Detergent composition for removing water-soluble flux residues

Abstract

The present invention relates to a detergent composition for removing water-soluble flux residues that has excellent removability of water-soluble flux residues in reduced pressure cleaning, wherein the mass ratio A / C of component A to component C is 0.01 to 0.05 inclusive and the mass ratio A / B of the component A to component B is 0.8 to 5 inclusive. Component A: An organic solvent which has a water-octanol partition coefficient (Log P value) of 1.3 or more and is composed of at least one compound selected from among compounds represented by formula (I) and formula (II). (I): R1-O-(AO)n-R2 In the formula (I): R1 is a phenyl group, a benzyl group, or an alkyl group having 6 to 9 carbon atoms; R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; AO is an ethyleneoxy group or a propyleneoxy group; and n is the number of moles of added AO and is an integer of 1 to 3. (II): R3-CH2OH In the formula (II), R3 is a phenyl group, a benzyl group, a cyclohexyl group, or an alkyl group having 5 to 10 carbon atoms. Component B: An amine compound. Component C: Water.

Description

Water-soluble flux residue removal cleaning agent composition

[0001] This disclosure relates to a water-soluble flux residue removal cleaning agent composition for use in vacuum cleaning of objects having water-soluble flux residue, a cleaning method using the same, and a method for manufacturing electronic components.

[0002] To reduce manufacturing costs, metals such as copper and copper alloys are used for electrodes that form circuits on electronic substrates such as semiconductor packages.

[0003] Surface mounting, which improves mounting density, is widely adopted as a method for mounting printed circuit boards. To improve mounting density, a technique is known in which a nanometal paste is applied between the wiring on the substrate and the terminals of the electronic elements, and the nanometal is melted and solidified by heating to bond the wiring on the substrate and the terminals of the electronic elements.

[0004] On the other hand, techniques for cleaning solder flux and resist from electronic components after soldering are known. There are two types of solder flux: rosin-based flux and water-soluble flux. Several methods for cleaning residue from water-soluble flux have been reported. For example, Japanese Patent Publication No. 7-185484 (Patent Document 1) describes a vacuum cleaning method in which ultrasonic waves are irradiated into a vacuum cleaning tank under reduced pressure to suppress the growth of cleaning liquid bubbles while cleaning. International Publication No. 2011 / 081071 (Patent Document 2) describes a series of steps including a depressurization step, a depressurization holding step, and a pressurization step in that order as one cycle, and that this cycle is performed within a specific time, so that the physical force generated due to the pressure change and the physical force generated due to the boiling of the cleaning agent composition during the depressurization holding step act on the flux residue present in the narrow gaps of the object to be cleaned. Japanese Patent Publication No. 2007-224165 (Patent Document 3) proposes a dual-purpose cleaning agent capable of simultaneously cleaning solder flux and dry film resist, characterized in that the amount of benzyl alcohol added is 5 to 94% by weight, the amount of amine compound is 1 to 50% by weight, and the amount of water is 3 to 90% by weight, relative to the total amount. Japanese Patent Publication No. 2024-60151 (Patent Document 4) proposes a cleaning agent composition comprising a hydrophilic glycol ether compound, an organic acid, a first compound, and water, wherein the first compound is a hydrophilic nitrogen-containing organic compound and / or a hydrophilic quaternary ammonium salt, the water content is 20% by mass or more, and the molar ratio of the first compound to the organic acid is 1 to 35. International Publication No. 2011 / 027673 (Patent Document 5) proposes a lead-free solder water-soluble flux removal cleaning agent containing 5 to 100 parts by weight of a glycol ether compound per 100 parts by weight of water.

[0005] This disclosure relates, in one aspect, to a water-soluble flux residue removal cleaning agent composition for use in vacuum cleaning of objects to be cleaned that have water-soluble flux residue, comprising the following components A, B, and C, wherein the mass ratio A / C of component A to component C is 0.01 or more and 0.05 or less, and the mass ratio A / B of component A to component B is 0.8 or more and 5 or less, to a water-soluble flux residue removal cleaning agent composition. Component A: An organic solvent having a water-octanol partition coefficient (LogP value) of 1.3 or more, and being at least one organic solvent selected from the compounds represented by the following formula (I) and the compounds represented by the following formula (II). 1 -O-(AO) n -R 2 (I) In the above formula (I), R 1 R is a phenyl group, a benzyl group, or an alkyl group having 6 to 9 carbon atoms. 2 R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethyleneoxy group or a propyleneoxy group, and n is the number of moles of AO added, which is an integer between 1 and 3. 3 -CH2OH (II) In the above formula (II), R 3 The group is a phenyl group, a benzyl group, a cyclohexyl group, or an alkyl group having 5 to 10 carbon atoms. Component B: Amine compound Component C: Water

[0006] This disclosure relates to a method for removing water-soluble flux residue from an object to be cleaned that has water-soluble flux residue, comprising the step of vacuum cleaning the object to be cleaned that has water-soluble flux residue using a water-soluble flux residue removal cleaning agent composition, wherein the water-soluble flux residue removal cleaning agent composition comprises the above components A, B, and C, the mass ratio A / C of component A to component C is 0.01 or more and 0.05 or less, and the mass ratio A / B of component A to component B is 0.8 or more and 5 or less.

[0007] This disclosure relates, in one embodiment, to a method for manufacturing an electronic component, comprising a flux cleaning step using the removal method of this disclosure.

[0008] Figure 1 is a schematic diagram of the test piece used in the cleaning test, where (a) is a top view and (b) is a side view. Figure 2 is a schematic diagram showing an example of a vacuum cleaning apparatus used in the cleaning test.

[0009] As a flux that can be washed with water, there is a water-soluble flux that is not hydrophobic like rosin flux, but rather a polyether resin with added activators, solvents, etc. Since the residue of water-soluble flux is hygroscopic, washing is essential. Such water-soluble flux is used when mounting other components (e.g., semiconductor chips, chip-type capacitors, other circuit boards, etc.) on a circuit board. In this case, a space (gap) is formed between the circuit board and the other components. The water-soluble flux used for mounting tends to remain in this gap as flux residue after soldering by reflow soldering, etc. In recent years, the size of the other components has tended to increase, increasing the area below the gap, and the gap itself tends to narrow, making it difficult to ensure sufficient cleaning with conventional cleaning methods. As an effective method for cleaning water-soluble flux residue below such gaps, a vacuum cleaning method can be mentioned. A vacuum cleaning method is a method in which the component to be cleaned is immersed in a cleaning tank and the pressure is reduced to expand the air present in the gap, degas it, and allow water to enter. However, if the area below the gap is large, water alone is insufficient for degassing the gap, and the residue and water do not come into contact, making it impossible to ensure sufficient cleaning performance (removal of water-soluble flux residue).

[0010] Therefore, this disclosure provides a water-soluble flux residue removal cleaning agent composition that can improve the removal performance of water-soluble flux residue in vacuum cleaning, as well as a cleaning method using the same and a method for manufacturing electronic components.

[0011] This disclosure provides, in one or more embodiments, a water-soluble flux residue removal agent composition capable of improving the removal performance of water-soluble flux residue in vacuum cleaning, a removal method using the same, and a method for manufacturing electronic components.

[0012] The present inventors have found that by using an aqueous cleaning agent containing a specific organic solvent, an amine, and water, with the mass ratio of the organic solvent to water within a predetermined range, in vacuum cleaning, the ability to remove water-soluble flux residue present in crevices can be improved.

[0013] That is, in one aspect, the present disclosure relates to a detergent composition for removing water-soluble flux residue, which is for use in reduced-pressure cleaning of an object to be cleaned having water-soluble flux residue, the detergent composition comprising the following component A, the following component B, and the following component C, wherein a mass ratio A / C of component A to component C is 0.01 or more and 0.05 or less, and a mass ratio A / B of component A to component B is 0.8 or more and 5 or less (hereinafter, also referred to as "the detergent composition of the present disclosure"). Component A: an organic solvent having a water-octanol partition coefficient (LogP value) of 1.3 or more, the organic solvent being at least one selected from the compound represented by the above formula (I) and the compound represented by the above formula (II) Component B: an amine compound Component C: water

[0014] According to the present disclosure, in one or more embodiments, there can be provided a detergent composition for removing water-soluble flux residue that can improve water-soluble flux residue removability in reduced-pressure cleaning. By using the detergent composition of the present disclosure, in one or more embodiments, water-soluble flux residue present in gaps of electronic components mounted using a water-soluble flux can be efficiently removed.

[0015] Although details of the action mechanism that exerts the effects of the present disclosure are unclear in some aspects, it is inferred as follows. In the present disclosure, by using, for reduced-pressure cleaning, a detergent composition that contains a specific organic solvent (component A), an amine compound (component B), and water (component C), and in which mass ratio A / C and mass ratio A / B fall within predetermined ranges, it is considered that component A promotes the degassing effect in the gaps, allowing the detergent composition to fill the gaps, thereby improving the removability of water-soluble flux residue. However, the present disclosure should not be construed as being limited to this mechanism.

[0016] In the present disclosure, the term "water-soluble flux residue" refers to a residue derived from water-soluble flux that remains on a substrate after forming a solder bump using a water-soluble flux, and / or on a substrate after soldering using a water-soluble flux. For example, when another component (e.g., a semiconductor chip, a chip capacitor, another circuit board, etc.) is stacked and mounted on a circuit board, a space (gap) is formed between the circuit board and the other component. The water-soluble flux used for said mounting may remain in this gap as a flux residue even after soldering by reflow or the like. In one or more embodiments of the present disclosure, a "cleaning composition" refers to a cleaning composition for cleaning and removing water-soluble flux residue after forming solder bumps and / or performing soldering using a water-soluble flux. Examples of the water-soluble flux residue to be cleaned by the cleaning composition of the present disclosure include: (a) water-soluble flux residue generated after soldering with a cream solder composed of powdered solder and a water-soluble flux; and (b) water-soluble flux residue generated after soldering an electrode formed of solder via a water-soluble flux.

[0017] In one or more embodiments of the present disclosure, the term "reduced-pressure cleaning" refers to cleaning that increases cleaning efficiency by: bringing an object to be cleaned having a water-soluble flux residue into contact with a cleaning composition in a cleaning tank, then depressurizing the cleaning tank to expand and deaerate air present in the gaps of the object to be cleaned, and allowing the cleaning composition to penetrate into said gaps.

[0018] In one or more embodiments of the present disclosure, "solder" is solder containing tin and / or copper. Examples of solders containing tin and / or copper include lead (Pb)-free solders such as Sn-Ag based solders, Sn-Cu based solders, Sn-Ag-Cu based solders, Sn-Zn based solders, and Sn-Sb based solders.

[0019] In this disclosure, "water-soluble flux" refers to a rosin-free water-soluble flux used to remove oxides that hinder the connection between metals such as electrodes and wiring and solder metal, and to promote such connection. Examples of the water-soluble flux include compositions mainly containing a resin, an activator, and a solvent. Examples of resins contained in the water-soluble flux include polyethylene glycol, polypropylene glycol, and copolymers thereof, and their derivatives; polyglycerin ester compounds; triazine compounds; vinyl group-containing compounds; carboxyl group-containing compounds; epoxy group-containing compounds, etc. Examples of activators contained in the water-soluble flux include halogen compounds, organic acids, amine compounds, amine salts, amino acids, amide compounds, etc. Examples of amine compounds include monoalkanolamines, dialkanolamines, trialkanolamines, etc. Examples of solvents contained in the water-soluble flux include water, aliphatic alcohols, aromatic alcohols, glycols, polyhydric alcohols, etc. The above-mentioned water-soluble flux is a flux that dissolves or disperses in water at the time of application to the substrate before heat treatment such as reflow, and is preferably a water-soluble flux with a solubility in water of 1% by mass or more at 20°C.

[0020] (Component A: Organic solvent with a water-octanol partition coefficient (LogP value) of 1.3 or higher) The detergent composition of this disclosure contains an organic solvent (hereinafter also referred to as "Component A") with a water-octanol partition coefficient (LogP value) of 1.3 or higher. Component A may be one type or a combination of two or more types.

[0021] From the viewpoint of degassing effect in the gaps, the LogP value of component A is preferably 1.3 or higher, more preferably 1.35 or higher, more preferably 1.4 or higher, and even more preferably 1.45 or higher. From the viewpoint of solubility in water, it is preferably 2.0 or lower, more preferably 1.8 or lower, and even more preferably 1.6 or lower. More specifically, the LogP value of component A is preferably 1.3 or higher and 2.0 or lower, more preferably 1.35 or higher and 2.0 or lower, more preferably 1.4 or higher and 1.8 or lower, and even more preferably 1.45 or higher and 1.6 or lower.

[0022] In the present disclosure, the water-octanol partition coefficient (LogP value) is a coefficient that indicates the affinity of an organic compound for water and 1-octanol. The 1-octanol / water partition coefficient P is the distribution equilibrium when a trace amount of a compound dissolves as a solute in a two-liquid-phase solvent of 1-octanol and water, and is the ratio of the equilibrium concentration of the compound in each solvent. It is generally expressed in the form of their logarithm LogP with base 10. LogP values of many compounds have been reported, and for example, many values are published in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS) and the like, which can be referred to. When no measured LogP value is available, it can be calculated using the program "PerkinElmer ChemDraw 19.1" available from HP of PerkinElmer, Inc. This program allows obtaining LogP values. The fragment approach is based on the chemical structure of a compound, and takes into account the number of atoms and the types of chemical bonds (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P.G. Sammens, J.B. Taylor and C.A. Ramsden, Eds., p.295, Pergamon Press, 1990). In the present disclosure, when a measured LogP value is available, that value is used; when no measured value is available, the LogP value calculated by the program PerkinElmer ChemDraw 19.1 is used.

[0023] In one or more embodiments, Component A is at least one selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II), from the viewpoint of promoting gap degassing during pressure reduction cleaning.

[0024] <Compound Represented by Formula (I)> R 1 -O-(AO) n -R 2 (I) In the above formula (I), R 1 is a phenyl group, a benzyl group, or an alkyl group having 6 or more and 9 or less carbon atoms, and R 2is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethylene oxy group or a propylene oxy group, and n is the number of moles of AO added, which is an integer between 1 and 3.

[0025] In the above formula (I), R 1 In one or more embodiments, R is a phenyl group, a benzyl group, or an alkyl group having 6 to 9 carbon atoms, and from the viewpoint of promoting crevice degassing during vacuum washing, a phenyl group or an alkyl group having 6 to 8 carbon atoms is preferred, and a phenyl group is more preferred. In the above formula (I), R 2 In one or more embodiments, is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and from a similar viewpoint, a hydrogen atom or an alkyl group having 2 to 4 carbon atoms is preferred, and a hydrogen atom is more preferred. In the above formula (I), AO is an ethylene oxy group or a propylene oxy group in one or more embodiments, and from a similar viewpoint, an ethylene oxy group is preferred. In the above formula (I), n is an integer from 1 to 3 in one or more embodiments, and from a similar viewpoint, 1 or 2 is preferred, and 1 is more preferred.

[0026] Compounds with a LogP value of 1.3 or higher that are represented by the above formula (I) include, for example, at least one selected from ethylene glycol monohexyl ether (LogP: 1.65), diethylene glycol monohexyl ether (LogP: 1.49), ethylene glycol-2-ethylhexyl ether (LogP: 2.46), diethylene glycol-2-ethylhexyl ether (LogP: 2.31), ethylene glycol monophenyl ether (LogP: 1.74), diethylene glycol monophenyl ether (LogP: 1.43), and ethylene glycol monobenzyl ether (LogP: 1.30). Among these, at least one selected from diethylene glycol monohexyl ether (LogP: 1.49), ethylene glycol monophenyl ether (LogP: 1.74), and diethylene glycol monophenyl ether (LogP: 1.43) is preferred from the viewpoint of promoting degassing in the gaps.

[0027] <Compound represented by formula (II)> R 3 -CH2OH (II) In the above formula (II), R 3 This is a phenyl group, a benzyl group, a cyclohexyl group, or an alkyl group having 5 to 10 carbon atoms.

[0028] In the above formula (II), R 3 In one or more embodiments, this is a phenyl group, a benzyl group, a cyclohexyl group, or an alkyl group having 5 to 10 carbon atoms. From the viewpoint of promoting crevice degassing during vacuum washing, a phenyl group or a cyclohexyl group is preferred, and a phenyl group is more preferred.

[0029] Compounds with a LogP value of 1.3 or higher that are represented by the above formula (II) include, for example, at least one selected from benzyl alcohol (LogP: 1.46), phenethyl alcohol (LogP: 1.74), and cyclohexanemethanol (LogP: 1.70). Among these, benzyl alcohol (LogP: 1.46) is preferred from the viewpoint of improving the removal of water-soluble flux residue.

[0030] As component A, from the viewpoint of improving the removal of water-soluble flux residue and promoting degassing in gaps, at least one selected from diethylene glycol monohexyl ether (LogP: 1.49), ethylene glycol monophenyl ether (LogP: 1.74), diethylene glycol monophenyl ether (LogP: 1.43), ethylene glycol-2-ethylhexyl ether (LogP: 2.46), and benzyl alcohol (LogP: 1.46) is preferred, and at least one of benzyl alcohol (LogP: 1.46) and ethylene glycol monophenyl ether (LogP: 1.74) is more preferred.

[0031] When using the cleaning agent composition of this disclosure, the content of component A is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, from the viewpoint of promoting crevice degassing during vacuum cleaning, and from the viewpoint of removing water-soluble flux residue, it is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. More specifically, when using the cleaning agent composition of this disclosure, the content of component A is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 4% by mass or less, and even more preferably 2% by mass or more and 3% by mass or less. When component A is a combination of two or more types, the content of component A refers to the total content of those types.

[0032] (Component B: Amine compound) In one or more embodiments, the detergent compositions of the present disclosure include an amine compound (hereinafter also simply referred to as "Component B"). Component B may be one type or a combination of two or more types.

[0033] In one or more embodiments, component B is a compound represented by the following formula (IV). In the above formula (IV), R 8 R represents a hydrogen atom, alkyl group, phenyl group, benzyl group, hydroxyethyl group, hydroxypropyl group, or aminoethyl group. 9 R represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, and an alkyl group. 10 This represents a hydroxyethyl group, a hydroxypropyl group, or an alkyl group. Examples of alkyl groups include alkyl groups having 1 to 6 carbon atoms.

[0034] In the above formula (IV), R 8 In one or more embodiments, is a hydrogen atom, an alkyl group, a phenyl group, a benzyl group, a hydroxyethyl group, a hydroxypropyl group, or an aminoethyl group. From the viewpoint of improving water-soluble flux residue removal and washing solution stability, an alkyl group is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred. 9 In one or more embodiments, R is a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, or an alkyl group, and from a similar viewpoint, a hydrogen atom is preferred.10 In one or more embodiments, is a hydroxyethyl group, a hydroxypropyl group, or an alkyl group, and from a similar viewpoint, a hydroxyethyl group or a hydroxypropyl group is preferred, and a hydroxyethyl group is more preferred.

[0035] Examples of compounds represented by the above formula (IV) include alkanolamines such as monoethanolamine (MEA), monoisopropanolamine, N-methylethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, N-butyldiethanolamine, and N,N-dibutylethanolamine (dibutylaminoethanol); and aromatic amines such as dimethylbenzylamine; at least one selected from these.

[0036] Component B is preferably a compound represented by the above formula (IV), and more preferably R in the above formula (IV), from the viewpoint of improving the removal of water-soluble flux residue, suppressing damage to the material, maintaining the solubility of tin ions, and suppressing the generation of insoluble tin precipitates. 10 The compound is an alkanolamine having a hydroxyethyl group or a hydroxypropyl group, more preferably at least one selected from N-methylethanolamine, N-butyldiethanolamine, and N-methyldiethanolamine, and even more preferably at least one of N-methylethanolamine and N-butyldiethanolamine.

[0037] When using the cleaning agent composition of this disclosure, the content of component B is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of improving the removal of water-soluble flux residues, and from the viewpoint of suppressing material damage, it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. More specifically, when using the cleaning agent composition of this disclosure, the content of component B is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and even more preferably 0.1% by mass or more and 3% by mass or less. When component B is a combination of two or more types, the content of component B refers to the total content of those types.

[0038] When using the detergent composition of this disclosure, the mass ratio A / B of component A to component B is preferably 0.8 or more, preferably 0.9 or more, more preferably 0.95 or more, and even more preferably 1.0 or more, from the viewpoint of degassing effect in gaps, and preferably 5 or less, preferably 4.5 or less, and more preferably 4.0 or less, from the viewpoint of improving water-soluble flux residue removal. More specifically, the mass ratio A / B is preferably 0.8 or more and 5 or less, preferably 0.9 or more and 5 or less, more preferably 0.95 or more and 4.5 or less, and even more preferably 1.0 or more and 4.0 or less.

[0039] (Component C: Water) The detergent composition of this disclosure contains water (hereinafter also referred to as "component C"). Examples of component C include ion-exchanged water, RO water (reverse osmosis treated water), distilled water, pure water, ultrapure water, etc. When using the detergent composition of this disclosure, the content of component C is preferably 85% by mass or more, more preferably 87% by mass or more, and even more preferably 90% by mass or more, from the viewpoint of rinsability, and from the viewpoint of degassing promotion effect during vacuum washing, it is preferably 99.4% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less. More specifically, when using the detergent composition of this disclosure, the content of component C is preferably 85% by mass or more and 99.4% by mass or less, more preferably 87% by mass or more and 98% by mass or less, and even more preferably 90% by mass or more and 97% by mass or less.

[0040] When using the detergent composition of this disclosure, the mass ratio A / C of component A to component C is preferably 0.01 or more, preferably 0.02 or more, and more preferably 0.03 or more, from the viewpoint of degassing effect in gaps, and preferably 0.05 or less, preferably 0.045 or less, and more preferably 0.04 or less, from the viewpoint of improving water-soluble flux residue removal. More specifically, the mass ratio A / C is preferably 0.01 or more and 0.05 or less, preferably 0.02 or more and 0.045 or less, and more preferably 0.03 or more and 0.04 or less.

[0041] When using the cleaning agent composition of this disclosure, the mass ratio B / C of component B to component C is preferably 0.001 or higher, more preferably 0.005 or higher, and even more preferably 0.007 or higher from the viewpoint of improving the removal of water-soluble flux residue, and preferably 0.1 or lower, more preferably 0.07 or lower, and even more preferably 0.05 or lower from the viewpoint of crevice cleaning performance. More specifically, the mass ratio B / C is preferably 0.001 or higher and 0.1 or lower, more preferably 0.005 or higher and 0.07 or lower, and even more preferably 0.007 or higher and 0.05 or lower.

[0042] The total content of component A, component B, and component C in the detergent composition of this disclosure is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and preferably 100% by mass or less, and more preferably 99.9% by mass or less, from the viewpoint of improving the removal of water-soluble flux residue.

[0043] (Component D: Benzotriazole or its derivative) In one or more embodiments, the detergent composition of the present disclosure may further contain benzotriazole or its derivative (hereinafter also referred to as "component D") from the viewpoint of improving the removal of water-soluble flux residue and suppressing copper discoloration. Component D may be one type or a combination of two or more types. Examples of component D include compounds represented by the following formula (V). In the above formula (V), R 12 and R 13 Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, a carboxyl group, an amino group, or a nitro group.

[0044] In the above equation (V), R 12 From the viewpoint of suppressing copper discoloration, hydrogen atoms are preferred. 13 From a similar viewpoint, a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is even more preferred.

[0045] Examples of compounds represented by the above formula (V) include at least one selected from benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, and toltriazole (a mixture of 4-methylbenzotriazole and 5-methylbenzotriazole), with benzotriazole being preferred from the viewpoint of suppressing copper discoloration.

[0046] From the viewpoint of suppressing copper discoloration, the content of component D when using the detergent composition of this disclosure is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more. From the viewpoint of solubility, it is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. More specifically, when using the detergent composition of this disclosure, the content of component D is preferably 0.005% by mass or more and 3% by mass or less, more preferably 0.01% by mass or more and 2% by mass or less, and even more preferably 0.05% by mass or more and 1% by mass or less. When component D is a combination of two or more types, the content of component D refers to the total content of those types.

[0047] (Component E: At least one organic acid selected from oxycarboxylic acids and phosphonic acids) In one or more embodiments, the detergent composition of the present disclosure may further contain at least one organic acid selected from oxycarboxylic acids and phosphonic acids (hereinafter also referred to as "component E") from the viewpoint of improving the removal of water-soluble flux residues. In one or more embodiments, component E may be in the form of a salt. In one or more embodiments, component E may form a salt with component B in the detergent composition. Component E may be one type or a combination of two or more types. Examples of oxycarboxylic acids in one or more embodiments include organic acids having one or more carboxyl groups and one or more hydroxyl groups in one molecule, such as citric acid, malic acid, tartaric acid, lactic acid, glycolic acid, gluconic acid and salts thereof. Examples of phosphonic acids include, in one or more embodiments, organic acids having one or more phosphonic acid groups in one molecule, such as 1-hydroxyethylidene-1,1-diphosphonic acid, methylenediphosphonic acid, 1,2-ethylenediphosphonic acid, 1,3-propylenediphosphonic acid, 1,4-butylenediphosphonic acid, 1,5-pentylenediphosphonic acid and 1,6-hexylenediphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) and salts thereof.Component E is preferably at least one selected from organic acids having one or more carboxyl groups and one or more hydroxyl groups in one molecule, and organic acids having one or more phosphonic acid groups in one molecule, from the viewpoint of removing metal residues (e.g., metal residues derived from solder metal), more preferably at least one selected from citric acid, malic acid, tartaric acid, lactic acid, glycolic acid, gluconic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, methylenediphosphonic acid, 1,2-ethylenediphosphonic acid, 1,3-propylenediphosphonic acid, 1,4-butylenediphosphonic acid, 1,5-pentylenediphosphonic acid and 1,6-hexylenediphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) and salts thereof, and even more preferably at least one selected from citric acid, malic acid, tartaric acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof. Preferred salts include sodium salts, alkali metal salts such as potassium salts, and amine salts.

[0048] From the viewpoint of metal residue removal, the content of component E when using the cleaning agent composition of this disclosure is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.1% by mass or more. From the same viewpoint, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. More specifically, when using the cleaning agent composition of this disclosure, the content of component E is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.02% by mass or more and 3% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less. If component E is a combination of two or more types, the content of component E refers to the total content of those types.

[0049] (Component F: Quaternary ammonium hydroxide) In one or more embodiments, the detergent composition of the present disclosure may further contain quaternary ammonium hydroxide (hereinafter also referred to as "component F") from the viewpoint of improving water-soluble flux residue removal. Component F may be one type or a combination of two or more types. Examples of component F in one or more embodiments include salts consisting of a quaternary ammonium cation and a hydroxide. Examples of cations in one or more embodiments include tetraalkylammonium cations (alkyl with 1 to 4 carbon atoms) such as tetramethylammonium, tetraethylammonium, tetra(n- or i-)propylammonium, tetra(n- or i-)butylammonium, and trimethylethylammonium, as well as alkylammonium cations (alkyl with 1 to 4 carbon atoms) having a hydroxyalkyl group such as trimethyl(2-hydroxyethyl)ammonium and triethyl(2-hydroxyethyl)ammonium. In one or more embodiments, component F is preferably a quaternary ammonium hydroxide represented by the following formula (III) from the viewpoint of improving water-soluble flux residue removal. In the above formula (III), R 4 , R 5 , R 6 and R 7 Each of these is independently at least one selected from a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group. In the above formula (III), R 4 , R 5 , R 6 and R 7 From the viewpoint of improving the removal of water-soluble flux residue, a methyl group is preferred.

[0050] Examples of quaternary ammonium hydroxides represented by the above formula (III) include at least one selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide. Among these, tetramethylammonium hydroxide (TMAH) is preferred from the viewpoint of maintaining the solubility of tin ions.

[0051] The content of component F when using the cleaning agent composition of this disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of improving the removal of water-soluble flux residue, and from the viewpoint of suppressing material damage, it is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 0.5% by mass or less. More specifically, the content of component F when using the cleaning agent composition of this disclosure is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, even more preferably 0.1% by mass or more and 3% by mass or less, and even more preferably 0.1% by mass or more and 0.5% by mass or less. When component F is a combination of two or more types, the content of component F refers to the total content of those types.

[0052] (Other Components) The cleaning agent compositions of this disclosure may contain other components as appropriate, to the extent that they do not impair the effects of this disclosure. Examples of other components include at least one selected from solvents other than component A, alkalis other than components B and F, acids other than component D, chelating agents, surfactants, rust inhibitors, thickeners, dispersants, polymer compounds, solubilizers, preservatives, disinfectants, antibacterial agents, defoamers, and antioxidants, which are commonly used in cleaning agents.

[0053] [Method for Manufacturing a Detergent Composition] The detergent composition of this disclosure can be manufactured, for example, by compounding component A, component B, component C, and optionally optional components (component D, component E, component F, and other components) in a known manner. In one or more embodiments, the detergent composition of this disclosure may consist of at least component A, component B, and component C. Accordingly, this disclosure relates, in one embodiment, to a method for manufacturing a detergent composition, which includes the step of compounding at least component A, component B, and component C. In this disclosure, "compounding" includes mixing component A, component B, component C, and optionally optional components (component D, component E, component F, and other components) simultaneously or in any order. In the method for manufacturing a detergent composition of this disclosure, the amount of each component compounded may be the same as the content of each component at the time of use of the composition of this disclosure as described above. In this disclosure, "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 processing or cleaning begins. The content of each component in the detergent composition of this disclosure when used can be considered as the amount of each component blended in the detergent composition of this disclosure in one or more embodiments. If neutralization is involved, the blending amount and content may differ, but they can be converted as appropriate.

[0054] The detergent composition of this disclosure may be used as is for cleaning, or it may be prepared as a concentrate, provided that separation or precipitation does not occur and impair storage stability. The concentrate of the detergent composition of this disclosure can be used after dilution so that each component is present in the above-described content (i.e., the content during cleaning). The concentrate of the detergent composition of this disclosure can also be used by adding each component separately at the time of use. In this disclosure, "at the time of use" of the concentrate means the state in which the concentrate has been diluted. Examples of concentrates in one or more embodiments include concentrates with dilution ratios of 2 to 300 times, 5 to 200 times, or 10 to 100 times.

[0055] Embodiments of the detergent composition of this disclosure may be a so-called one-component type, in which all components are supplied to the market in a pre-mixed state, or a so-called two-component type, in which the components are mixed at the time of use.

[0056] [pH of the cleaning agent composition] From the viewpoint of suppressing damage to materials, the pH of the cleaning agent composition of this disclosure is preferably 7.5 or higher, more preferably 7.7 or higher, even more preferably 8.0 or higher, and from the viewpoint of suppressing damage to materials, it is preferably 12.5 or lower, more preferably 12.0 or lower, and even more preferably 11.5 or lower. More specifically, the pH of the cleaning agent composition of this disclosure is preferably 7.5 or higher and 12.5 or lower, more preferably 7.7 or higher and 12.0 or lower, and even more preferably 8.0 or higher and 11.5 or lower. The pH of the cleaning agent composition of this disclosure can be adjusted using component B or known pH adjusting agents. In this disclosure, the pH of the cleaning agent composition is the pH when the composition is used at 25°C, and can be measured by the method described in the examples.

[0057] The cleaning agent compositions of the present disclosure are used in one or more embodiments for vacuum cleaning of objects to be cleaned that have water-soluble flux residue. The cleaning agent compositions of the present disclosure are suitably used in one or more embodiments for removing water-soluble flux residue (vacuum cleaning) from electronic components mounted using solder. That is, the cleaning agent compositions of the present disclosure are water-soluble flux residue removers for removing water-soluble flux residue (vacuum cleaning) from electronic components mounted using solder, in one or more embodiments.

[0058] [Objects to be cleaned] In one or more embodiments, objects to be cleaned that have water-soluble flux residue are substrates having water-soluble flux residue. In one or more embodiments, objects to be cleaned that have water-soluble flux residue include reflowed solder and objects to be cleaned that have water-soluble flux residue. In one or more embodiments, the solder is solder containing tin and / or copper. Examples of objects to be cleaned that have water-soluble flux residue include, for example, electronic components and their manufacturing intermediates having water-soluble flux residue, more specifically, soldered electronic components and their manufacturing intermediates having water-soluble flux residue, more specifically, electronic components and their manufacturing intermediates having water-soluble flux residue where the components are soldered with solder, electronic components and their manufacturing intermediates having water-soluble flux residue where the components are connected via solder, electronic components and their manufacturing intermediates containing water-soluble flux residue in the gaps of soldered components, electronic components and their manufacturing intermediates containing water-soluble flux residue in the gaps of components connected via solder, etc. The aforementioned manufacturing intermediate is an intermediate product in the manufacturing process of electronic components, including semiconductor packages and semiconductor devices, and includes, for example, a circuit board on which at least one component selected from semiconductor chips, chip capacitors, and circuit boards is mounted by soldering using a water-soluble flux, and / or a circuit board on which solder bumps for soldering the component are formed. The gap in the object to be cleaned is, for example, the space formed between a circuit board and a component (semiconductor chip, chip capacitor, other circuit board, etc.) soldered and mounted on that circuit board, and refers to a space whose height (distance between components) is, for example, 5 to 500 μm, 10 to 250 μm, or 20 to 100 μm. The width and depth of the gap depend on the size and spacing of the mounted components and electrodes (lands) on the circuit board. In one or more embodiments, the object to be cleaned having water-soluble flux residue includes a water-soluble flux residue present in the gaps between components connected via solder, where the distance between the components is 5 μm or more, or 10 μm or more, or 20 μm or more, and the gap is 500 μm or less, or 250 μm or less, or 100 μm or less.

[0059] [Cleaning Method] In one embodiment, this disclosure relates to a cleaning method (hereinafter also referred to as "the cleaning method of this disclosure") which includes a cleaning step of cleaning an object to be cleaned having a water-soluble flux residue using the cleaning agent composition of this disclosure under reduced pressure. The object to be cleaned is the object to be cleaned as described above.

[0060] The cleaning process, in one or more embodiments, includes the following steps 1 to 4: Step 1: Immersion step in which an object to be cleaned having a water-soluble flux residue is placed in a pressure-adjustable cleaning tank, filled with cleaning solution, and immersed in the water. Step 2: Depressurization step in which the pressure inside the cleaning tank is reduced until it reaches a predetermined value. Step 3: Depressurization holding step in which the pressure inside the cleaning tank, reduced in step 2, is continuously maintained within a predetermined pressure range, and the temperature of the cleaning agent composition inside the cleaning tank is maintained within a predetermined temperature range, for a predetermined time. Step 4: Pressurization step in which, after step 3, the pressure inside the cleaning tank is increased until it reaches a predetermined value.

[0061] In one or more embodiments, the cleaning step includes repeating a series of steps, at least steps 2 to 4, in that order, 1 to 50 times.

[0062] The cleaning process may, in one or more embodiments, further include the following step 5: Step 5: After step 4, a step of reducing the pressure inside the cleaning tank after dewatering by removing the cleaning liquid from the cleaning tank. In one or more embodiments, the cleaning process includes, after step 5, a series of steps including at least steps 1 to 5 in this order, repeated 1 to 50 times. This further improves the water-soluble flux residue removal (cleaning performance).

[0063] The following provides a detailed explanation of each of the above-mentioned steps 1 to 5.

[0064] (Step 1: Immersion Step) Step 1, in one or more embodiments, includes immersing an object to be cleaned having a water-soluble flux residue in a cleaning tank containing the cleaning agent composition of the present disclosure. The amount of cleaning agent composition to be filled into the cleaning tank is not particularly limited, as long as it is enough to immerse the object to be cleaned. As the cleaning tank, for example, a pressure vessel equipped with a heating means, an ultrasonic transducer, etc. can be used. The inside of the cleaning tank is in communication with an air pipe connected to a suction device such as a vacuum pump, and the air pipe includes a branch pipe not connected to the suction device. By controlling the opening and closing of a switching control valve provided in this branch pipe, the inside of the cleaning tank can be reduced to a desired pressure or increased to a desired pressure. In one or more embodiments, the cleaning agent composition of the present disclosure may be used for cleaning as is without dilution. In step 1, the temperature of the cleaning agent composition filled in the cleaning tank (immersion temperature) is preferably 50 to 70°C, more preferably 55 to 70°C, and even more preferably 60 to 70°C, immediately before the start of reduced pressure, from the viewpoint of improving the removal of water-soluble flux residue.

[0065] (Step 2: Depressurization Step) Step 2 includes, in one or more embodiments, reducing the pressure in the washing tank until it reaches P1 (kPa). Therefore, in one or more embodiments, the washing step includes reducing the pressure in the washing tank in which the object to be washed having the water-soluble flux residue is immersed in the water-soluble flux residue removal washing agent composition until it reaches P1 (kPa). However, P1 satisfies the relational expression P1 ≤ 30 (kPa). In Step 2, the pressure in the washing tank is preferably 5 (kPa) or more, more preferably 10 (kPa) or more, and even more preferably 15 (kPa) or more, from the viewpoint of volatilization of the washing liquid due to depressurization, and from the viewpoint of improving the removal of water-soluble flux residue present in narrow gaps of the object to be washed and shortening the washing time, it is preferably 30 (kPa) or less, more preferably 25 (kPa) or less, and even more preferably 20 (kPa) or less. More specifically, the pressure inside the washing tank is preferably 5 kPa or more and 30 kPa or less, more preferably 10 kPa or more and 25 kPa or less, and even more preferably 15 kPa or more and 20 kPa or less.

[0066] (Step 3: Reduced pressure holding step) Step 3, in one or more embodiments, includes continuously holding the pressure in the cleaning tank, which was reduced in Step 2, to P1 ± 0.4 kPa, and the temperature of the cleaning agent composition in the cleaning tank at 50 to 70°C for 5 to 600 seconds.

[0067] (Step 4: Pressurization Step) Step 4 includes, in one or more embodiments, increasing the pressure in the washing tank until it reaches P2 (kPa). P2 satisfies the relation 50 ≤ P2 ≤ 120 (kPa). In Step 4, the pressure in the washing tank is preferably in the range of 50 to 102 kPa, more preferably in the range of 80 to 102 kPa, and even more preferably at atmospheric pressure, from the viewpoint of improving the removal of water-soluble flux residue present in the gaps. Here, atmospheric pressure is the pressure when no special depressurization or pressurization is performed, and is usually equal to atmospheric pressure, approximately 1 atmosphere (101.3 (kPa)).

[0068] (Step 5) In one or more embodiments, Step 5 is performed after dewatering from the washing tank, and the pressure (P1) in the washing tank satisfies the relation P1 ≤ 30 (kPa). The duration for which the state of the above relation is maintained may be 5 to 600 seconds continuously. In Step 5, the pressure in the washing tank is preferably 5 (kPa) or more, more preferably 10 (kPa) or more, and even more preferably 15 (kPa) or more, from the viewpoint of volatilization of the washing liquid due to reduced pressure. Furthermore, from the viewpoint of effectively discharging the washing liquid present in narrow gaps of the object to be washed, it is preferably 30 (kPa) or less, more preferably 25 (kPa) or less, and even more preferably 20 (kPa) or less. More specifically, the pressure in the washing tank is preferably 5 (kPa) or more and 30 (kPa) or less, more preferably 10 (kPa) or more and 25 (kPa) or less, and even more preferably 15 (kPa) or more and 20 (kPa) or less.

[0069] In addition, the cleaning step may include reduced pressure in air in one or more embodiments. The cleaning step may also include repeating reduced pressure cleaning and reduced pressure in air in one or more embodiments.

[0070] (Rinsing Step) In one or more embodiments, the cleaning method of the present disclosure may further include a rinsing step in which the cleaning step is followed by rinsing with water or a rinsing agent. In one or more embodiments, the rinsing agent may be a water-soluble solvent with a boiling point of 100°C or less, such as alcohols like ethanol or isopropyl alcohol. In one or more embodiments, the rinsing step is a step of rinsing off dirt such as the cleaning agent composition, residue of water-soluble flux residue, or re-adhered water-soluble flux residue that has adhered to the object to be cleaned, and can be carried out under the same conditions as the cleaning step. The rinsing step may be carried out using one rinsing tank or using two or more rinsing tanks.

[0071] (Drying step) In one or more embodiments of the cleaning method of the present disclosure, it is preferable to include a drying step after the rinsing step. Known drying methods can be used as the drying method, for example, a forced-air dryer can be used.

[0072] In one or more embodiments, the cleaning step in the cleaning method of the present disclosure is a step (removal step) of removing water-soluble flux residue from an object to be cleaned that has water-soluble flux residue using the cleaning agent composition of the present disclosure. That is, the cleaning method of the present disclosure is a method for removing water-soluble flux residue from an object to be cleaned that has water-soluble flux residue, and includes a step of cleaning the object to be cleaned that has water-soluble flux residue under reduced pressure using the cleaning agent composition for removing water-soluble flux residue of the present disclosure (hereinafter also referred to as the "removal method of the present disclosure").

[0073] [Method for Manufacturing Electronic Components] This disclosure relates, in one embodiment, to a method for manufacturing electronic components (hereinafter also referred to as "the Method for Manufacturing Electronic Components of the Disclosure") which includes a flux cleaning step using the cleaning method or removal method of the Disclosure. The flux cleaning step is, in one or more embodiments, a step of cleaning an object to be cleaned using the cleaning method or removal method of the Disclosure. The object to be cleaned is the object to be cleaned as described above. For example, the Method for Manufacturing Electronic Components of the Disclosure, in one or more embodiments, includes at least one step selected from a semiconductor chip, a chip capacitor, and a circuit board, which is mounted on a circuit board by soldering using a water-soluble flux, and a step of forming solder bumps on the circuit board for connecting the component, etc., and a step of cleaning at least one selected from the circuit board on which the component is mounted and the circuit board on which the solder bumps are formed using the cleaning method of the Disclosure (flux cleaning step). Soldering using a water-soluble flux may be, for example, performed with lead-free solder, and may be done by reflow soldering or flow soldering. Electronic components include semiconductor packages without semiconductor chips, semiconductor packages with semiconductor chips, and semiconductor devices. The manufacturing method of electronic components according to this disclosure reduces water-soluble flux residue remaining in gaps and around solder bumps of soldered components by cleaning using the cleaning method or removal method according to this disclosure. This suppresses short circuits and poor adhesion between electrodes caused by the remaining water-soluble flux residue, thus enabling the manufacture of highly reliable electronic components.

[0074] This disclosure further relates to one or more embodiments described below. <1> A water-soluble flux residue removal cleaning agent composition for use in vacuum cleaning of an object to be cleaned having water-soluble flux residue, comprising the following component A, component B, and component C, wherein the mass ratio A / C of component A to component C is 0.01 or more and 0.05 or less, and the mass ratio A / B of component A to component B is 0.8 or more and 5 or less, respectively. Component A: An organic solvent having a water-octanol partition coefficient (LogP value) of 1.3 or more, and being at least one selected from the compounds represented by the following formula (I) and the compounds represented by the following formula (II) R 1 -O-(AO) n -R 2 (I) In the above formula (I), R 1 R is a phenyl group, a benzyl group, or an alkyl group having 6 to 9 carbon atoms. 2 R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethyleneoxy group or a propyleneoxy group, and n is the number of moles of AO added, which is an integer between 1 and 3. 3 -CH2OH (II) In the above formula (II), R 3 The group is a phenyl group, a benzyl group, a cyclohexyl group, or an alkyl group having 5 to 10 carbon atoms. Component B: amine compound Component C: water <2> The water-soluble flux residue removal detergent composition according to <1>, wherein component A is at least one selected from diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, ethylene glycol-2-ethylhexyl ether, and benzyl alcohol. <3> The water-soluble flux residue removal detergent composition according to <1> or <2>, wherein component A is at least one of benzyl alcohol and ethylene glycol monophenyl ether. <4> The water-soluble flux residue removal detergent composition according to any one of <1> to <3>, wherein component B is a compound represented by the following formula (IV). In the above formula (IV), R 8R represents a hydrogen atom, alkyl group, phenyl group, benzyl group, hydroxyethyl group, hydroxypropyl group, or aminoethyl group. 9 R represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, and an alkyl group. 10 R represents a hydroxyethyl group, a hydroxypropyl group, or an alkyl group. <5> In the above formula (IV), R 8 R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group, a hydroxyethyl group, a hydroxypropyl group, or an aminoethyl group. 9 R represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, and an alkyl group having 1 to 6 carbon atoms. 10 <4> is a water-soluble flux residue removal cleaning agent composition, wherein R represents a hydroxyethyl group, a hydroxypropyl group, or an alkyl group having 1 to 6 carbon atoms. <6> In the above formula (IV), R 8 R represents an alkyl group having 1 to 6 carbon atoms. 9 R represents a hydrogen atom. 10The water-soluble flux residue removal detergent composition according to <4>, wherein component B is at least one of an alkanolamine and an aromatic amine. <8> A water-soluble flux residue removal cleaning agent composition according to any one of <1> to <7>, wherein component B is at least one selected from monoethanolamine, monoisopropanolamine, N-methylethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, N-butyldiethanolamine, N,N-dibutylethanolamine, and dimethylbenzylamine. <9> The water-soluble flux residue removal cleaning agent composition according to any one of <1> to <8>, wherein component B is at least one of N-methylethanolamine and N-butyldiethanolamine. <10> The water-soluble flux residue removal cleaning agent composition according to any one of <1> to <9>, wherein the mass ratio B / C of component B to component C is 0.001 or more, or 0.005 or more, or 0.007 or more, and 0.1 or less, or 0.07 or less, or 0.05 or less. <11> The water-soluble flux residue removal cleaning agent composition according to any one of <1> to <10>, wherein the content of component A is 0.5% by mass or more, or 1% by mass or more, or 2% by mass or more, and 5% by mass or less, or 4% by mass or less, or 3% by mass or less.<12> A water-soluble flux residue removal cleaning agent composition according to any one of <1> to <11>, wherein the content of component B is 0.01% by mass or more, or 0.05% by mass or more, or 0.1% by mass or more, and 10% by mass or less, or 5% by mass or less, or 3% by mass or less. <13> A water-soluble flux residue removal cleaning agent composition according to any one of <1> to <12>, wherein the mass ratio A / B of component A to component B is 0.8 or more, or 0.9 or more, or 0.95 or more, or 1.0 or more, and 5 or less, or 4.5 or less, or 4.0 or less. <14> A water-soluble flux residue removal cleaning agent composition according to any one of <1> to <13>, wherein the content of component C is 85% by mass or more, or 87% by mass or more, or 90% by mass or more, and 99.4% by mass or less, or 98% by mass or less, or 97% by mass or less. <15> A water-soluble flux residue removal cleaning agent composition according to any one of <1> to <14>, wherein the mass ratio A / C of component A to component C is 0.01 or more, or 0.02 or more, or 0.03 or more, and 0.05 or less, or 0.045 or less, or 0.04 or less. <16> A water-soluble flux residue removal cleaning agent composition according to any one of <1> to <15>, wherein the total content of component A, component B, and component C is 90% by mass or more, or 95% by mass or more, or 99% by mass or more, and 100% by mass or less, or 99.9% by mass or less. <17> A method for removing water-soluble flux residue from an object to be cleaned which has water-soluble flux residue, comprising a cleaning step of cleaning the object to be cleaned which has water-soluble flux residue under reduced pressure using a water-soluble flux residue removal cleaning agent composition, wherein the water-soluble flux residue removal cleaning agent composition contains the following component A, the following component B, and the following component C, the mass ratio A / C of component A to component C is 0.01 or more and 0.05 or less, and the mass ratio A / B of component A to component B is 0.8 or more and 5 or less. Component A: An organic solvent R having a water-octanol partition coefficient (LogP value) of 1.3 or higher, and being at least one selected from the compounds represented by the following formula (I) and the compounds represented by the following formula (II). 1 -O-(AO) n -R2 (I) In the above formula (I), R 1 R is a phenyl group, a benzyl group, or an alkyl group having 6 to 9 carbon atoms. 2 R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethyleneoxy group or a propyleneoxy group, and n is the number of moles of AO added, which is an integer between 1 and 3. 3 -CH2OH (II) In the above formula (II), R 3 The group is a phenyl group, a benzyl group, a cyclohexyl group, or an alkyl group having 5 to 10 carbon atoms. Component B: amine compound Component C: water <18> The water-soluble flux residue removal method according to <17>, wherein the object to be cleaned has water-soluble flux residue in the gaps between components connected via solder, and the distance between the components is 5 μm or more, or 10 μm or more, or 20 μm or more, and 500 μm or less, or 250 μm or less, or 100 μm or less. <19> The water-soluble flux residue removal method according to <17> or <18>, wherein the cleaning step includes reducing the pressure in a cleaning tank in which the object to be cleaned is immersed in the water-soluble flux residue removal cleaning agent composition until the pressure becomes P1 (kPa). However, P1 satisfies the relational expression P1 ≤ 30 (kPa). <20> A method for removing water-soluble flux residue according to any one of <17> to <19>, wherein P1 is 5 (kPa) or more, or 10 (kPa) or more, or 15 (kPa) or more, and 25 (kPa) or less, or 20 (kPa) or less. <21> A method for manufacturing an electronic component, comprising a flux cleaning step using the water-soluble flux residue removal method according to any one of <17> to <20>.

[0075] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited in any way by these examples.

[0076] 1. Preparation of Detergent Compositions (Examples 1-7, Comparative Examples 1-4) Detergent compositions for Examples 1-7 and Comparative Examples 1-4 were prepared by mixing each component in a 100 mL glass beaker to the composition shown in Table 1 below and mixing under the following conditions. Unless otherwise noted, the numerical values ​​for each component in the table indicate the amount (mass %) used in the prepared detergent composition. <Mixing Conditions> Liquid temperature: 25°C Stirrer: Magnetic stirrer (50 mm rotor) Rotation speed: 300 rpm Stirring time: 10 minutes

[0077] The following were used to prepare each detergent composition: (Component A) Benzyl alcohol [manufactured by Tokyo Chemical Industry Co., Ltd.] Diethylene glycol monohexyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] Ethylene glycol monophenyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] Ethylene glycol-2-ethylhexyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] (Non-Component A) Diethylene glycol monobutyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] (Component B) N-methylethanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.] N-butyldiethanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.] (Component C) Water [Pure water with a purity of 1 μS / cm or less produced by Organo Corporation's G-10DSTSET pure water system] (Component D) Benzotriazole [manufactured by Tokyo Chemical Industry Co., Ltd.] (Component E) Etidronic acid: 1-hydroxyethylidene-1,1-diphosphonic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0078] [pH Measurement] pH was measured using the following procedure. 20 g of each detergent composition was added to a 50 mL glass beaker, and the pH at 25°C was measured using a pH meter (manufactured by Toa TDK Co., Ltd.). The reading was taken 3 minutes after immersing the electrode in the detergent composition.

[0079] 2. Evaluation of the cleaning agent compositions The cleaning agent compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were used to perform the following tests and evaluate their ability to remove water-soluble flux residues.

[0080] [Evaluation of gap cleaning performance (removal of water-soluble flux residue)] <Water-soluble flux residue model used> A commercially available water-soluble flux (Sparkle Flux WF6317) and solder metal (Sn-3Ag-0.5Cu) were placed in a copper container and heated at 250°C for 30 minutes in an atmospheric environment to remove the solvent. The flux portion was recovered and used as the water-soluble flux residue model. <Test piece> As shown in Figure 1, the test piece 10 was made by placing a glass substrate 2 on a glass epoxy substrate 1 via a spacer 3 to form a gap (height 25 μm, length 50 mm, width 50 mm). The above water-soluble flux residue model 4 was filled into this gap and used for the cleaning performance test. <Cleaning method (vacuum cleaning)> The following cleaning test was performed using the vacuum cleaning apparatus shown in Figure 2. The cleaning tank 11 was placed in a water bath and the cleaning solution (cleaning agent composition) 12 in the cleaning tank 11 was heated and maintained at 60°C. Next, the test piece 10 was immersed in the cleaning solution 12 in the cleaning tank 11 (step 1). Next, the air in the cleaning tank 11 was removed from the vacuum pump line 13 to reduce the pressure in the cleaning tank 11 to 17 kPa (step 2), the reduced pressure state was maintained for 5 minutes (step 3), and the cleaning tank 11 was opened to the atmosphere and the pressure was increased to atmospheric pressure (step 4). Then, the test piece 10 was removed from the cleaning tank 11, rinsed by immersion in deionized water under atmospheric pressure (25°C, 3 minutes), and dried in a forced-air low-temperature dryer (80°C, 5 minutes). <Evaluation method> The water-soluble flux residue remaining under the glass plate of the test substrate after drying was measured using the area measurement function of a digital microscope (Keyence VHX-6000), and the residue area before and after cleaning was calculated. The removal rate was calculated from the following formula, and the gap cleaning performance (water-soluble flux residue removal performance) was evaluated based on the evaluation criteria below. The results are shown in Table 1. Removal rate (%) = [(Area with water-soluble flux residue before cleaning) - (Area with water-soluble flux residue after cleaning)] / (Area with water-soluble flux residue before cleaning) × 100

[0081]

[0082] As shown in Table 1 above, the cleaning agent compositions of Examples 1 to 7 showed superior removal of water-soluble flux residue in vacuum cleaning compared to Comparative Examples 1 to 4.

[0083] By using the cleaning agent composition of this disclosure in vacuum cleaning, water-soluble flux residue can be efficiently removed. For example, this makes it possible to shorten the cleaning process for water-soluble flux residue in the manufacturing process of semiconductor devices and improve the performance and reliability of the manufactured semiconductor devices, thereby improving the productivity of semiconductor devices.

[0084] 1: Glass epoxy substrate, 2: Glass substrate, 3: Spacer, 4: Water-soluble flux residue model, 10: Test piece, 11: Washing tank, 12: Washing solution, 13: Vacuum pump line

Claims

A water-soluble flux residue removal cleaning agent composition for use in vacuum cleaning of objects to be cleaned that have water-soluble flux residue, It contains the following ingredients A, B, and C: The mass ratio A / C of component A to component C is 0.01 or more and 0.05 or less. A water-soluble flux residue removal cleaning agent composition having a mass ratio A / B of component A to component B of 0.8 or more and 5 or less. Component A: An organic solvent having a water-octanol partition coefficient (LogP value) of 1.3 or higher, and being at least one selected from the compounds represented by the following formula (I) and the compounds represented by the following formula (II). R 1 -O-(AO) n -R 2 (I) In the above formula (I), R 1 R is a phenyl group, a benzyl group, or an alkyl group having 6 to 9 carbon atoms. 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethylene oxy group or a propylene oxy group, and n is the number of moles of AO added, which is an integer between 1 and 3. ( 3 ________________________________ In the above formula (II), R 3 This is a phenyl group, a benzyl group, a cyclohexyl group, or an alkyl group having 5 to 10 carbon atoms. Component B: Amine compound Component C: water The water-soluble flux residue removal cleaning agent composition according to claim 1, wherein component A is at least one of benzyl alcohol and ethylene glycol monophenyl ether. The water-soluble flux residue removal cleaning agent composition according to claim 1 or 2, wherein component B is a compound represented by the following formula (IV). In the above formula (IV), R 8 represents a hydrogen atom, an alkyl group, a phenyl group, a benzyl group, a hydroxyethyl group, a hydroxypropyl group, or an aminoethyl group, and R 9 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, or an alkyl group, and R 10 represents a hydroxyethyl group, a hydroxypropyl group, or an alkyl group. 　 A water-soluble flux residue removal cleaning agent composition according to any one of claims 1 to 3, wherein component B is at least one of N-methylethanolamine and N-butyldiethanolamine. 　 A water-soluble flux residue removal cleaning agent composition according to any one of claims 1 to 4, wherein the mass ratio B / C of component B to component C is 0.001 or more and 0.1 or less. 　 A water-soluble flux residue removal cleaning agent composition according to any one of claims 1 to 5, wherein the content of component A is 0.5% by mass or more and 5% by mass or less. 　 A water-soluble flux residue removal cleaning agent composition according to any one of claims 1 to 6, wherein the content of component B is 0.01% by mass or more and 10% by mass or less. A water-soluble flux residue removal cleaning agent composition according to any one of claims 1 to 7, wherein the content of component C is 85% by mass or more and 99.4% by mass or less. 　 The water-soluble flux residue removal cleaning agent composition according to any one of claims 1 to 8, wherein the total content of component A, component B, and component C is 90% by mass or more. A method for removing water-soluble flux residue from an object to be cleaned that has water-soluble flux residue, The process includes a cleaning step of cleaning an object having water-soluble flux residue under reduced pressure using a water-soluble flux residue removal cleaning agent composition, The aforementioned water-soluble flux residue removal cleaning agent composition comprises the following components A, B, and C: The mass ratio A / C of component A to component C is 0.01 or more and 0.05 or less. A method for removing water-soluble flux residue, wherein the mass ratio A / B of component A to component B is 0.8 or more and 5 or less. Component A: An organic solvent having a water-octanol partition coefficient (LogP value) of 1.3 or higher, An organic solvent, at least one selected from the compounds represented by formula (I) and the compounds represented by formula (II) below. R 1 -O-(AO) n -R 2 (I) In the above formula (I), R 1 R is a phenyl group, a benzyl group, or an alkyl group having 6 to 9 carbon atoms. 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethylene oxy group or a propylene oxy group, and n is the number of moles of AO added, which is an integer between 1 and 3. ( 3 ________________________________ In the above formula (II), R 3 This is a phenyl group, a benzyl group, a cyclohexyl group, or an alkyl group having 5 to 10 carbon atoms. Component B: Amine compound Component C: water The method for removing water-soluble flux residue according to claim 10, wherein the object to be cleaned has water-soluble flux residue in the gaps between components connected via solder, and the distance between the components is 5 μm or more and 500 μm or less. 　 The method for removing water-soluble flux residue according to claim 10 or 11, wherein the washing step includes reducing the pressure in a washing tank in which the object to be washed is immersed in the water-soluble flux residue removal washing agent composition until the pressure becomes P1 (kPa). However, P1 satisfies the relation P1 ≤ 30 (kPa). 　 A method for manufacturing an electronic component, comprising a flux cleaning step using the water-soluble flux residue removal method described in any one of claims 10 to 12.

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