Cleaning composition for removing flux residue

Abstract

To provide, in one aspect, a detergent composition for flux residue removal with an excellent flux residue removal property, while suppressing metal corrosion and damage to organic films.SOLUTION: The present disclosure, in one embodiment, relates to a detergent composition for flux residue removal comprising a compound (component A) represented by the following formula (I), a benzotriazole derivative (component B), and an imidazole derivative or a pyrazole derivative (component C). R1-O-(AO)n-R2 (I) In the formula (I), R1 is a phenyl group or an alkyl group having 1 or more and 8 or less carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms, and AO is an ethylene oxide group (EO) or a propylene oxide group (PO), and n is an additional mole number of AO and is an integer of 1 or more and 3 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a cleaning composition for removing flux residue, a cleaning method using the cleaning composition, and a method for producing electronic components. [Background technology]

[0002] 2. Description of the Related Art Metals such as copper and copper alloys are used for electrodes forming circuits on electronic substrates such as semiconductor packages in order to reduce manufacturing costs.

[0003] Surface mounting, which has improved mounting density, is widely used as a mounting method for printed wiring boards. To improve mounting density, a technology is known in which a nanometal paste is applied between the wiring on the board and the terminals of the electronic element, and the nanometal is melted and solidified by heating to bond the wiring on the board and the terminals of the electronic element. For example, Patent Document 1 discloses a semiconductor element fixed on a substrate by bonding via a die attach material made of a paste composition containing specific silver fine particles, specific silver powder, and a silicon-containing triazine compound, and further containing as a sintering aid a carboxylic acid compound that is an acid anhydride having a boiling point of 100 to 300° C. Paragraph 0051 of the same document discloses that if the boiling point of the carboxylic acid compound exceeds 300° C., it is not preferable because it will not volatilize during sintering and flux components (organic substances such as organic acids) will remain in the film.

[0004] Meanwhile, there is known a technique for cleaning solder flux from electronic components after soldering. For example, Patent Document 2 proposes a cleaning method for cleaning an object having flux residue by using a cleaning agent composition containing an organic solvent and a compound having an alkyl group having 1 to 4 carbon atoms on a nitrogen atom of an imidazole ring or a piperazine ring. Patent Document 3 proposes a processing liquid for semiconductor devices that contains water, an organic solvent, and two or more kinds of nitrogen-containing aromatic heterocyclic compounds. Patent Document 4 proposes a cleaning agent composition for tin-containing alloy parts, which contains an organic carboxylate, a nitrogen-based heterocyclic compound, and an organic solvent as active ingredients. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2020-35721 A [Patent Document 2] International Publication No. 2020 / 116534 [Patent Document 3] International Publication No. 2019 / 044463 [Patent Document 4] JP 2005-41989 A Summary of the Invention [Problem to be solved by the invention]

[0006] When applying a nanometal paste containing acid (flux component) and melting and solidifying the nanometal by heating to bond between the wiring on the substrate and the terminals of the electronic element, a process of holding the substrate at a high temperature of 200°C or higher (sintering process) is required to melt the metal. If flux residue, mainly composed of acid, remains on the substrate after this sintering process, it must be cleaned, so the cleaning agent composition is required to have high cleaning properties for flux residue (flux residue removal properties). In addition, an organic film (surface protection film) may be formed on the surface of a substrate or a metal component using a water-soluble preflux. When sintering and flux removal are performed partially on the same substrate surface, or when metal components are present on both sides of the same substrate, the cleaning composition may come into contact with the organic film. In order to prevent the organic film from being removed during flux residue cleaning, the cleaning composition is required to cause little damage to the organic film. Furthermore, since corrosion of metals used in the substrate surface or metal components leads to a decrease in the quality and value of the package substrate, the cleaning composition is also required to have a high metal corrosion prevention ability (corrosion prevention property).

[0007] In view of this, the present disclosure provides a cleaning composition for removing flux residue that is excellent in flux residue removability while suppressing metal corrosion and damage to organic coatings, and a cleaning method thereof. [Means for solving the problem]

[0008] In one aspect, the present disclosure relates to a cleaning composition for removing flux residue, comprising a compound represented by the following formula (I) (component A), a benzotriazole derivative (component B), and an imidazole derivative or a pyrazole derivative (component C): R 1 -O-(AO) n -R 2 (I) In the above formula (I), R 1 is a phenyl group or an alkyl group having 1 to 8 carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethylene oxide group (EO) or a propylene oxide group (PO), and n is the number of moles of AO added and is an integer of 1 to 3.

[0009] In one aspect, the present disclosure relates to a cleaning method including a cleaning step of cleaning an object having flux residue with the cleaning agent composition of the present disclosure. Effect of the Invention

[0010] The present disclosure can provide a cleaning composition for removing flux residue and a cleaning method that are excellent in flux residue removability while suppressing metal corrosion and damage to an organic coating. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present inventors have discovered that by using a combination of a compound represented by the above formula (I) (component A), a benzotriazole derivative (component B), and an imidazole derivative or a pyrazole derivative (component C), flux residue can be efficiently removed while suppressing metal corrosion and damage to organic coatings.

[0012] That is, in one aspect, the present disclosure relates to a cleaning composition for removing flux residue (hereinafter also referred to as the "cleaning composition of the present disclosure") that contains a compound represented by the above formula (I) (component A), a benzotriazole derivative (component B), and an imidazole derivative or a pyrazole derivative (component C).

[0013] The present disclosure provides a cleaning composition for removing flux residue that is excellent in flux residue removability while suppressing metal corrosion and damage to organic coatings.

[0014] Although the details of the mechanism by which the effects of the present disclosure are expressed are still unclear, it is speculated as follows. Component B (benzotriazole derivative) and component C (imidazole derivative or pyrazole derivative), which are nitrogen-containing aromatic heterocyclic compounds, can be coordinated to metals via nitrogen atoms. It is believed that copper ions are generated by dissolving the organic coating with component A (a compound represented by formula (I)), and the generated copper ions react with components B and C to reform the organic coating. It is presumed that the presence of two types of components B and C at this time results in the formation of a dense organic coating with significantly superior corrosion prevention properties compared to the case in which each component exists alone. As a result, it is believed that the flux residue removal properties are excellent while suppressing metal corrosion and damage to the organic coating. However, the present disclosure need not be construed as being limited to this mechanism.

[0015] In one or more embodiments, the "flux" in the present disclosure refers to a flux used to bond two members together by a sintering process (e.g., a process of maintaining at a high temperature of 200°C or higher), and is used, for example, to bond a heat sink to a semiconductor element or to bond a heat sink to a substrate. In one or more embodiments, the flux is a bonding aid containing an acid as a main component. In one or more embodiments, the "cleaning composition for removing flux residue" in the present disclosure refers to a cleaning composition for removing flux residue remaining after two members are joined by a sintering step.

[0016] [Component A: Compound represented by formula (I)] The cleaning composition of the present disclosure contains a compound represented by the following formula (I) (hereinafter also referred to as "Component A"). Component A may be one type or a combination of two or more types. R 1 -O-(AO) n -R 2 (I)

[0017] In the above formula (I), R 1 is a phenyl group or an alkyl group having 1 to 8 carbon atoms, and R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethylene oxide group (EO) or a propylene oxide group (PO), and n is the number of moles of AO added and is an integer of 1 to 3. In the above formula (I), R 1 From the viewpoint of improving the removability of flux residue, R is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 4 to 6 carbon atoms. 2 From the same viewpoint, is preferably a hydrogen atom or an alkyl group having 2 to 4 carbon atoms, and more preferably a hydrogen atom. From the same viewpoint, AO is preferably an ethylene oxide group (EO). From the same viewpoint, n is preferably 2 or 3, and more preferably 2.

[0018] Examples of component A include monophenyl ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether; monoalkyl ethers having an alkyl group having from 1 to 8 carbon atoms, such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, and tripropylene glycol monoalkyl ether; dialkyl ethers having an alkyl group having from 1 to 8 carbon atoms and an alkyl group having from 1 to 4 carbon atoms, such as ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, and triethylene glycol dialkyl ether; phenyl alkyl ethers having a phenyl group and an alkyl group having from 1 to 4 carbon atoms, such as ethylene glycol phenyl alkyl ether, diethylene glycol phenyl alkyl ether, and triethylene glycol phenyl alkyl ether; and the like. Among these, from the viewpoints of improving the removability of flux residue, inhibiting metal corrosion, and inhibiting damage to the organic coating, Component A is preferably at least one selected from diethylene glycol monoalkyl ethers and dipropylene glycol monoalkyl ethers, and examples thereof include at least one selected from diethylene glycol monobutyl ether (butyl diglycol, BDG), dipropylene glycol monobutyl ether (BFDG), and diethylene glycol monohexyl ether (hexyl diglycol).

[0019] The content of component A when using the cleaning composition of the present disclosure is preferably 35% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more from the viewpoint of improving flux residue removability, and is preferably 99.5% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less from the viewpoint of suppressing metal corrosion and damage to organic coatings. More specifically, the content of component A when using the cleaning composition of the present disclosure is preferably 35% by mass or more and 99.5% by mass or less, more preferably 50% by mass or more and 95% by mass or less, and even more preferably 75% by mass or more and 90% by mass or less from the viewpoint of improving flux residue removability, suppressing metal corrosion and suppressing damage to organic coatings. When component A is a combination of two or more kinds, the content of component A refers to the total content thereof.

[0020] [Component B: Benzotriazole derivative] The cleaning composition of the present disclosure contains a benzotriazole derivative (hereinafter, also referred to as "component B"). Examples of component B include a compound represented by the following formula (II) or a compound represented by the following formula (III). From the viewpoints of improving flux residue removability, inhibiting metal corrosion, and inhibiting damage to organic coatings, the compound represented by formula (III) is preferred. Component B may be one type or a combination of two or more types.

[0021] <Compound represented by formula (II)> [ka]

[0022] In the above formula (II), R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, a carboxy group, an amino group, or a nitro group. In the above formula (II), R 3 From the viewpoints of inhibiting metal corrosion and inhibiting damage to the organic coating, R is preferably a hydrogen atom. 4From the same viewpoint, is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0023] Examples of the compound represented by the above formula (II) include benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, and tolyltriazole (a mixture of 4-methylbenzotriazole and 5-methylbenzotriazole).

[0024] <Compound represented by formula (III)> [ka]

[0025] In the above formula (III), R 5 and R 6 are each independently an alkyl group having 1 to 8 carbon atoms; R 7 represents a hydrogen atom or a methyl group. In the above formula (III), R 5 and R 6 From the viewpoints of inhibiting metal corrosion and inhibiting damage to the organic coating, R is preferably an alkyl group having 6 to 8 carbon atoms, and more preferably an alkyl group having 8 carbon atoms. 7 From the same viewpoint, is preferably a hydrogen atom.

[0026] Examples of the compound represented by the above formula (III) include 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (BT-LX), 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole (TT-LX), and the like.

[0027] The content of component B when using the cleaning composition of the present disclosure is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, from the viewpoint of suppressing metal corrosion and suppressing damage to organic coatings, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, from the viewpoint of solubility in component A. More specifically, the content of component B when using the cleaning composition of the present disclosure is preferably 0.05% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and even more preferably 0.3% by mass or more and 1% 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 thereof.

[0028] The mass ratio A / B of component A to component B (content of A / content of B) in the cleaning composition of the present disclosure is preferably 50 or more, preferably 100 or more, preferably 150 or more, or may be 200 or more, from the viewpoints of improving flux residue removability and solubility in component A. Furthermore, from the viewpoints of inhibiting metal corrosion and inhibiting damage to an organic coating, it is preferably 1000 or less, preferably 500 or less, preferably 300 or less, or may be 250 or less. More specifically, the mass ratio A / B is preferably 50 or more and 1000 or less, more preferably 100 or more and 500 or less, and even more preferably 150 or more and 300 or less.

[0029] [Component C: Imidazole derivative or pyrazole derivative] The cleaning composition of the present disclosure contains an imidazole derivative or a pyrazole derivative (hereinafter, also referred to as "component C"). Component C may be one type or a combination of two or more types.

[0030] <Imidazole derivatives> The imidazole derivative includes, for example, a compound represented by the following formula (IV). [ka]

[0031] In the above formula (IV), R 8 , R 9, R 10 and R 11 are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, or a phenyl group; R 10 and R 11 may form a benzene ring together with the carbon atoms a and b. In the above formula (IV), R 8 , R 9 , R 10 and R 11 are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or a methyl group, from the viewpoints of improving flux residue removability, inhibiting metal corrosion, and inhibiting damage to the organic coating.

[0032] Examples of the compound represented by the following formula (IV) include imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-isopropylimidazole, 1-acetylimidazole, 1-aminopropylimidazole, 1-hydroxyethylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2-acetyl ... At least one selected from the group consisting of imidazole, 2-aminopropylimidazole, 2-hydroxyethylimidazole, 4-methylimidazole, 4-ethylimidazole, 4-propylimidazole, 4-isopropylimidazole, 4-acetylimidazole, 4-aminopropylimidazole, 4-hydroxyethylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 2-ethyl-4-methylimidazole and benzimidazole can be mentioned. Among these, the compound represented by the following formula (IV) is preferably at least one selected from imidazole, 1-methylimidazole, 2-methylimidazole, and benzimidazole, more preferably imidazole and 2-methylimidazole, and even more preferably 2-methylimidazole, from the viewpoints of improving flux residue removability, inhibiting metal corrosion, and inhibiting damage to the organic coating.

[0033] <Pyrazole derivatives> An example of the pyrazole derivative is a compound represented by the following formula (V). [ka]

[0034] In the above formula (V), R 12 , R 13 , R 14 and R 15 are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, or a phenyl group; R 14 and R 15 may be bonded to each other to form a ring. In the above formula (V), R 12 , R 13 , R 14 and R 15 is preferably a hydrogen atom from the viewpoints of improving the removability of flux residue, inhibiting metal corrosion, and inhibiting damage to the organic coating.

[0035] Examples of the compound represented by the following formula (V) include pyrazole and 3,5-dimethylpyrazole.

[0036] The content of component C when using the cleaning composition of the present disclosure is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, from the viewpoint of suppressing metal corrosion and suppressing damage to organic coatings, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, from the viewpoint of solubility in component A. More specifically, the content of component C when using the cleaning composition of the present disclosure is preferably 0.05% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and even more preferably 0.3% by mass or more and 1% by mass or less. When component C is a combination of two or more types, the content of component C refers to the total content thereof.

[0037] In the cleaning composition of the present disclosure, the mass ratio B / C of component B to component C (content of B / content of C) is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 0.5 or more, from the viewpoints of inhibiting metal corrosion and inhibiting damage to an organic coating, and from the same viewpoints, is preferably 100 or less, more preferably 10 or less, and even more preferably 5 or less. More specifically, the mass ratio B / C is preferably 0.01 or more and 100 or less, more preferably 0.1 or more and 10 or less, and even more preferably 0.5 or more and 5 or less.

[0038] In the cleaning composition of the present disclosure, the mass ratio A / C of components A and C (content of component A / content of component C) is preferably 20 or more, preferably 50 or more, and preferably 70 or more from the viewpoints of improving flux residue removability and solubility in component A, and is preferably 500 or less, preferably 300 or less, and preferably 200 or less from the viewpoints of metal corrosion and damage to organic coatings. More specifically, the mass ratio A / C is preferably 20 or more and 500 or less, more preferably 50 or more and 300 or less, and even more preferably 70 or more and 200 or less.

[0039] The total content of components A, B, and C in the cleaning composition of the present disclosure is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 85% by mass or more, from the viewpoint of improving flux residue removability. Also, from the viewpoint of lowering the flash point, it is preferably 100% by mass or less, more preferably 95% by mass or less, and more preferably 90% by mass or less. More specifically, the total content of components A, B, and C is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 95% by mass or less, even more preferably 80% by mass or more and 90% by mass or less, and even more preferably 85% by mass or more and 90% by mass or less.

[0040] [Component D: Water] In one or more embodiments, the cleaning agent composition of the present disclosure may further contain water (hereinafter also referred to as "component D"). Examples of component D include ion-exchanged water, RO water (water treated with a reverse osmosis membrane), distilled water, pure water, and ultrapure water. When the cleaning composition of the present disclosure contains Component D, the content of Component D during use of the cleaning composition of the present disclosure is preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 8 mass% or more from the viewpoint of lowering the flash point, and is preferably 15 mass% or less, more preferably 14 mass% or less, and even more preferably 13 mass% or less from the viewpoint of improving flux residue removability. More specifically, the content of Component D in the cleaning composition of the present disclosure is preferably 1 mass% or more and 15 mass% or less, more preferably 5 mass% or more and 14 mass% or less, and even more preferably 8 mass% or more and 13 mass% or less.

[0041] [Other ingredients] The cleaning agent composition of the present disclosure may contain, as necessary, an appropriate amount of a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), which is typically used in cleaning agents, a rust inhibitor, a thickener, a dispersant, a solvent other than component A, a basic substance (e.g., dibutylaminoethanol, diisopropanolamine, etc.), a pH adjuster, a polymer compound, a surfactant, a solubilizing agent, a preservative, a germicide, an antibacterial agent, an antifoaming agent, an antioxidant, or an organic carboxylate (e.g., stannous octoate, etc.), within a range that does not impair the effects of the present disclosure. The content of other components in the cleaning composition of the present disclosure is preferably from 0 to 10% by mass, more preferably from 0 to 8% by mass, and even more preferably from 0 to 6% by mass.

[0042] [Method of producing the cleaning composition] The cleaning composition of the present disclosure can be produced, for example, by blending component A, component B, component C, and optional components (component D and other components) as needed by a known method. In one or more embodiments, the cleaning composition of the present disclosure can be produced by blending at least component A, component B, and component C. Thus, in one aspect, the present disclosure relates to a method for producing a cleaning composition, comprising a step of blending at least component A, component B, and component C. In the present disclosure, "blending" includes mixing component A, component B, component C, and optional components (component D and other components) as needed simultaneously or in any order. In the method for producing the cleaning composition of the present disclosure, the blended amount of each component can be the same as the content of each component when the cleaning composition of the present disclosure is used as described above. In the present disclosure, "the content of each component in the cleaning composition at the time of use" refers to the content of each component at the time of cleaning, i.e., at the time when the use of the cleaning composition for cleaning is started.

[0043] In one or more embodiments, the cleaning composition of the present disclosure is used for cleaning an object having flux residue, particularly an object having flux residue remaining after joining two members by a sintering process. In one or more embodiments, the cleaning composition of the present disclosure can be used as a cleaning agent for removing flux residue from an object to be cleaned having flux residue. Thus, in one aspect, the present disclosure relates to use of a cleaning composition containing Component A, Component B, and Component C (i.e., the cleaning composition of the present disclosure) as a flux residue cleaning agent. In one or more other embodiments, the cleaning composition of the present disclosure can be used as a remover for removing flux residue from an object to be cleaned having flux residue. Thus, in another aspect, the present disclosure relates to a flux residue cleaning remover composition comprising the cleaning composition of the present disclosure (hereinafter also referred to as the "flux residue cleaning remover composition of the present disclosure"). In another aspect, the present disclosure relates to use of the cleaning composition of the present disclosure or the flux residue cleaning remover composition of the present disclosure as a flux residue remover.

[0044] [Item to be cleaned] In one or more embodiments, the object to be cleaned may be a substrate having flux residue that has been subjected to a step of heating to 200° C. or higher, and in one or more embodiments, the object may have a copper-containing metal member on the substrate having flux residue that has been subjected to the step of heating to 200° C. or higher. In one or more embodiments, the step of heating to 200° C. or higher is a step of maintaining the substrate at a high temperature of 200° C. or higher (sintering step). In one or more embodiments, the object to be cleaned may be an object to be cleaned having flux residue. In one or more embodiments, the object to be cleaned having flux residue may be a substrate having flux residue, which has undergone a step of heating to 200°C or higher (sintering step) after applying a flux-containing slurry between a substrate and a metal member or between two metal members on a substrate. Thus, in one aspect, the present disclosure relates to the use of the cleaning agent composition of the present disclosure in cleaning a substrate having flux residue, which has undergone a step of heating to 200°C or higher (sintering step) after applying a flux-containing slurry between a substrate and a metal member or between two metal members on a substrate. In the sintering step, the heating temperature is, for example, 200° C. to 350° C. The heating time is, for example, 3 minutes to 5 hours. From the viewpoint of exerting cleaning properties against thermal denaturation of the flux, the object to be cleaned is preferably heated for 1 hour or more. In one or a plurality of embodiments, the substrate surface and / or metal member of the object to be cleaned includes a portion where the metal has been discolored by heating, that is, a portion where the metal has been oxidized (metal oxide). In one or more embodiments, the substrate surface and / or metal member of the object to be cleaned includes an organic coating containing an imidazole derivative. In one or more embodiments, the substrate surface and / or metal member of the object to be cleaned includes an organic coating contacted with an agent containing an imidazole derivative. In one or more embodiments, the organic coating is a surface protective film for protecting the substrate surface and / or metal member. In one or more embodiments, the organic coating is formed by a water-soluble preflux (OSP, Organic Solderability Preservative) treatment. In one or more embodiments, a method for forming the organic coating includes a method of immersing the substrate surface and / or the metal member surface in a water-soluble preflux. The immersion temperature is, for example, 30° C. to 50° C., and the immersion time is, for example, 30 seconds to 90 seconds. The thickness of the organic coating is, for example, 0.1 μm to 0.3 μm. In one or more embodiments, the water-soluble preflux is an aqueous solution mainly composed of an imidazole derivative. In one or more embodiments, the OSP treatment is a Cu-OSP treatment. In one or more embodiments, the object to be cleaned is a substrate having flux residue, which has been subjected to a process of applying a slurry containing flux between a substrate and a metal member or between two metal members on a substrate and then heating to 200°C or higher (sintering process), and which includes an organic coating containing an imidazole derivative. In one or more embodiments, the flux contains an acid as a main component, for example, an organic acid such as abietic acid. In one or more embodiments, the flux-containing slurry may further contain metal particles. The metal particles are preferably metal particles having a sintering temperature (curing temperature) of 300° C. or less, and examples thereof include tin, copper, silver, or a mixture of these metals. In one or more embodiments, the metal particles serve as a bonding material capable of bonding between a substrate and a metal member or between two metal members on a substrate. In one or more embodiments, the flux-containing slurry can be used as a die attachment paste. When the flux-containing slurry further contains metal particles, the slurry can be used as a conductive die attachment paste in one or more embodiments. In one or a plurality of embodiments, the metal member is fixed onto a substrate. In one or more embodiments, the metal of the metal member includes copper, iron, etc. Examples of the metal member include a heat sink, an electric circuit, etc. In one or a plurality of embodiments, the substrate may be a substrate having a metal surface, such as a copper plate, a steel plate, a stainless steel plate, a tough pitch copper plate, or a copper wiring printed circuit board. In one or more embodiments, the substrate surface and / or the metal member of the object to be cleaned contains copper.

[0045] [Cleaning method] In one aspect, the present disclosure relates to a cleaning method (hereinafter also referred to as the "cleaning method of the present disclosure") including a cleaning step of cleaning an object having flux residue with the cleaning composition of the present disclosure. The object to be cleaned may be any of the above-mentioned objects. In one or more embodiments, the cleaning step includes contacting the object to be cleaned having flux residue with the cleaning composition of the present disclosure. According to the cleaning method of the present disclosure, the flux residue can be efficiently removed while suppressing metal corrosion and damage to an organic coating. Examples of a method for cleaning an object to be cleaned with the cleaning composition of the present disclosure, or a method for bringing the cleaning composition of the present disclosure into contact with an object to be cleaned, include a method for contacting the object in a bathtub of an ultrasonic cleaning device, a method for contacting the object by ejecting the cleaning composition in a spray form (shower method), etc. In one or more embodiments, the cleaning composition of the present disclosure can be used for cleaning as it is without dilution. In one or more embodiments, the cleaning step is a step of immersing the object to be cleaned in the cleaning composition of the present disclosure. From the viewpoints of improving flux residue removability, inhibiting metal corrosion, and inhibiting damage to an organic coating, the immersion temperature is preferably 80° C. or lower, more preferably 70° C. or lower, and even more preferably 60° C. or lower, and is preferably 20° C. or higher, more preferably 30° C. or higher, and even more preferably 40° C. or higher. For example, in one or more embodiments, the cleaning step is preferably a step of immersing the object to be cleaned in the cleaning composition of the present disclosure at 80° C. or lower. From the same viewpoint, the immersion time is preferably 5 minutes or longer, more preferably 10 minutes or longer, and even more preferably 30 minutes or longer, and is preferably 3 hours or shorter, more preferably 2 hours or shorter, and even more preferably 1 hour or shorter. In one or more embodiments, the cleaning method of the present disclosure preferably includes a step of contacting the object to be cleaned with the cleaning composition, rinsing the object with water and / or an alcohol such as methanol, and drying the object. In the cleaning method of the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning composition of the present disclosure comes into contact with the object to be cleaned, and it is more preferable that the ultrasonic waves are relatively strong, from the viewpoint that the cleaning power of the cleaning composition of the present disclosure is easily exhibited. From the same viewpoint, the frequency of the ultrasonic waves is preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

[0046] In one or more other embodiments, the cleaning step in the cleaning method of the present disclosure is a step (removal step) of cleaning and removing flux residue from an object to be cleaned with a flux residue remover. Examples of the flux residue remover in the removal step include the flux residue cleaning remover composition of the present disclosure described above. That is, in one or more embodiments, the cleaning method of the present disclosure is a method for cleaning and removing flux residue, which includes a step of cleaning and removing flux residue from an object to be cleaned with the deflux remover composition of the present disclosure, and the object to be cleaned is a substrate having flux residue that has been subjected to a step of heating to 200° C. or higher (sintering step).

[0047] [Electronic component manufacturing method] In one aspect, the present disclosure relates to a method for manufacturing an electronic component using the cleaning method of the present disclosure (hereinafter also referred to as the "method for manufacturing an electronic component of the present disclosure"). In one or more embodiments, the method for producing electronic devices according to the present disclosure includes a step of applying a flux-containing slurry between a substrate and a metal member or between two metal members on a substrate, followed by heating to 200° C. or higher (sintering step), and a step of cleaning the substrate (object to be cleaned) having flux residue after the sintering step, with the cleaning composition of the present disclosure or the cleaning method of the present disclosure (cleaning step). In one or more embodiments, the cleaning step includes contacting an object to be cleaned having flux residue with the cleaning composition of the present disclosure. The cleaning method in the cleaning step may be the same as the cleaning method of the present disclosure described above. The object to be cleaned may be the object to be cleaned described above. EXAMPLES

[0048] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples in any way.

[0049] 1. Preparation of cleaning compositions (Examples 1 to 18, Comparative Examples 1 to 9) The components were blended in a 100 mL glass beaker to give the compositions shown in Tables 1 and 2 below, and mixed under the conditions described below to prepare the cleaning compositions of Examples 1 to 18 and Comparative Examples 1 to 9. Unless otherwise specified, the numerical value of each component in the tables indicates the content (mass%) of the prepared cleaning composition. <Mixing conditions> Liquid temperature: 25℃ Stirrer: Magnetic stirrer (50mm rotor) Rotation speed: 300 rpm Stirring time: 10 minutes

[0050] The following components are used in the cleaning composition: (Component A) Diethylene glycol monobutyl ether [manufactured by Nippon Nyukazai Co., Ltd.] Dipropylene glycol monobutyl ether [manufactured by Nippon Nyukazai Co., Ltd.] Diethylene glycol monohexyl ether [manufactured by Nippon Nyukazai Co., Ltd.] (Non-ingredient A) Benzyl alcohol [LANXESS KK] (Component B) Benzotriazole [Tokyo Chemical Industry Co., Ltd.] 5-Methylbenzotriazole [Tokyo Chemical Industry Co., Ltd.] BT-LX [N,N-bis(2-ethylhexyl)(1H-benzotriazol-1-yl)methylamine, manufactured by Johoku Chemical Industry Co., Ltd.] (Component C) 2-Methylimidazole [Tokyo Chemical Industry Co., Ltd.] 1-Methylimidazole [Tokyo Chemical Industry Co., Ltd.] Imidazole [FUJIFILM Wako Pure Chemical Industries, Ltd.] Benzimidazole [Tokyo Chemical Industry Co., Ltd.] Pyrazole [Tokyo Chemical Industry Co., Ltd.] (Non-ingredient C) 1,2,3-Triazole [Tokyo Chemical Industry Co., Ltd.] Tetrazole [Tokyo Chemical Industry Co., Ltd.] (Component D) Water [Pure water of 1μS / cm or less produced using the Organo Corporation pure water system G-10DSTSET] (Other Ingredients) Dibutylaminoethanol [Nippon Nyukazai Co., Ltd.] (basic substance) Diisopropanolamine [Nippon Nyukazai Co., Ltd.] (basic substance) 1-Hydroxyethylidene-1,1-diphosphonic acid [Italmatch Japan Co., Ltd., Dequest 2010] (chelating agent) Stannous octylate (stannous octanoate) [Tokyo Chemical Industry Co., Ltd.] (organic carboxylate metal salt)

[0051] 2. Evaluation of cleaning agent compositions The cleaning compositions prepared in Examples 1 to 18 and Comparative Examples 1 to 9 were used to carry out the following tests to evaluate damage to organic coatings, metal corrosion ability (corrosion prevention), and flux residue removability.

[0052] [Test substrate 1 (evaluation of damage to organic coating and corrosion resistance)] A test substrate 1 used for evaluating damage to an organic coating and corrosion resistance was prepared as follows. <Pre-flux treatment of substrate (formation of organic coating)> The test substrate was subjected to a pre-flux treatment (Cu-OSP treatment) in the following steps and under the following conditions. [Test board] A tough pitch copper plate (50 mm×20 mm) was used as the test substrate. [Preflux treatment] The preflux treatment was carried out according to a procedure including the following steps (a) to (d). (a) Degreasing process The test substrate was immersed in a degreasing liquid (manufactured by Shikoku Chemical Industry Co., Ltd., product name: Tough Cleaner W40G) at 20 to 30° C. for 30 seconds, and then the substrate was taken out and washed with water for 1 minute. (b) Soft etching process The above substrate was immersed in a soft etching solution (manufactured by Shikoku Chemical Industry Co., Ltd., trade name: Tough Cleaner GB-1400, sulfuric acid-hydrogen peroxide type) at 30° C. for 30 seconds, and then the substrate was taken out and washed with water for 1 minute. (c) Acid washing process The above substrate was immersed in an acid cleaning solution (aqueous 5% sulfuric acid solution) at 20 to 30° C. for 30 seconds, then taken out and washed with water for 1 minute, after which the water was removed from the substrate using an air knife. (d) Preflux treatment process The above substrate was immersed in metal treatment agent A (water-soluble preflux, manufactured by Shikoku Chemical Industry Co., Ltd., product name: Tough Ace F2 (LX) PK) containing an imidazole compound at 40°C for 30 to 90 seconds, and then the substrate was taken out and washed with water for 1 minute. Next, the substrate was drained with an air knife and dried at 100°C for 1 minute. A test substrate 1 was produced by forming an organic coating (OSP film) with a thickness of about 0.1 to 0.3 μm on the copper surface.

[0053] [Test board 2 (evaluation of cleaning ability)] Using a stencil mask, flux (manufactured by Senju Metal Industry Co., Ltd., product name: Deltalux M B-T100) was printed to a thickness of 100 μm on a copper wiring printed circuit board (10 mm x 15 mm), and 300 μm solder balls with a composition of Sn-3Ag-0.5Cu (all values ​​are mass %) were placed on the flux printed areas. Test board 2 was produced by using a reflow furnace to reflow for 30 seconds at a heating rate of 2.5°C / sec and a peak temperature of 250°C (oxygen concentration of 100 ppm). The test substrate 2 produced here is a model that simulates the joining of metals on a substrate from the heating temperature and holding time. The sintering conditions assumed were a heating temperature of 250°C and a heating time of 4 minutes (this heating time includes the holding time at 250°C (30 seconds), the temperature rise time, and the cooling time).

[0054] [Cleaning test] The cleaning test was carried out according to the following procedure. First, an ultrasonic cleaning tank, a first rinsing tank, and a second rinsing tank are prepared under the following conditions. The frequency of the ultrasonic cleaning tank was set to 40 kHz, and the output was set to 400 W. 100 g of each cleaning composition was added to a 500 mL glass beaker, which was then placed in an ultrasonic cleaning tank and heated to 60°C. The first and second rinsing tanks were prepared by preparing two 100 mL glass beakers each containing a 50 mm rotor, adding 100 g of pure water to each, placing them in a warm bath, and heating them to 40°C while stirring at a rotation speed of 100 rpm. Next, the test substrate is held with tweezers and inserted into the ultrasonic cleaning tank, and immersed at 60° C. for 5 minutes (ultrasonic cleaning, 40 kHz, 400 W). Next, the test substrate is held with tweezers and inserted into the first rinsing tank, and is immersed for 1 minute at 40° C. while being stirred at a rotation speed of 100 rpm (water rinsing). Furthermore, the test substrate is held with tweezers and inserted into a second rinsing tank, and is immersed for 1 minute at 40° C. while being stirred at a rotation speed of 100 rpm (water rinsing). Finally, the test substrate is dried with a nitrogen purge.

[0055] [Evaluation of damage to organic coatings] After the above cleaning test, the contact angle of water on the surface of the test substrate 1 was measured by a drop method. Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DMo-501), the value was read 20 seconds after the droplet was created, and the water contact angle X was calculated as the average of five points. Test substrate 1 was washed in the same manner using an aqueous sulfuric acid solution adjusted to pH 1, and the water contact angle Y on the copper plate was calculated separately. The survival of the organic coating was evaluated by subtracting Y from X. The results are shown in Tables 1 and 2. It can be evaluated that the larger the XY value, the more the organic coating survives and the more damage to the organic coating is suppressed.

[0056] [Table 1]

[0057] [Table 2]

[0058] As shown in Tables 1 and 2 above, the cleaning compositions of Examples 1 to 18 caused less damage to the organic coating than the cleaning compositions of Comparative Examples 1 to 9.

[0059] [Corrosion prevention evaluation] After the organic coating was evaluated, the test substrate 1 was observed using an optical microscope (VHX-2000, manufactured by Keyence Corporation). The test substrate 1 was placed in a thermohygrostat (PR-1J, manufactured by Espec Corporation) and left to stand for 24 hours under conditions of a temperature of 85°C and a relative humidity of 85%rh, after which the test substrate 1 was removed. The test substrate 1 was visually observed using the optical microscope VHX-2000, and the appearance was compared before and after storage under constant temperature and humidity conditions, and the corrosion resistance was evaluated according to the following criteria. The results are shown in Tables 1 and 2. <Judgment criteria> A: There is no color unevenness or discoloration. B: No color unevenness, no discoloration. C: Discoloration is observed, with some areas turning brown. D: The whole area is browned. The cleaning composition of Example 1, which contained components B and C, was superior in inhibiting discoloration of copper (anticorrosion properties) compared to Comparative Examples 3 and 5, which did not contain components B or C (Example 1: A, Comparative Examples 3 and 5: D). The cleaning composition, which had a large XY value in the evaluation of the water contact angle after cleaning and was capable of leaving an organic coating, was superior in anticorrosion properties, and Examples 2 to 18 also showed excellent anticorrosion properties.

[0060] [Evaluation of cleaning ability (flux residue removal)] After the above cleaning test, the test substrate 2 was observed using an optical microscope (Keyence Corporation, VHX-2000), and the areas of the flux residue before and after cleaning were determined using an attached area calculation mode based on color identification, to calculate the flux residue cleaning rate. The cleaning composition of Example 1 containing Component A had a 100% flux residue cleaning rate (complete cleaning) and was excellent in flux residue removal. Examples 2 to 18 containing Component A also showed excellent flux residue removal. [Industrial Applicability]

[0061] The cleaning composition of the present disclosure can efficiently remove flux residue while suppressing metal corrosion and damage to organic coatings. This makes it possible, for example, to shorten the flux cleaning step in the semiconductor device manufacturing process and improve the performance and reliability of the manufactured semiconductor device, thereby improving the productivity of semiconductor devices.

Claims

1. The composition comprises a compound represented by the following formula (I) (component A), a benzotriazole derivative (component B), and an imidazole derivative or a pyrazole derivative (component C), A cleaning composition for removing flux residue, comprising a component B content of 0.05 mass % or more and 5 mass % or less. R 1 -O-(AO) n -R 2 (I) In the above formula (I), R 1 is a phenyl group or an alkyl group having 1 to 8 carbon atoms; R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO represents an ethylene oxide group (EO) or a propylene oxide group (PO), and n represents the number of moles of AO added and is an integer of 1 to 3.

2. The cleaning composition according to claim 1, wherein the content of component A is 35% by mass or more and 99.5% by mass or less.

3. 2. The cleaning composition according to claim 1, wherein a mass ratio B / C of component B to component C is 0.01 or more and 100 or less.

4. 2. The cleaning composition according to claim 1, wherein a mass ratio B / C of component B to component C is 0.01 or more and 10 or less.

5. 10. The cleaning composition of claim 1, further comprising water (component D).

6. The cleaning composition according to claim 5, wherein the content of component D is 15 mass% or less.

7. A cleaning method comprising a cleaning step of cleaning an object having flux residue with the cleaning agent composition according to claim 1.

8. 8. The cleaning method according to claim 7, wherein the object to be cleaned having flux residue is a substrate having flux residue that has been subjected to a process of applying a flux-containing slurry between a substrate and a metal member or between two metal members on a substrate, and then heating the applied slurry to 200° C. or higher.

9. The object to be cleaned has a metal component on a substrate having flux residue, which has been subjected to a process of heating to 200°C or higher; 8. The cleaning method according to claim 7, wherein the substrate surface and / or the metal member of the object to be cleaned contains an organic coating containing an imidazole derivative.

10. The object to be cleaned has a metal component on a substrate having flux residue, which has been subjected to a process of heating to 200°C or higher; 8. The cleaning method according to claim 7, wherein the substrate surface and / or the metal member of the object to be cleaned includes an organic coating in contact with an agent containing an imidazole derivative.

11. The cleaning method according to claim 7 , wherein the cleaning step is a step of immersing the object to be cleaned in the cleaning agent composition for removing flux residue at a temperature of 80° C. or less.

12. The object to be cleaned has a metal component on a substrate having flux residue, which has been subjected to a process of heating to 200°C or higher; The cleaning method according to claim 7 , wherein the substrate surface and / or the metal member of the object to be cleaned contains copper.

13. A method for manufacturing electronic parts, using the cleaning method according to any one of claims 7 to 12.

14. A composition comprising a compound (component A) represented by the following formula (I), a benzotriazole derivative (component B), and an imidazole derivative or a pyrazole derivative (component C), A cleaning composition for removing flux residue, wherein a mass ratio B / C of component B to component C is 0.01 or more and 100 or less. R 1 -O-(AO) n -R 2 (I) In the above formula (I), R 1 is a phenyl group or an alkyl group having 1 to 8 carbon atoms, R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethylene oxide group (EO) or a propylene oxide group (PO), and n is the number of moles of AO added and is an integer of 1 to 3.

15. A cleaning composition as described in claim 14, wherein the content of component B is 0.05 mass% or more and 5 mass% or less.

16. A cleaning method comprising a cleaning step of cleaning an object having flux residue with the cleaning composition described in claim 14.

17. The cleaning method described in claim 16, wherein the object to be cleaned having flux residue is a substrate having flux residue that has undergone a process of applying a flux-containing slurry between a substrate and a metal member or between two metal members on a substrate, and then heating to 200°C or higher.

18. The object to be cleaned has a metal component on a substrate having flux residue, which has been subjected to a process of heating to 200°C or higher; The cleaning method according to claim 16, wherein the substrate surface and / or the metal member of the object to be cleaned contains copper.

19. A method for manufacturing electronic components using a cleaning method described in any one of claims 16 to 18.

Images