Cleaning agent composition for removing flux residue

Abstract

The present disclosure provides, in one embodiment, a cleaning agent composition for removing flux residues, which has excellent removability for both a metal that has been discolored after heat treatment at 200°C or higher and flux residues. The present disclosure relates, in one embodiment, to a cleaning agent composition for removing flux residues, which comprises at least one organic solvent (component A) selected from a compound represented by the following formula (I) and a compound represented by the following formula (II), an imidazole compound (component B) represented by the following formula (III), a carboxylic acid (component C), and water (component D). 1 -O-(AO) n -R 2 (I) R 3 -CH2OH (II)

Description

Technical Field

[0001] This disclosure relates to a cleaning composition for removing flux residues and a cleaning method using the cleaning composition. Background Technology

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

[0003] Surface mounting, which increases mounting density, is widely used as a mounting method for printed circuit boards. To further increase mounting density, a known technique involves applying a nano-metal paste between wiring on the substrate and terminals of electronic components, then heating the nano-metal to melt and solidify it, thereby bonding the wiring on the substrate to the terminals of the electronic components.

[0004] On the other hand, there are known techniques for cleaning the solder flux from soldered electronic components.

[0005] For example, in International Publication No. 2020 / 116524 (Patent Document 1), a cleaning agent composition for removing flux residue was proposed, which includes a solvent, an amine with a polarity term δp of Hansen solubility parameter of 7.8 or less, and a specific diphosphonic acid.

[0006] International Publication No. 2020 / 116534 (Patent Document 2) discloses a cleaning method that includes the step of cleaning an object with flux residue using a cleaning agent composition, wherein the cleaning agent composition contains an organic solvent and a compound having an alkyl group having 1 or more and 4 or fewer carbon atoms in the nitrogen atom of the imidazole ring or piperazine ring.

[0007] Japanese Patent Application Publication No. 7-179893 (Patent Document 3) discloses a cleaning agent composition containing N-methyl-2-pyrrolidone comprising 0 to 30% by weight of water, and one or more compounds selected from phosphine, phenol, imidazolidinone, imidazolium or fluorene compounds.

[0008] Japanese Patent Application Publication No. 2015-203047 (Patent Document 4) disclosed a substrate cleaning solution for semiconductor devices. This solution has a pH of 8 or higher and is used to clean semiconductor device substrates that have Cu wiring and a low dielectric constant insulating film on their surface and have undergone chemical mechanical polishing. The solution comprises tetramethylammonium hydroxide, a diamine selected from ethylenediamine and 1,2-diaminopropane, an organic acid selected from oxalic acid, citric acid, tartaric acid, malic acid and pyridinecarboxylic acid, histidine or its derivatives, at least one selected from benzotriazole, imidazole, triazole, tetraazole and its derivatives, and water.

[0009] Japanese Patent Application Publication No. 2023-14099 (Patent Document 5) discloses a cleaning composition comprising about 0.5 to 20% by weight of hydroxylamine, about 0.01 to 1% by weight of a chelating agent containing at least two nitrogen-containing groups, alkylene glycol, and water, wherein the pH of the composition is about 7.5 to 11, and the composition is designed to remove residues from a semiconductor substrate comprising an interconnect structure containing cobalt.

[0010] Japanese Patent Application Publication No. 2021-102773 (Patent Document 6) disclosed a cleaning composition comprising hydroxylamine, alkanolamine, alkylene glycol and water, with a pH of 7 or higher and 11 or lower. Summary of the Invention

[0011] This disclosure relates, in one aspect, to a cleaning composition for removing flux residue, comprising at least one organic solvent (component A) selected from compounds represented by formula (I) and compounds represented by formula (II), an imidazole compound represented by formula (III) (component B), a carboxylic acid (component C), and water (component D).

[0012] R 1 -O- (AO) n -R 2 (I)

[0013] In the above equation (I), R 1 It is a phenyl group or an alkyl group having 1 or more but less than 8 carbon atoms, R 2 It is a hydrogen atom or an alkyl group with 1 or more carbon atoms and less than 4 carbon atoms. AO is ethylene oxide or propylene oxide. n is the number of moles of AO added, which is an integer of 1 or more and less than 3.

[0014] R 3 -CH2OH (II)

[0015] In equation (II) above, R 3 It can be phenyl, benzyl, cyclohexyl, furanyl, tetrahydrofuranyl, furfuryl, or tetrahydrofuryl.

[0016] [Chemistry 1]

[0017]

[0018] In equation (III), R 4 R 5 R 6 and R 7 Each can independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a phenyl group, an aldehyde group, a carboxyl group, an aminoethyl group, an aminopropyl group, an acetyl group, a hydroxyethyl group, or a hydroxypropyl group.

[0019] In one aspect, this disclosure relates to a cleaning method comprising a cleaning step of cleaning an object having flux residues with a cleaning agent composition of the present disclosure for cleaning with flux residue removal, wherein the object being cleaned is a substrate that has undergone a process of heating to above 200°C. Detailed Implementation

[0020] When applying a nano-metal paste containing acid (flux component) and bonding the wiring on the substrate to the terminals of electronic components by heating to melt and solidify the nano-metal, a process is required to hold the substrate at a high temperature above 200°C in order to melt the metal. If flux residue, mainly composed of acid, remains on the substrate after this process, it needs to be cleaned.

[0021] Furthermore, depending on the type of metal on the substrate surface and the metal components, surface oxidation and discoloration may sometimes occur due to being kept at high temperatures above 200°C. Therefore, there is a need for a cleaning agent composition that can remove the discolored portions caused by heat treatment at temperatures above 200°C, i.e., the oxidized metal (metal oxides).

[0022] Therefore, this disclosure provides a cleaning agent composition and cleaning method for removing flux residues that have excellent removal properties for both discolored metals after heat treatment at temperatures above 200°C and flux residues.

[0023] The inventors have observed that by using at least one organic solvent (component A) selected from compounds represented by formula (I) and formula (II), an imidazole compound (component B) represented by formula (III), a carboxylic acid (component C), and water (component D), the removal of both discolored metal (metal oxide) and flux residue after heat treatment at 200°C or higher can be improved. Furthermore, it has been observed that using a carboxylic acid with 8 or more carbon atoms as component C reduces damage to other components of the apparatus (e.g., iron components such as cleaning tanks, cleaning pipes, and nozzles), components mounted on the substrate (e.g., iron components such as cover plates).

[0024] That is, in one aspect, this disclosure relates to a flux residue removal cleaning composition (hereinafter also referred to as "the cleaning composition of this disclosure") for removing flux residue remaining after two components are joined together in a sintering process, comprising at least one organic solvent (component A) selected from compounds represented by formula (I) and compounds represented by formula (II), an imidazole compound represented by formula (III) (component B), a carboxylic acid (component C), and water (component D).

[0025] According to this disclosure, a cleaning agent composition for removing flux residue can be provided, which exhibits excellent removal properties for both discolored metal (metal oxides) and flux residue after heat treatment at temperatures above 200°C. Furthermore, this disclosure provides, in one or more embodiments, a cleaning agent composition for removing flux residue that can further reduce damage to other components such as iron components.

[0026] There are still some unclear details regarding the mechanism of action by which the effects of this disclosure are manifested; however, it can be speculated as follows.

[0027] In the cleaning agent composition disclosed herein, a specific imidazole compound (component B) adsorbs onto discolored metals (e.g., metal oxides such as copper oxide) to form imidazole compound metal complexes (e.g., imidazole compound copper complexes). These complexes have low affinity for common organic solvents, hindering diffusion from the surface of metal oxides such as copper oxides and preventing removal. However, in this disclosure, a specific organic solvent (component A) solvates the imidazole compound copper complexes, forming clusters with high affinity. As a result, diffusion into the specific organic solvent (component A) is advanced. Based on this effect, the dissolution reaction of the metal oxides is advanced, thereby achieving the removal of metal oxides such as copper oxides. Furthermore, regarding flux residue removal, it is believed that the solubility of the flux residue is improved through the neutralization reaction between the rosin acid contained in the flux residue and the imidazole compound.

[0028] Furthermore, it can be considered that the cleaning agent composition disclosed herein, due to the presence of carboxylic acid (component C), becomes a carboxylic acid-imidazole compound complex, exhibiting greater solvent versatility and faster diffusion, thus promoting the removal of metal oxides. Additionally, it can be considered that when using carboxylic acids with 8 or more carbon atoms, selective adsorption to metal species occurs, thereby demonstrating a reduction in damage to other components.

[0029] Furthermore, it can be considered that, in this disclosure, by using a specific organic solvent (component A) in the presence of a specific imidazole compound (component B) and a carboxylic acid (component C), the solubility of flux residues is further enhanced, enabling effective cleaning (removal) of flux residues.

[0030] Based on the above, it can be concluded that the cleaning agent composition disclosed herein exhibits good flux residue removal and discolored metal (metal oxide) removal properties. Furthermore, it can be concluded that it can reduce damage to other components such as apparatus parts (e.g., iron components such as cleaning tanks, cleaning pipes, nozzles), components mounted on the substrate (e.g., iron components such as cover plates).

[0031] However, this disclosure may also be interpreted in ways that are not limited to this mechanism.

[0032] The term "flux" in this disclosure, in one or more embodiments, refers to a flux used to join two components together via a sintering process (e.g., a process held at a high temperature above 200°C), such as for joining a heat sink to a semiconductor element, or for joining a heat sink to a substrate. In one or more embodiments, the flux is a bonding agent with acid as its main component.

[0033] The term "flux residue" in this disclosure refers to flux-derived residue remaining in a substrate after solder bumps have been formed using flux, and / or on a substrate after soldering using flux. For example, if other components (e.g., semiconductor chips, chip capacitors, other circuit boards, etc.) are stacked and mounted on a circuit board, a space (gap) will be formed between the circuit board and the other components. The flux used for mounting these components may remain in this gap as flux residue after being soldered by reflow or the like.

[0034] The "cleaning composition for removing flux residue" disclosed herein refers to a cleaning composition for removing flux residue remaining after two components are joined together in a sintering process.

[0035] [Component A: Organic solvent]

[0036] The cleaning composition disclosed herein may contain one or a combination of two or more organic solvents selected from compounds represented by formula (I) and compounds represented by formula (II) below (hereinafter also referred to as "component A").

[0037] <Compounds represented by formula (I)>

[0038] R 1 -O- (AO) n -R 2 (I)

[0039] In the above equation (I), R 1 The alkyl group is phenyl or has 1 or more but less than 8 carbon atoms. From the viewpoint of improving the removal of flux residue, phenyl or alkyl group with 4 or more but less than 6 carbon atoms is preferred, and alkyl group with 4 or more but less than 6 carbon atoms is more preferred.

[0040] R 2 The component is a hydrogen atom or an alkyl group having 1 or more but less than 4 carbon atoms. From the viewpoint of ease of rinsing, a hydrogen atom is preferred. From the viewpoint of improving the removal of flux residues, an alkyl group having 2 or more but less than 4 carbon atoms is preferred, and n-butyl is more preferred.

[0041] AO is oxyvinyl (EO) or oxypropylene (PO), and from the same point of view, oxyvinyl is preferred.

[0042] n is the number of moles added to AO, representing an integer greater than 1 and less than 3. From the same point of view, it is preferably 1 or 2, and more preferably 2.

[0043] Examples of compounds represented by formula (I) include monophenyl glycol ethers such as ethylene glycol monophenyl ether (PHG-S, 2-phenoxyethanol), diethylene glycol monophenyl ether, and propylene glycol monophenyl ether; monobenzyl glycol ethers such as ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, and propylene glycol monobenzyl ether; monoalkyl ethers such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and triethylene glycol monoalkyl ether having an alkyl group with 1 or more but less than 8 carbon atoms; dialkyl ethers such as ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, and triethylene glycol dialkyl ether having an alkyl group with 1 or more but less than 8 carbon atoms and an alkyl group with 1 or more but less than 4 carbon atoms; phenylalkyl ethers such as ethylene glycol phenylalkyl ether, diethylene glycol phenylalkyl ether, and triethylene glycol phenylalkyl ether having a phenyl group and an alkyl group with 1 or more but less than 4 carbon atoms; etc. Among them, as compounds represented by the above formula (I), from the viewpoint of improving flux residue removal, at least one of ethylene glycol monophenyl ether (PHG-S), diethylene glycol monobutyl ether (BDG), dipropylene glycol monobutyl ether (BFDG), diethylene glycol dibutyl ether (DBDG) and diethylene glycol diethyl ether is preferred, and diethylene glycol monobutyl ether (BDG) is even more preferred.

[0044] <Compounds represented by formula (II)>

[0045] R 3 -CH2OH (II)

[0046] In equation (II) above, R 3 The solvent is phenyl, benzyl, cyclohexyl, furanyl, tetrahydrofuranyl, furfuryl, or tetrahydrofuranyl. From the viewpoint of improving flux residue removal, phenyl, cyclohexyl, or tetrahydrofuranyl is preferred, and phenyl or tetrahydrofuranyl is more preferred.

[0047] Examples of compounds represented by formula (II) include at least one selected from benzyl alcohol, phenylethanol, cyclohexane-methanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol. From the viewpoint of improving flux residue removal, compounds represented by formula (II) are preferably selected from at least one selected from benzyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol, and more preferably from at least one selected from benzyl alcohol (BzOH) and tetrahydrofurfuryl alcohol.

[0048] Regarding the content of component A in the cleaning agent composition of this disclosure, from the viewpoint of improving the removal of discolored metal, it is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably greater than 25% by mass, and even more preferably 40% by mass or more. From the viewpoint of improving the metal solubility of component B, it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. More specifically, the content of component A in the cleaning agent composition of this disclosure is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 85% by mass or less, further preferably greater than 25% by mass and 80% by mass or less, and even more preferably 40% by mass or more and 80% by mass or less. When there is a combination of two or more components A, the content of component A refers to their total content.

[0049] [Component B: Imidazole compound represented by formula (III)]

[0050] The cleaning composition disclosed herein may contain one or a combination of two or more imidazole compounds represented by the following formula (III).

[0051] [Chemistry 2]

[0052]

[0053] In equation (III) above, R 4 R 5 R 6 and R 7 Each can independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a phenyl group, an aldehyde group, a carboxyl group, an aminoethyl group, an aminopropyl group, an acetyl group, a hydroxyethyl group, or a hydroxypropyl group.

[0054] From the perspective of improving the removal of discolored metals, R in the above formula (III) 4 R 5 R 6 and R 7 Each of the following is preferred independently: hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, phenyl, aminoethyl, aminopropyl, acetyl, hydroxyethyl, or hydroxypropyl; more preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or hydroxyethyl; and even more preferably methyl or ethyl.

[0055] As component B, from the viewpoint of improving the removal of both discolored metal and flux residue, at least one of the following can be selected: imidazole, 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, 1-isopropylimidazolium, 1-acetylimidazolium, 1-aminopropylimidazolium, 1-hydroxyethylimidazolium, 2-methylimidazolium, 2-ethylimidazolium, 2-propylimidazolium, 2-isopropylimidazolium, 2-acetylimidazolium, 2-aminopropylimidazolium, 2-hydroxyethylimidazolium, 4-methylimidazolium, 4-ethylimidazolium, 4-propylimidazolium, 4-isopropylimidazolium, 4-acetylimidazolium, 4-aminopropylimidazolium, 4-hydroxyethylimidazolium, 1,2-dimethylimidazolium, 1-isobutyl-2-methylimidazolium, and 2-ethyl-4-methylimidazolium. From the same point of view, component B is preferably selected from at least one of 1-methylimidazole, 2-methylimidazole, 1-isobutyl-2-methylimidazole and 2-ethyl-4-methylimidazole.

[0056] Regarding the content of component B in the cleaning agent composition of this disclosure, from the viewpoint of improving the removal of both discolored metal and flux residue, it is preferably 0.5% by mass or more, preferably 0.75% by mass or more, more preferably 1% by mass or more, and from the same viewpoint, preferably 15% by mass or less, more preferably 10% by mass or less, more preferably 8% by mass or less. More specifically, the content of component B in the cleaning agent composition of this disclosure is preferably 0.5% by mass or more and 15% by mass or less, more preferably 0.75% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 10% by mass or less. Furthermore, more specifically, the content of component B in the cleaning agent composition of this disclosure is further preferably 0.75% by mass or more and 8% by mass or less, more preferably 1% by mass or more and 8% by mass or less. When there is a combination of two or more components B, the content of component B refers to their total content.

[0057] In the cleaning agent composition disclosed herein, regarding the mass ratio of component B to component A (B / A) (content of component B (mass%) / content of component A (mass%)), from the viewpoint of improving the removal of discolored metal, it is preferably 0.005 or more, more preferably 0.008 or more, further preferably 0.01 or more, further preferably 0.03 or more, and further preferably 0.05 or more. Moreover, from the same viewpoint, it is preferably 1.0 or less, more preferably 0.5 or less, further preferably 0.3 or less, further preferably 0.2 or less, and further preferably 0.1 or less. More specifically, the mass ratio (B / A) is preferably 0.005 or more and 1.0 or less, more preferably 0.008 or more and 0.5 or less, further preferably 0.01 or more and 0.3 or less, 0.03 or more and 0.2 or less, or 0.01 or more and 0.1 or less.

[0058] [Ingredient C: Carboxylic Acid]

[0059] The cleaning agent composition disclosed herein may contain one or more carboxylic acids (hereinafter also referred to as "component C").

[0060] Regarding the carbon number of component C, from the viewpoint of improving the removal of both discolored metal and flux residue, it is preferably 2 or more; from the viewpoint of reducing damage to other components such as iron components, it is preferably 8 or more; and from the viewpoint of improving the removal of both discolored metal and flux residue, and reducing damage to other components such as iron components, it is preferably 22 or less, more preferably 18 or less, and even more preferably 16 or less. More specifically, the carbon number of component C is preferably 2 or more and 22 or less, or 8 or more and 22 or less, more preferably 8 or more and 18 or less, and even more preferably 8 or more and 16 or less.

[0061] As component C, from the viewpoint of improving the removal of both discolored metal and flux residue, and from the viewpoint of reducing damage to other components such as iron components, a carboxylic acid with 8 or more carbon atoms is preferred, for example, at least one selected from octanoic acid, capric acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid and behenic acid.

[0062] Regarding the content of component C in the cleaning agent composition of this disclosure, from the viewpoint of improving the removal of both discolored metal and flux residue, it is preferably 0.5% by mass or more, more preferably 3.5% by mass or more, and from the same viewpoint, preferably 10% by mass or less, more preferably 5% by mass or less. More specifically, the content of component C in the cleaning agent composition of this disclosure is preferably 0.5% by mass or more and 10% by mass or less, more preferably 3.5% by mass or more and 5% by mass or less. When there is a combination of two or more components C, the content of component C refers to their total content.

[0063] Regarding the mass ratio (C / A) of component C to component A in the cleaning agent composition of this disclosure (content of component C (mass%) / content of component A (mass%)), from the viewpoint of improving the removal of discolored metal, it is preferably 0.0001 or more, more preferably 0.005 or more, and even more preferably 0.01 or more. Moreover, from the same viewpoint, it is preferably 1.0 or less, more preferably 0.5 or less, even more preferably 0.1 or less, and even more preferably 0.05 or less. More specifically, the mass ratio (C / A) of component C to component A is preferably 0.0001 or more and 1.0 or less, more preferably 0.005 or more and 0.5 or less, even more preferably 0.01 or more and 0.1 or less, and even more preferably 0.01 or more and 0.05 or less.

[0064] Regarding the mass ratio (B / C) of component B to component C in the cleaning agent composition of this disclosure (content of component B (mass%) / content of component C (mass%)), from the viewpoint of improving the removal of discolored metal, it is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 0.5 or more. Moreover, from the same viewpoint, it is preferably 25 or less, more preferably 15 or less, even more preferably 5 or less, and even more preferably 2 or less. More specifically, the mass ratio (B / C) of component B to component C is preferably 0.01 or more and 25 or less, more preferably 0.1 or more and 15 or less, and even more preferably 0.5 or more and 5 or less.

[0065] [Ingredient D: Water]

[0066] Examples of water contained in the cleaning agent composition disclosed herein (hereinafter also referred to as "component D") include ion-exchanged water, RO water (reverse osmosis membrane treated water), distilled water, pure water, and ultrapure water.

[0067] Regarding the content of component D when using the cleaning agent composition of this disclosure, from the viewpoint of improving the removal of discolored metal, it is preferably 0.5% by mass or more, more preferably 5% by mass or more, and from the viewpoint of improving the removal of both discolored metal and flux residue, it is preferably 20% by mass or less, and even more preferably 10% by mass or less. More specifically, the content of component D when using the cleaning agent composition of this disclosure is preferably 0.5% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 10% by mass or less.

[0068] [Component E: An amine represented by formula (IV)]

[0069] The cleaning composition disclosed herein may further comprise an amine represented by formula (IV) (hereinafter also referred to as "component E") in one or more embodiments. Component E may be one or a combination of two or more.

[0070] [Chemistry 3]

[0071]

[0072] In equation (IV) above, 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, hydroxyethyl, hydroxypropyl, or alkyl group. 10 This refers to hydroxyethyl, hydroxypropyl, or alkyl. From the viewpoint of improving the removal of both discolored metal and flux residue, alkyl groups with 1 or more carbon atoms and 6 or fewer carbon atoms can be cited as alkyl groups.

[0073] As component E, examples include at least one alkanoylamine selected from monoethanolamine (MEA), monoisopropanolamine, N-methylmonoethanolamine, 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, and N,N-dibutylethanolamine (dibutylaminoethanol); and at least one aromatic amine selected from dimethylbenzylamine. From the viewpoint of improving the removal of both discolored metal and flux residue, component E is preferably selected from at least one of diisopropanolamine and N,N-dibutylethanolamine (dibutylaminoethanol).

[0074] When the cleaning composition of this disclosure includes component E, the content of component E when using the cleaning composition of this disclosure, from the viewpoint of improving flux residue removal, is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. Furthermore, from the same viewpoint, it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. More specifically, the content of component E when using the cleaning composition of this disclosure is preferably 0.2% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and even more preferably 1% by mass or more and 5% by mass or less. When there is a combination of two or more components E, the content of component E refers to their total content.

[0075] [Other ingredients]

[0076] The cleaning composition disclosed herein may, as needed, contain at least one selected from the following, except for component A: organic solvents, except for component B: fatty acids, except for component C: fatty acids, chelating agents, rust inhibitors, thickeners, dispersants, pH adjusters, polymers, surfactants, solubilizers, preservatives, bactericides, antibacterial agents, defoamers, and antioxidants, without impairing the effects of this disclosure.

[0077] The cleaning composition disclosed herein may substantially not contain bisphosphonic acid in one or more embodiments. For example, the content of bisphosphonic acid in the cleaning composition of this disclosure is preferably less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably 0% by mass (i.e., not contained).

[0078] [Method for manufacturing the cleaning agent composition]

[0079] The cleaning composition of this disclosure can be manufactured, for example, by combining components A, B, C, D, and optional components (component E, other components) as needed, using known methods. In one or more embodiments, the cleaning composition of this disclosure can be prepared by combining at least components A, B, C, and D. Thus, this disclosure relates in one aspect to a method of manufacturing a cleaning composition, which includes the step of combining at least components A, B, C, and D. The term "combining" in this disclosure includes mixing components A, B, C, D, and optional components (component E, other components) simultaneously or in any order.

[0080] In the method for manufacturing the cleaning agent composition disclosed herein, the amount of each component can be set to be the same as the content of each component when the cleaning agent composition disclosed herein is used.

[0081] The term "content of each component when using the cleaning agent composition" in this disclosure refers to the content of each component at the time of cleaning, that is, at the moment when the cleaning agent composition is first used in cleaning.

[0082] [pH of the cleaning agent composition]

[0083] Regarding the pH of the cleaning agent composition of this disclosure, from the viewpoint of improving the removal of both metal discoloration and flux residue, it is preferably 5 or higher, more preferably 6 or higher, and from the same viewpoint, preferably 12 or lower, more preferably 11 or lower, and even more preferably 10 or lower. More specifically, the pH of the cleaning agent composition of this disclosure is preferably 5 or higher and 12 or lower, more preferably 6 or higher and 11 or lower, and even more preferably 6 or higher and 10 or lower. As needed, the pH can be adjusted using inorganic acids such as nitric acid and sulfuric acid, organic acids such as hydroxycarboxylic acids, polycarboxylic acids, amino polycarboxylic acids, and amino acids, as well as their metal salts, ammonium salts, ammonia, sodium hydroxide, potassium hydroxide, amines, carboxylic acids (component C), etc. The pH of the cleaning agent composition in this disclosure is the pH of the cleaning agent composition at 25°C when used, and can be determined using the method described in the examples.

[0084] The cleaning composition disclosed herein is used in one or more embodiments for cleaning a workpiece having flux residue, particularly for cleaning a workpiece having flux residue remaining after two components are joined together by a sintering process.

[0085] The cleaning composition of this disclosure can be used as a cleaning agent for removing flux residues from a workpiece having flux residues in one or more embodiments. Therefore, this disclosure relates in one aspect to the use of a cleaning composition comprising components A, B, C, and D (i.e., the cleaning composition of this disclosure) as a flux residue cleaning agent.

[0086] The cleaning composition of this disclosure can be used as a flux remover in one or more other embodiments as a flux residue remover to remove flux residue from a workpiece having flux residue. Therefore, this disclosure relates in other ways to the use of the cleaning composition of this disclosure as a flux residue remover.

[0087] [Items to be cleaned]

[0088] As the object to be cleaned, in one or more embodiments, a substrate that has undergone a process of heating to 200°C or higher can be cited. In one or more embodiments, the substrate may also have a metal component containing copper. The process of heating to 200°C or higher in one or more embodiments is a process of maintaining a high temperature of 200°C or higher (sintering process).

[0089] As a cleaned object, in one or more embodiments, an object having flux residue can be cited as an example. As a cleaned object having flux residue, in one or more embodiments, a substrate having flux residue can be cited as an example of a substrate that has undergone a process of heating to 200°C or higher (sintering process) after applying a flux-containing slurry between the substrate and a metal component or between two metal components on the substrate. Therefore, this disclosure relates in one aspect to the use of the cleaning agent composition of this disclosure in cleaning a substrate having flux residue after applying a flux-containing slurry between the substrate and a metal component or between two metal components on the substrate and then heating to 200°C or higher (sintering process).

[0090] In the above sintering process, the heating temperature can be, for example, 200°C to 350°C. The heating time can be, for example, 3 minutes to 5 hours. From the viewpoint of utilizing the cleaning properties of the flux due to heat-induced denaturation, the object to be cleaned is preferably heated for more than 1 hour.

[0091] In one or more embodiments, the substrate surface and / or metal components of the object being cleaned include portions of the metal that have changed color due to heating, i.e. portions of the metal that have oxidized (metal oxides).

[0092] In one or more embodiments, the flux described above contains an acid as a main component. Examples of acids include organic acids such as rosin acid.

[0093] In one or more embodiments, the flux-containing paste may further contain metal particles. The metal particles are preferably metal particles with a sintering temperature (hardening temperature) of 300°C or lower, such as tin, copper, silver, or mixtures thereof, with copper, silver, or mixtures thereof being more preferred, and silver being even more preferred. In one or more embodiments, the metal particles serve as a bonding material capable of bonding a substrate to a metal component or between two metal components on a substrate. In one or more embodiments, the flux-containing paste can be used as a chip mounting adhesive. When the flux-containing paste further contains metal particles, the paste can be used as a conductive chip mounting adhesive in one or more embodiments.

[0094] In one or more embodiments, the aforementioned metal component is fixed to the substrate.

[0095] In one or more embodiments, the metal in the aforementioned metal component includes metals such as copper and iron. Examples of such metal components include heat sinks and circuits.

[0096] As the substrate described above, in one or more embodiments, a substrate having a metal surface can be cited, such as a copper plate, a steel plate, a stainless steel plate, etc.

[0097] The substrate surface and / or metal components of the object being cleaned contain copper in one or more embodiments.

[0098] [Cleaning Method]

[0099] This disclosure relates, in one embodiment, to a cleaning method (hereinafter also referred to as "the cleaning method of this disclosure"), comprising a cleaning step of cleaning a workpiece containing flux residue with a cleaning agent composition of this disclosure. The workpiece described above can be cited as an example. In one or more embodiments, the cleaning step includes contacting the workpiece containing flux residue with the cleaning agent composition of this disclosure. According to the cleaning method of this disclosure, both discolored metal (metal oxides) and flux residue after high-temperature treatment at 200°C or above can be efficiently removed.

[0100] The cleaning process described above, in one or more embodiments, includes using the cleaning agent composition of this disclosure to remove discolored metal. Therefore, this disclosure relates, in one aspect, to the use of the cleaning agent composition of this disclosure in the removal of discolored metal and flux residue. The discolored metal, in one or more embodiments, comprises portions of the metal that have oxidized due to heating (metal oxides).

[0101] Methods for cleaning objects with the cleaning agent composition disclosed herein, or methods for bringing the cleaning agent composition of the present disclosure into contact with the objects to be cleaned, include, for example, immersing the object in the bath of an ultrasonic cleaning apparatus, or spraying the cleaning agent composition in a spray form (spraying method). In one or more embodiments, the cleaning agent composition of the present disclosure can be used directly for cleaning without dilution.

[0102] In one or more embodiments, the above-described cleaning process involves immersing the object to be cleaned in the cleaning agent composition disclosed herein. Regarding the immersion temperature, from the viewpoint of improving the removal of both discolored metal and flux residue, it is preferably 20°C or higher, more preferably 30°C or higher, and even more preferably 40°C or higher. Furthermore, from the viewpoint of operational safety and reducing device load, it is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower. Regarding the immersion time, from the same viewpoint, it is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 30 minutes or more. Furthermore, it is preferably 3 hours or less, more preferably 2 hours or less, and even more preferably 1 hour or less.

[0103] The cleaning method disclosed herein preferably includes, in one or more embodiments, a step of rinsing and drying the object to be cleaned with water and / or an alcohol such as methanol after contacting the object with the cleaning agent composition.

[0104] In the cleaning method disclosed herein, from the viewpoint of easily exerting the cleaning power of the cleaning agent composition of the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning agent composition of the present disclosure comes into contact with the object to be cleaned, and more preferably the ultrasonic waves are relatively strong.

[0105] The cleaning step in the cleaning method of this disclosure is, in one or more other embodiments, a step (removal step) of removing flux residue from the object to be cleaned using a flux residue remover. The flux residue remover composition of this disclosure described above can be cited as an example of the flux residue cleaning and removing agent used in the removal step.

[0106] That is, the cleaning method disclosed herein is a flux residue cleaning and removal method in one or more embodiments, which includes the step of cleaning and removing flux residue from the object to be cleaned using the flux cleaning and removal agent composition disclosed herein, wherein the object to be cleaned is a substrate containing flux residue that has undergone a process of heating to above 200°C (sintering process).

[0107] [Manufacturing methods for electronic components]

[0108] This disclosure relates, in one aspect, to a method for manufacturing an electronic component (hereinafter also referred to as "the method for manufacturing an electronic component of this disclosure"), which uses the cleaning method of this disclosure.

[0109] The method for manufacturing electronic components disclosed herein includes, in one or more embodiments, a step of applying a slurry containing flux between a substrate and a metal component or between two metal components on a substrate and heating it to 200°C or higher (sintering step), and a step of cleaning the substrate (the object to be cleaned) having flux residue after the above-mentioned sintering step using the cleaning agent composition of the present disclosure or the cleaning method of the present disclosure (cleaning step).

[0110] In one or more embodiments, the cleaning process described above includes contacting the workpiece containing flux residue with the cleaning agent composition of this disclosure. As a cleaning method in the above cleaning process, methods identical to those described in this disclosure can be cited. As a workpiece to be cleaned, the aforementioned workpiece can be cited.

[0111] This disclosure further relates to one or more of the following embodiments.

[0112] <1>

[0113] A cleaning composition for removing flux residues comprises at least one organic solvent (component A) selected from compounds represented by formula (I) and compounds represented by formula (II), an imidazole compound represented by formula (III) (component B), a carboxylic acid (component C), and water (component D).

[0114] R1 -O- (AO) n -R 2 (I)

[0115] In the above equation (I), R 1 It is a phenyl group or an alkyl group having 1 or more but less than 8 carbon atoms, R 2 It is a hydrogen atom or an alkyl group with 1 or more carbon atoms and less than 4 carbon atoms. AO is ethylene oxide or propylene oxide. n is the number of moles of AO added, which is an integer of 1 or more and less than 3.

[0116] R 3 -CH2OH (II)

[0117] In equation (II) above, R 3 It can be phenyl, benzyl, cyclohexyl, furanyl, tetrahydrofuranyl, furfuryl, or tetrahydrofuryl.

[0118] [Chemistry 4]

[0119]

[0120] In equation (III), R 4 R 5 R 6 and R 7 Each can independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a phenyl group, an aldehyde group, a carboxyl group, an aminoethyl group, an aminopropyl group, an acetyl group, a hydroxyethyl group, or a hydroxypropyl group.

[0121] <2>

[0122] According to the flux residue removal cleaning agent composition described in <1>, the content of component A is 10% or more by mass and 90% or less by mass, 20% or more by mass and 85% or less by mass, 25% or more by mass and 80% or less by mass, or 40% or more by mass and 80% or less by mass.

[0123] <3>

[0124] According to the flux residue removal cleaning agent composition described in <1> or <2>, the content of component B is 0.5% by mass or more and 15% by mass or less, 0.75% by mass or more and 8% by mass or less, or 1% by mass or more and 8% by mass or less.

[0125] <4>

[0126] The flux residue removal cleaning agent composition according to any one of <1> to <3>, wherein component B is selected from at least one of imidazole, 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, 1-isopropylimidazolium, 1-acetylimidazolium, 1-aminopropylimidazolium, 1-hydroxyethylimidazolium, 2-methylimidazolium, 2-ethylimidazolium, 2-propylimidazolium, 2-isopropylimidazolium, 2-acetylimidazolium, 2-aminopropylimidazolium, 2-hydroxyethylimidazolium, 4-methylimidazolium, 4-ethylimidazolium, 4-propylimidazolium, 4-isopropylimidazolium, 4-acetylimidazolium, 4-aminopropylimidazolium, 4-hydroxyethylimidazolium, 1,2-dimethylimidazolium, 1-isobutyl-2-methylimidazolium, and 2-ethyl-4-methylimidazolium.

[0127] <5>

[0128] The flux residue removal cleaning agent composition according to any one of <1> to <4>, wherein component B is selected from at least one of 1-methylimidazole, 2-methylimidazole, 1-isobutyl-2-methylimidazole, and 2-ethyl-4-methylimidazole.

[0129] The content of component A is 20% or more by mass and 85% by mass.

[0130] <6>

[0131] The flux residue removal cleaning agent composition according to any one of <1> to <5>, wherein the content of component C is 0.5% by mass or more and 10% by mass or less, or 3.5% by mass or more and 5% by mass or less.

[0132] <7>

[0133] The flux residue removal cleaning agent composition according to any one of <1> to <6>, wherein the mass ratio (C / A) of component C to component A is 0.0001 or more and 1.0 or less, 0.005 or more and 0.5 or less, or 0.01 or more and 0.05 or less.

[0134] <8>

[0135] The flux residue removal cleaning agent composition according to any one of <1> to <7>, wherein the mass ratio (B / A) of component B to component A is 0.005 or more and 1.0 or less, 0.008 or more and 0.5 or less, 0.01 or more and 0.3 or less, or 0.03 or more and 0.2 or less.

[0136] <9>

[0137] The flux residue removal cleaning agent composition according to any one of <1> to <8>, wherein component A is selected from at least one of ethylene glycol monophenyl ether (PHG-S), diethylene glycol monobutyl ether (BDG), dipropylene glycol monobutyl ether (BFDG), diethylene glycol dibutyl ether (DBDG), and diethylene glycol diethyl ether.

[0138] Component B is selected from one or more of 1-methylimidazole, 2-methylimidazole, 1-isobutyl-2-methylimidazole, and 2-ethyl-4-methylimidazole.

[0139] The mass ratio of component B to component A (B / A) is greater than 0.005 and less than 1.0.

[0140] <10>

[0141] The 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 0.01 or more and 25 or less, 0.1 or more and 15 or less, or 0.5 or more and 5 or less.

[0142] <11>

[0143] The flux residue removal cleaning agent composition according to any one of <1> to <10>, wherein the content of component D is 0.5% or more by mass and 20% or less by mass, or 5% or more by mass and 10% or less by mass.

[0144] <12>

[0145] A cleaning agent composition for removing flux residues according to any one of <1> to <11>, wherein component C is a carboxylic acid with 8 or more carbon atoms.

[0146] <13>

[0147] A cleaning agent composition for removing flux residues according to any one of <1> to <12>, wherein component C is selected from at least one of caprylic acid, decanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid and behenic acid.

[0148] <14>

[0149] According to any one of <1> to <13>, a cleaning agent composition for removing flux residue is provided, wherein component A is selected from at least one of ethylene glycol monophenyl ether (PHG-S), diethylene glycol monobutyl ether (BDG), dipropylene glycol monobutyl ether (BFDG), diethylene glycol dibutyl ether (DBDG), and diethylene glycol diethyl ether.

[0150] Component C is selected from at least one of the following: caprylic acid, capric acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, and behenic acid.

[0151] The mass ratio (C / A) of component C to component A is greater than 0.0001 and less than 1.0.

[0152] <15>

[0153] A cleaning agent composition for removing flux residue according to any one of <1> to <14>, wherein component B is selected from one or more of 1-methylimidazole, 2-methylimidazole, 1-isobutyl-2-methylimidazole, and 2-ethyl-4-methylimidazole.

[0154] Component C is selected from at least one of the following: caprylic acid, capric acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, and behenic acid.

[0155] The mass ratio (B / C) of component B to component C is greater than 0.01 and less than 25.

[0156] <16>

[0157] A cleaning method comprising a cleaning step of cleaning an object having flux residues by cleaning with a flux residue removal cleaning agent composition described in any one of <1> to <15>, wherein the object being cleaned is a substrate that has undergone a process of being heated to 200°C or higher.

[0158] <17>

[0159] According to the cleaning method described in <16>, the object to be cleaned has a metal component containing copper on the aforementioned substrate.

[0160] <18>

[0161] According to the cleaning method described in <17>, the substrate surface and / or metal components of the object being cleaned include portions of the metal that have been oxidized.

[0162] Example

[0163] The present disclosure will now be described in detail with reference to the embodiments; however, the present disclosure is not limited to these embodiments in any way.

[0164] 1. Preparation of cleaning agent compositions (Examples 1-33, Comparative Examples 1-5)

[0165] The cleaning agent compositions of Examples 1-33 and Comparative Examples 1-5 were prepared by mixing the components according to the compositions described in Tables 1-1, 1-2 and 2 below in a 100 mL glass beaker under the following conditions. Unless otherwise specified, the values ​​of each component in the tables indicate the content (mass %) in the prepared cleaning agent composition.

[0166] <Mixed Conditions>

[0167] Liquid temperature: 60℃

[0168] Mixer: Magnetic stirrer (50mm rotor)

[0169] Speed: 300 rpm

[0170] Mixing time: 1 hour

[0171] The following substances are used as components of the cleaning agent composition.

[0172] (ingredient A)

[0173] 2-Phenoxyethanol (PHG-S) [Ethylene glycol monophenyl ether, manufactured by Tokyo Chemical Industry Co., Ltd.]

[0174] Benzyl alcohol [manufactured by LANXESS Co., Ltd.]

[0175] Butyl carbitol solvent (BDG) [diethylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd.]

[0176] DBDG [Diethylene glycol dibutyl ether, manufactured by Nippon Emulsifier Co., Ltd.]

[0177] BFDG [Dipropylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd.]

[0178] Tetrahydrofurfuryl alcohol [manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.]

[0179] (Ingredient B)

[0180] 2-Methylimidazole [Manufactured by Tokyo Chemical Industry Co., Ltd.]

[0181] 2-Ethyl-4-methylimidazol [Manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.]

[0182] 1-Methylimidazole [Manufactured by Tokyo Chemical Industry Co., Ltd.]

[0183] 1-Isobutyl-2-methylimidazolium [Manufactured by Tokyo Chemical Industry Co., Ltd.]

[0184] (Component C)

[0185] Caprylic acid [carbon number 8, Kao product]

[0186] Decanoic acid [10 carbon atoms, manufactured by Kao Corporation]

[0187] Dodecanedioic acid [C12, manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.]

[0188] Lauric acid [carbon number 12, manufactured by Kao Corporation]

[0189] Myristic acid [carbon number 14, manufactured by Fujifilm and Kazumitsu Chemical Co., Ltd.]

[0190] Palmitic acid [carbon number 16, manufactured by Fujifilm and Kazumitsu Chemical Co., Ltd.]

[0191] Oleic acid [carbon number 18, manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.]

[0192] Stearic acid [carbon number 18, manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.]

[0193] Behenic acid [carbon number 22, manufactured by Kao Corporation]

[0194] Lactic acid [carbon number 2, manufactured by Fujifilm and Koichi Chemical Co., Ltd.]

[0195] Malonic acid [carbon number 3, manufactured by Fujifilm and Koichi Chemical Co., Ltd.]

[0196] Malic acid [carbon number 4, manufactured by Fujifilm and Koichi Chemical Co., Ltd.]

[0197] (Component D)

[0198] Water [Pure water with a concentration of less than 1 μS / cm produced using ORGANO Corporation's G-10DSTSET pure water system]

[0199] (Component E)

[0200] Diisopropanolamine [Made by Mitsui Chemicals Fine Chemicals Co., Ltd.]

[0201] Dibutylaminoethanol [Manufactured by Nippon Emulsifier Co., Ltd.]

[0202] (Inorganic acid)

[0203] 2M Sulfuric Acid (17%) [Manufactured by Fujifilm and Waku Pure Chemical Industries, Ltd.] *Prepared by diluting the reagent.

[0204] 35% Hydrochloric Acid (11.3M) [Manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.]

[0205] It should be noted that the content of inorganic acids in the table also includes the water content in the sulfuric acid or hydrochloric acid aqueous solution.

[0206] [pH measurement]

[0207] The pH of the cleaning agent composition is the pH of the cleaning agent composition at 25°C, measured by immersing the electrode of a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G) in the cleaning agent composition for 3 minutes.

[0208] 2. Evaluation of the cleaning agent composition

[0209] [Evaluation of oxide film removal rate (removal of discolored metals)]

[0210] Using the cleaning agent compositions of Examples 1-33 and Comparative Examples 1-5, the oxide film removal rate (removal of discolored metal) was evaluated as follows.

[0211] Add 15g of each cleaning agent composition (Examples 1-33, Comparative Examples 1-5) heated to 60°C to 0.3g of Cu2O reagent, and irradiate with ultrasound (38kHz, 600W output power) for 6 minutes. This ultrasound irradiation is a model simulating ultrasonic cleaning (cleaning time: 6 minutes) of discolored metal (Cu2O, oxide film).

[0212] Subsequently, the cleaning agent composition was filtered through a 0.45 μm filter membrane, and the amount of metal ions dissolved in the cleaning agent composition (dissolved copper ions, ppm) was determined by ICP measurement. Then, the oxide film removal rate was calculated using the following formula, and the results are shown in Tables 1-1, 1-2, and 2.

[0213] Oxide film removal rate = amount of dissolved copper ions (ppm) / cleaning time (minutes)

[0214] [Evaluation of the damage to iron components]

[0215] Using the cleaning agent compositions of Examples 1, 3, 4, 7-9, and Examples 31-33, the damage to Fe components used in the device and substrate was evaluated as follows.

[0216] Add 50g of each cleaning agent composition heated to 60°C to an SPCCB component (20mm×50mm, steel plate as specified in JIS G 3141) and store it in a 60°C constant temperature bath for 1 week. This is a model of the potential damage to the device and the components used in the substrate (in this case, Fe components).

[0217] The cleaning agent composition was collected and stored for one week, filtered through a 5 μm filter membrane, and the amount of dissolved metal ions (dissolved iron ions, ppm) was determined by ICP measurement. The results are shown in Tables 1-1 and 2. It should be noted that comparative examples 1-5 were not evaluated for damage due to their slow cleaning speed.

[0218] [Evaluation of flux residue removal]

[0219] The following cleaning tests were performed using the test substrates described below, and the flux residue removal performance was evaluated.

[0220] <Test substrate>

[0221] A test substrate was prepared by coating 0.05g of rosin acid (flux) onto a 50mm×20mm toughened copper plate and heating it at 250℃ for 1 hour using a hot plate. The rosin acid was a portion of the copper plate surface.

[0222] The test substrate produced here is a model that simulates bonding the metals on the substrate to each other by controlling the heating temperature and holding time. The envisioned substrate has flux residue after a sintering process.

[0223] <Cleaning Test>

[0224] The test substrate was immersed in 100g of each cleaning agent composition heated to 60°C and cleaned for 15 minutes using ultrasound at 38kHz and 400W output power. Afterward, the test substrate was pulled out of the cleaning agent composition, rinsed with water, and dried by a blower to obtain the cleaned substrate.

[0225] <Fluoride Residue Removal Rate>

[0226] Observe the appearance of the substrate before and after cleaning, and calculate the flux residue removal rate using the following formula.

[0227] Flux residue removal rate (%) = Area with flux residue removed after cleaning / Area with flux residue before cleaning × 100

[0228] The area with flux residue removed after cleaning = (area with flux residue before cleaning) - (area with flux residue after cleaning)

[0229] Examples 1-33 and Comparative Examples 1-5 all showed flux residue removal rates close to 100%. Therefore, the cleaning agent compositions of Examples 1-33 and Comparative Examples 1-5 can be evaluated as having excellent flux residue removal properties.

[0230] [Table 1-1]

[0231]

[0232] [Table 1-2]

[0233]

[0234] [Table 2]

[0235]

[0236] As shown in Tables 1-1, 1-2, and 2 above, the cleaning agent compositions of Examples 1-33 exhibit superior removal properties of discolored metal (oxide film) compared to Comparative Examples 1-5. It should be noted that Examples 1-33 and Comparative Examples 1-5 all demonstrate excellent flux residue removal properties.

[0237] Furthermore, it is known that the cleaning agent compositions of Examples 1, 3, 4, 7-9, which use carboxylic acids with 8 or more carbon atoms as component C, cause less damage to iron components compared to Examples 31-33, which use carboxylic acids with 2 to 4 carbon atoms as component C. The cleaning agent compositions of Examples 2, 5, and 6 can also be considered to cause less damage to iron components.

[0238] Industrial availability

[0239] By using the cleaning agent composition disclosed herein, both discolored metal and flux residue can be removed efficiently. Therefore, for example, it is possible to shorten the flux cleaning process in the manufacturing process of semiconductor devices and improve the performance and reliability of the manufactured semiconductor devices, thereby increasing the productivity of semiconductor devices.

Claims

1. A cleaning agent composition for removing flux residue, comprising: At least one organic solvent selected from compounds represented by formula (I) and compounds represented by formula (II) below, i.e., component A, The imidazole compound represented by the following formula (III), i.e., component B, Carboxylic acid, i.e. component C, and Water, i.e., component D; R 1 -O-(AO) n -R 2 (I) In the above equation (I), R 1 It is a phenyl group or an alkyl group having 1 or more but less than 8 carbon atoms, R 2 It is a hydrogen atom or an alkyl group with 1 or more carbon atoms and less than 4 carbon atoms. AO is ethylene oxide or propylene oxide. n is the number of moles of AO added, which is an integer of 1 or more and less than 3. R 3 -CH2OH (II) In equation (II) above, R 3 It can be phenyl, benzyl, cyclohexyl, furanyl, tetrahydrofuranyl, furfuryl, or tetrahydrofuryl; In equation (III), R 4 R 5 R 6 and R 7 Each can independently represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a phenyl group, an aldehyde group, a carboxyl group, an aminoethyl group, an aminopropyl group, an acetyl group, a hydroxyethyl group, or a hydroxypropyl group.

2. The cleaning agent composition for removing flux residue according to claim 1, wherein, The content of component A is 10% by mass or more and 90% by mass or less.

3. The cleaning agent composition for removing flux residue according to claim 1 or 2, wherein, The content of component B is 0.5% by mass or more and 15% by mass or less.

4. The cleaning composition for removing flux residue according to any one of claims 1 to 3, wherein, Component B is selected from at least one of imidazole, 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, 1-isopropylimidazolium, 1-acetylimidazolium, 1-aminopropylimidazolium, 1-hydroxyethylimidazolium, 2-methylimidazolium, 2-ethylimidazolium, 2-propylimidazolium, 2-isopropylimidazolium, 2-acetylimidazolium, 2-aminopropylimidazolium, 2-hydroxyethylimidazolium, 4-methylimidazolium, 4-ethylimidazolium, 4-propylimidazolium, 4-isopropylimidazolium, 4-acetylimidazolium, 4-aminopropylimidazolium, 4-hydroxyethylimidazolium, 1,2-dimethylimidazolium, 1-isobutyl-2-methylimidazolium, and 2-ethyl-4-methylimidazolium.

5. The cleaning composition for removing flux residue according to any one of claims 1 to 4, wherein, The content of component C is 0.5% by mass or more and 10% by mass or less.

6. The cleaning composition for removing flux residue according to any one of claims 1 to 5, wherein, The mass ratio of component C to component A, i.e., C / A, is greater than 0.0001.

7. The cleaning composition for removing flux residue according to any one of claims 1 to 6, wherein, The mass ratio of component B to component A, i.e., B / A, is greater than 0.005 and less than 1.

0.

8. The cleaning composition for removing flux residue according to any one of claims 1 to 7, wherein, The mass ratio of component B to component C, i.e., B / C, is greater than 0.01 and less than 25.

9. The cleaning composition for removing flux residue according to any one of claims 1 to 8, wherein, The content of component D is 0.5% or more by mass and less than 20% by mass.

10. The cleaning composition for removing flux residue according to any one of claims 1 to 9, wherein, Component C is a carboxylic acid with 8 or more carbon atoms.

11. A cleaning method comprising a cleaning step of cleaning an object having flux residue with a cleaning agent composition according to any one of claims 1 to 10, wherein the object being cleaned is a substrate that has undergone a process of heating to 200°C or higher.

12. The cleaning method according to claim 11, wherein, The object being cleaned has a copper-containing metal component on the substrate.

13. The cleaning method according to claim 12, wherein, The substrate surface and / or metal components of the object being cleaned contain portions of the metal that have undergone oxidation.

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