containing dimethylsulfinium (DMSO) (component S), glycol ether (component T), an amine having an acid dissociation constant pKa of 9.0 or higher in an aqueous solution at 25 ° C, and And / or quaternary ammonium hydroxide (component U) and water (component V).

<29> An application of the detergent composition as described in <28> as the detergent composition in step (6) of the method for manufacturing a circuit board according to any one of <11> to <25>.

<30> A method for cleaning a circuit substrate, comprising the step of cleaning the circuit substrate using a detergent composition such as <26> or <28>.

<31> A kit for use in a manufacturing method such as any one of <14> to <25>, comprising a detergent composition such as <26> used in step (5), And the detergent composition such as <28> used in step (6).

<32> Use of a detergent composition such as <26> as a detergent in the manufacture of circuit boards.

[Example]

The following examples are for the purpose of illustration of the present invention, and they are not intended to limit the present invention in any sense. In the examples,% is mass% unless otherwise specified.

<Examples 1 to 30 and Comparative Examples 1 to 12>

A circuit board on which solder bumps were formed was produced using the following detergent composition for a resin mask layer and a circuit board.

[Preparation of Detergent Composition for Resin Masking Layer]

1 part by mass of tetramethylammonium hydroxide, 5 parts by mass of monoethanolamine, 1 part by mass of ammonium formate, 12 parts by mass of diethylene glycol butyl ether, 4 parts by mass of dimethyl sulfene, and 77 parts by mass of water (total 100 parts by mass) Parts), and the mixture was uniformly mixed to prepare a detergent composition for a resin masking layer of Example 1. The pH was 10.9. It should be noted that the pH value is the pH value of the polishing liquid composition at 25 ° C., which can be measured using a pH meter, and is a value after 40 minutes after the electrode is immersed in the polishing liquid composition (the same applies hereinafter).

Instead of the composition of the detergent composition for the resin masking layer of Example 1 shown in Tables 1 and 2, the resin masking layers for Examples 2 to 30 and Comparative Examples 1 to 12 were prepared in the same manner as in Example 1. Detergent composition.

[Circuit Board]

The circuit substrate used in the formation of the solder bump is a glass epoxy substrate having a thickness of 300 μm and a size of 15 mm × 15 mm. For this substrate, there are 3600 electrodes with a copper surface of 25 μm in diameter at a distance of 50 μm per wafer. The electrodes on the surface of the substrate are surrounded by a solder resist layer having a height of 15 μm above the electrodes.

[Manufacturing of a circuit board with solder bumps]

In Examples 1 to 30 and Comparative Examples 1 to 12, circuit boards on which solder bumps were formed were manufactured according to the following steps (1) to (5b).

Step (1) Paste on a solder resist layer (sun ink: AUS410) formed on the circuit board A resist film (DuPont: WB-5030) was attached to form a resin mask layer.

In step (2), openings are formed in the resin mask layer and the solder resist layer on the electrodes of the circuit substrate by exposure and development processes.

Step (3) Apply a commercially available solder paste (Eco solder M705-GRN360-K2-V (manufactured by Senju Metal Industries, a mixture of solder metal (Sn-3Ag-0.5Cu) and flux auxiliary (rosin acid, additives and solvents) ) Mixture, liquidus temperature 217 ° C).

Step (4): heating on a hot plate at 250 ° C. for 1 minute to re-solder, and forming solder bumps on the electrodes of the circuit substrate. This circuit board was cut to a size of 1 cm square to prepare a test piece.

Step (5) In a 200 ml beaker containing 100 g of a detergent composition for a resin masking layer kept at a temperature of 60 ° C., immerse the above 1 cm square test piece for 3 minutes, wash it, and remove it from the beaker. Test piece.

Step (5a): immerse the test piece in ion-exchanged water maintained at a temperature of 60 ° C. for 5 minutes, rinse it, and remove the test piece.

In step (5b), the test piece is dried at a temperature of 85 ° C. for 15 minutes by using a low-temperature air dryer.

Removability of the resin masking layer in the test pieces of Examples 1 to 30 and Comparative Examples 1 to 12 was evaluated under the following conditions. The results are shown in Table 2.

<Resin Mask Removability Evaluation>

Use a light microscope to observe (magnification: 900 times) the test piece after the circuit board is manufactured. Select 5 fields of view from the 1 cm square test piece, and use the area measurement mode of the optical microscope to calculate the area of the resin mask remaining on the substrate. Calculate the washing rate. The calculation method for the removal rate and the optical microscope used in the measurement are shown below. Examples 1 to 30 and Comparative Examples 1 to 12 were evaluated at positions other than the periphery of the bumps. It should be noted that the positions other than the perimeter of the bumps are difficult to clean, and therefore the positions are easy to show differences.

Removal rate = (total area of 5 fields of view-area of the resin mask residue on the substrate after cleaning) ÷ total area of 5 fields of view × 100

Measuring machine: Digital microscope VHX-2000 manufactured by KEYENCE

<Solubility of tin>

In 20 g of the detergent composition for resin masking layers of Examples 1 to 30 and Comparative Examples 1 to 12, 1.8 g of tin (granular) manufactured by Wako Pure Chemical Industries was impregnated while stirring at 50 ° C for 20 minutes. Measure the concentration of tin dissolved in the detergent composition. The higher the tin concentration, the higher the solder corrosivity.

The measurement of tin concentration was performed by the following method.

With respect to the detergent composition, the luminous intensity of tin was measured with an ICP emission analyzer (PerkinElmer, Optima 5300) to quantify the amount of Sn etching.

As shown in Table 2, when the detergent composition for a resin masking layer of Examples 1 to 30 is used in step (5), the resin mask can be washed and removed better than Comparative Examples 1 to 12 Layer, and can inhibit the corrosion of solder.

<Solder SEM observation>

In the detergent composition for resin masking layer of Example 10 and Comparative Example 1, a substrate on which solder (Sn-3Ag-0.5Cu, diameter 80 μm) manufactured by Senju Metal Industry was mounted was immersed at 50 ° C. for 20 minutes. . FE-SEM (S-4000, manufactured by Hitachi HighTech) was used to enlarge the solder surface before and after dipping the cleaning composition to 900 times, and observe the presence or absence of corrosion such as pore corrosion. Observation photos are shown in Figure 2. In the case of dipping in Example 10, no change in the surface of the solder was observed. In the case of immersion in Comparative Example 1, solder surface hole corrosion was observed.

<Examples 31 to 48 and Comparative Examples 13 to 26>

[Manufacturing of a circuit board with solder bumps]

The detergent composition for the resin masking layer of Example 24 (Examples 31 to 39, Comparative Examples 13 to 19) and the detergent composition for the resin masking layer of Example 9 (Examples 40 to 48) were used. (Comparative Examples 20 to 26). A circuit board having solder bumps formed thereon was manufactured according to the following steps (1) to (6b). It should be noted that the circuit substrate used in the formation of the solder bump is the same substrate as described above.

Step (1) A resist film (DuPont: WB-5030) is attached to a solder resist layer (sun ink: AUS410) formed on a circuit substrate to form a resin masking layer.

In step (2), openings are formed in the resin mask layer and the solder resist layer on the electrodes of the circuit substrate by exposure and development processes.

Step (3) Apply a commercially available solder paste (Eco solder M705-GRN360-K2-V (manufactured by Senju Metal, solder metal (Sn-3Ag-0.5Cu) and flux auxiliary agent (mixture of rosin acid, additives and solvent)) Mixture, liquidus temperature 217 ° C).

Step (4): heating on a hot plate at 250 ° C. for 1 minute to re-solder, and forming solder bumps on the electrodes of the circuit substrate. This circuit board was cut to a size of 1 cm square to prepare a test piece.

Step (5) In a 200 ml beaker containing 100 g of the detergent composition for a resin masking layer kept at a temperature of 60 ° C., immerse the 1 cm square test piece for 1 minute and wash it, and remove the test piece from the beaker. .

Step (5a): immerse the test piece in ion-exchanged water maintained at a temperature of 60 ° C. for 5 minutes, rinse it, and remove the test piece.

In step (5b), the test piece is dried at a temperature of 85 ° C. for 15 minutes by using a low-temperature air dryer.

Step (6) In a 200 ml beaker containing 100 g of the detergent composition kept at a temperature of 60 ° C., immerse the 1 cm square test piece for 1 minute and wash it, and then remove the test piece from the beaker.

Step (6a): immerse the test piece in ion-exchanged water maintained at a temperature of 60 ° C. for 5 minutes, rinse it, and remove the test piece.

In step (6b), the test piece is dried at a temperature of 85 ° C. for 15 minutes by using a blower low-temperature dryer.

[Preparation of the detergent composition of step (6)]

40 parts by mass of dimethyl sulfene, 40 parts by mass of diethylene glycol monobutyl ether, 5 parts by mass of tetramethylammonium hydroxide, and 15 parts by mass of water (total 100 parts by mass) were prepared, and these were uniformed Mix to prepare the detergent composition of step (6) of Example 31. In addition, the detergent composition of step (6) of Examples 32 to 48 and Comparative Examples 13 to 26 was the same as that of Example 31 except that the components were formulated in predetermined mass parts according to the composition described in Tables 3 and 4. The preparation was carried out in the same manner. It should be noted that Examples 31 to 39 (Table 3) and Examples 40 to 48 (Table 4) are the detergent compositions of step (6) of the same composition, and Comparative Examples 13 to 19 (Table 3) and Comparative Examples 20 to 26 (Table 4) are the detergent compositions of step (6) of the same composition, respectively. Tables 3 and 4 show the pH of the detergent composition. The pH column "> 14" in these tables refers to the case where the pH value exceeds 14.

About the resin mask layer in the test pieces of Examples 31 to 48 and Comparative Examples 13 to 26 Removability was evaluated under the same conditions as above. The results are shown in Tables 3 and 4.

As shown in Tables 3 and 4, if the detergent compositions of Examples 31 to 48 were used in step (6), the resin masking layer could be washed and removed better than Comparative Examples 13 to 26.

Claims (24)

A method for manufacturing a circuit board includes the following steps (1) to (5), step (1): forming a resin masking layer on a surface of a substrate provided with a soldering portion, and step (2): forming a resin masking layer on the resin masking layer In step (3), a solder bump forming material is filled in the opening, and step (4): heating to melt the solder bump forming material, thereby fixing the solder bump. In the welding part, step (5): the substrate obtained in step (4) is washed with a detergent composition at a pH value of 10.0 or more and 14.0 or less, wherein the detergent composition is a detergent 100 parts by mass of the composition contains 0.5 parts by mass or more and 3.0 parts by mass or less of quaternary ammonium hydroxide (component A) represented by the following formula (I), and a water-soluble amine represented by the following formula (II) ( Component B) 3.0 parts by mass or more and 14.0 parts by mass or less, containing 0.3 parts by mass or more of one or more components (component C) selected from the group consisting of ammonium formate, ammonium acetate, ammonium oxalate, ammonium succinate, and ammonium citrate, and 2.5 parts by mass or less, containing 50.0 parts by mass or more and 95.0 parts by mass or less of water (ingredient D) , In formula (I), R ₁ , R ₂ , and R ₃ are each the same or different, and are alkyl groups having 1 to 4 carbon atoms; R ₄ is an alkyl group having 1 to 4 carbon atoms or a hydroxy substituted alkyl group having 1 to 4 carbon atoms; base, In formula (II), R ₅ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms, and R ₆ and R ₇ are each the same or The difference is that it is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms. R ₅ , R ₆ , and R ₇ are not hydrogen atoms at the same time. . For example, the method for manufacturing a circuit board according to claim 1, wherein the heating temperature in the above step (4) is 200 ° C or higher and 260 ° C or lower. For example, the method for manufacturing a circuit board according to claim 1, wherein the heating temperature in the step (4) is a temperature higher than the liquidus temperature of the solder bump forming material and lower than 260 ° C. The method for manufacturing a circuit board according to any one of claims 1 to 3, further comprising the following steps (6) and (6): using a detergent composition containing the following ingredients (S) to (V) The substrate obtained in step (5) is cleaned, and the component S: dimethylsulfinium (DMSO), the component T: a glycol ether, and the component U: an amine having an acid dissociation constant pKa of 9.0 or higher in an aqueous solution at 25 ° C. And / or quaternary ammonium hydroxide and component V: water. The method for manufacturing a circuit board according to claim 4, wherein the glycol ether (component T) in the detergent composition of step (6) is a glycol ether represented by the following formula (III), and R ₈ O (AO ) _n R ₉ (III) In formula (III), R ₈ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, R ₉ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, AO It is an alkyleneoxy group having 2 or 3 carbon atoms, n is an average addition mole number and is 1 to 4. The method for manufacturing a circuit board according to claim 4, wherein the amine and / or quaternary ammonium hydroxide (component U) in the detergent composition of step (6) is an amine represented by the following formula (IV), and / Or quaternary ammonium hydroxide represented by the following formula (V), (R ₁₀ ) ₃ N (IV) (in formula (IV), R _{10 is the} same as or different from each other, and is a hydrogen atom and a carbon number of 1 to 6) hydrocarbon group, a hydroxyalkyl group having a carbon number of 1 to 6, carbon atoms, or an alkyl group of 1 to 6, R ₁₀ 3 not simultaneously hydrogen _{atoms), [(R 11) 3} -NR 12] + OH - ( V) (In the formula (V), R _{11 is the} same or different and is an alkyl group having 1 to 3 carbon atoms, and R ₁₂ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms). The method for manufacturing a circuit board according to claim 4, wherein the detergent composition of step (6) contains 10.0 parts by mass or more of dimethyl fluorene (component S) with respect to 100 parts by mass of the detergent composition. 50.0 parts by mass or less, glycol ether (component T) 30.0 parts by mass or more and 70.0 parts by mass or less, amine and / or quaternary ammonium hydroxide (component U) 0.5 part by mass or more and 20.0 parts by mass or less, and water (component V) 3.0 parts by mass or more and 20.0 parts by mass or less. For example, the method for manufacturing a circuit board according to claim 4, wherein the mass ratio of the dimethyl sulfene (component S) to the glycol ether (component T) in the detergent composition of step (6) is (S) / ( T) is 0.15 or more and 2.00 or less. The method for manufacturing a circuit board according to claim 4, wherein a step of rinsing is included between the step (5) and the step (6). A method for manufacturing a circuit board includes the following steps (1) to (5), step (1): forming a resin masking layer on a surface of a substrate provided with a soldering portion, and step (2): forming a resin masking layer on the resin masking layer In step (3), a solder bump forming material is filled in the opening, and step (4): heating to melt the solder bump forming material, thereby fixing the solder bump. In the welding part, step (5): the substrate obtained in step (4) is washed with a detergent composition at a pH value of 10.0 or more and 14.0 or less, wherein the detergent composition is a detergent To 100 parts by mass of the composition, 0.5 to 3.0 parts by mass of the quaternary ammonium hydroxide (component A) represented by the following formula (I) is blended, and a water-soluble amine represented by the following formula (II) is blended ( Component B) 3.0 parts by mass or more and 14.0 parts by mass or less, and 0.3 or more parts by mass selected from the group consisting of formic acid, acetic acid, oxalic acid, succinic acid, citric acid, and their ammonium salts (component C) And 2.5 parts by mass or less, 50.0 parts by mass or more and 95.0 parts by mass of water (ingredient D) are prepared under, In formula (I), R ₁ , R ₂ , and R ₃ are each the same or different, and are alkyl groups having 1 to 4 carbon atoms; R ₄ is an alkyl group having 1 to 4 carbon atoms or a hydroxy substituted alkyl group having 1 to 4 carbon atoms; base, In formula (II), R ₅ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms, and R ₆ and R ₇ are each the same or The difference is that it is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms. R ₅ , R ₆ , and R ₇ are not hydrogen atoms at the same time. . The method for manufacturing a circuit board according to claim 10, wherein the component C is at least one selected from the group consisting of ammonium formate, ammonium acetate, ammonium oxalate, ammonium succinate, and ammonium citrate. For example, the method for manufacturing a circuit board according to claim 10, wherein the heating temperature in the step (4) is 200 ° C or higher and 260 ° C or lower. For example, the method for manufacturing a circuit board according to claim 10, wherein the heating temperature in the step (4) is a temperature above the liquidus temperature of the solder bump forming material and below 260 ° C. The method for manufacturing a circuit board according to any one of claims 10 to 13, further comprising the following steps (6) and (6): using a detergent composition containing the following ingredients (S) to (V) The substrate obtained in step (5) is cleaned, and the component S: dimethylsulfinium (DMSO), the component T: a glycol ether, and the component U: an amine having an acid dissociation constant pKa of 9.0 or higher in an aqueous solution at 25 ° C. And / or quaternary ammonium hydroxide and component V: water. The method for manufacturing a circuit board according to claim 14, wherein the glycol ether (component T) in the detergent composition of step (6) is a glycol ether represented by the following formula (III), and R ₈ O (AO ) _n R ₉ (III) In formula (III), R ₈ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms, R ₉ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, AO It is an alkyleneoxy group having 2 or 3 carbon atoms, n is an average addition mole number and is 1 to 4. The method for manufacturing a circuit board according to claim 14, wherein the amine and / or quaternary ammonium hydroxide (component U) in the detergent composition of step (6) is an amine represented by the following formula (IV), and / Or quaternary ammonium hydroxide represented by the following formula (V), (R ₁₀ ) ₃ N (IV) (in formula (IV), R _{10 is the} same as or different from each other, and is a hydrogen atom and a carbon number of 1 to 6) hydrocarbon group, a hydroxyalkyl group having a carbon number of 1 to 6, carbon atoms, or an alkyl group of 1 to 6, R ₁₀ 3 not simultaneously hydrogen _{atoms), [(R 11) 3} -NR 12] + OH - ( V) (In the formula (V), R _{11 is the} same or different and is an alkyl group having 1 to 3 carbon atoms, and R ₁₂ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms). The method for manufacturing a circuit board according to claim 14, wherein the detergent composition of step (6) contains 10.0 parts by mass or more of dimethyl sulfene (component S) with respect to 100 parts by mass of the detergent composition. 50.0 parts by mass or less, glycol ether (component T) 30.0 parts by mass or more and 70.0 parts by mass or less, amine and / or quaternary ammonium hydroxide (component U) 0.5 part by mass or more and 20.0 parts by mass or less, and water (component V) 3.0 parts by mass or more and 20.0 parts by mass or less. For example, the method for manufacturing a circuit board according to claim 14, wherein the mass ratio of the dimethyl sulfene (component S) to the glycol ether (component T) in the detergent composition of step (6) is (S) / ( T) is 0.15 or more and 2.00 or less. The method for manufacturing a circuit board according to claim 14, wherein a step of rinsing is included between the step (5) and the step (6). A detergent composition having a pH value of 10.0 to 14.0, which is contained in 100 parts by mass of the detergent composition, and contains quaternary ammonium hydroxide (component A) 0.5 represented by the following formula (I) Part by mass or more and 3.0 parts by mass or less, containing 3.0 parts by mass or more and 14.0 parts by mass or less of the water-soluble amine (component B) represented by the following formula (II), selected from the group consisting of ammonium formate, ammonium acetate, ammonium oxalate, and succinic acid One or more of the group consisting of ammonium and ammonium citrate (component C) 0.3 mass parts or more and 2.5 mass parts or less, containing water (component D) 50.0 mass parts or more and 95.0 mass parts or less, In formula (I), R ₁ , R ₂ , and R ₃ are each the same or different, and are an alkyl group having 1 to 4 carbon atoms; R ₄ is an alkyl group having 1 to 4 carbon atoms or a hydroxy substituted alkyl group having 1 to 4 carbon atoms; base, In formula (II), R ₅ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms, and R ₆ and R ₇ are each the same or The difference is that it is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms. R ₅ , R ₆ , and R ₇ are not hydrogen atoms at the same time. . A detergent composition having a pH value of 10.0 or more and 14.0 or less, which is contained in 100 parts by mass of the detergent composition, and a quaternary ammonium hydroxide (component A) represented by the following formula (I) is added to 0.5 3.0 mass parts or more and 3.0 mass parts or less, blending of 3.0 mass parts or more and 14.0 mass parts or less of the water-soluble amine (ingredient B) represented by the following formula (II), formulating and selecting from formic acid, acetic acid, oxalic acid, succinic acid, and citric acid One or more of the group consisting of ammonium salts and the like (component C) is 0.3 parts by mass or more and 2.5 parts by mass or less, and water (component D) is prepared by 50.0 parts by mass or more and 95.0 parts by mass or less, In formula (I), R ₁ , R ₂ , and R ₃ are each the same or different, and are an alkyl group having 1 to 4 carbon atoms; R ₄ is an alkyl group having 1 to 4 carbon atoms or a hydroxy substituted alkyl group having 1 to 4 carbon atoms; base, In formula (II), R ₅ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms, and R ₆ and R ₇ are each the same or The difference is that it is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an amino alkyl group having 1 to 6 carbon atoms. R ₅ , R ₆ , and R ₇ are not hydrogen atoms at the same time. . A detergent composition comprising component S: dimethylsulfinium (DMSO), component T: glycol ether, component U: amine and / or hydrogen having an acid dissociation constant pKa of 9.0 or more in an aqueous solution at 25 ° C. Quaternary ammonium oxide and component V: water. A kit for use in a manufacturing method according to any one of claims 4 to 9, 14 to 19, comprising a detergent combination such as claim 20 or 21 used in step (5) And the detergent composition as claimed in claim 22 used in step (6). Use of a detergent composition as claimed in claim 20 or 21 as a detergent in the manufacture of circuit boards.