Cleaning agent composition for removing flux residue

Abstract

In one embodiment of the present invention, provided is a cleaning agent composition for removing flux residue, the composition exhibiting excellent flux residue removal properties while suppressing metal corrosion and damage to organic coating films.　One embodiment of the present disclosure relates to a cleaning agent composition for removing flux residue, the composition containing a compound represented by formula (I) (component A), a benzotriazole derivative (component B), and an imidazole derivative or a pyrazole derivative (component C).　Formula (I): R1-O-(AO)n-R2. In formula (I), R1 is a phenyl group or an alkyl group having 1-8 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1-4 carbon atoms, AO is ethylene oxide group (EO) or propylene oxide group (PO), and n is the number of added moles of AO, and is an integer between 1 and 3.

Description

Cleaning composition for removing flux residue

[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.

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

[0003] Surface mounting, which improves mounting density, is widely adopted as a mounting method for printed wiring boards. To improve mounting density, a known technique involves applying a nanometal paste between the wiring on a substrate and the terminals of an electronic element, melting and solidifying the nanometal by heating, and bonding the wiring on the substrate and the terminals of the electronic element. For example, Japanese Patent Laid-Open Publication No. 2020-35721 (Patent Document 1) discloses a semiconductor element fixed to a substrate by bonding it 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 a carboxylic acid compound, which is an acid anhydride with a boiling point of 100 to 300°C, as a sintering aid. Paragraph 0051 of the same document discloses that if the boiling point of the carboxylic acid compound exceeds 300°C, it is undesirable because it will not volatilize during sintering and flux components (organic substances such as organic acids) will remain in the film.

[0004] Meanwhile, techniques for cleaning solder flux from electronic components after soldering are known. For example, International Publication No. 2020 / 116534 (Patent Document 2) proposes a cleaning method for cleaning an object having flux residue using a cleaning 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. International Publication No. 2019 / 044463 (Patent Document 3) proposes a semiconductor device treatment solution containing water, an organic solvent, and two or more nitrogen-containing aromatic heterocyclic compounds. Japanese Patent Laid-Open Publication No. 2005-41989 (Patent Document 4) proposes a cleaning composition for tin-containing alloy parts containing an organic carboxylate, a nitrogen-based heterocyclic compound, and an organic solvent as active ingredients.

[0005] In one aspect, the present disclosure relates to a cleaning composition for removing flux residue, which 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): 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.

[0006] 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 composition of the present disclosure.

[0007] When applying a nanometal paste containing an acid (flux component) and then heating to melt and solidify the nanometal to bond the wiring on the substrate to the terminals of the electronic device, a sintering process is required in which the substrate is held at a high temperature of 200°C or higher to melt the metal. If acid-based flux residue remains on the substrate after the sintering process, it must be cleaned. Therefore, the cleaning composition must have high cleaning ability against flux residue (flux residue removal ability). Furthermore, an organic coating (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 coating. To prevent the organic coating from being removed during flux residue cleaning, the cleaning composition must minimize damage to the organic coating. Furthermore, because corrosion of the metal used on the substrate surface or metal component reduces the quality and value of the package substrate, the cleaning composition must also have high metal corrosion prevention ability (corrosion prevention).

[0008] Therefore, the present disclosure provides a cleaning composition for removing flux residue that has excellent flux residue removability while suppressing metal corrosion and damage to organic coatings, and a cleaning method.

[0009] The present disclosure can provide a cleaning composition for removing flux residue and a cleaning method that are excellent in flux residue removal ability while suppressing metal corrosion and damage to organic coatings.

[0010] The present inventors have discovered that by using 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) in combination, flux residue can be efficiently removed while suppressing metal corrosion and damage to organic coatings.

[0011] 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"), which comprises a compound represented by formula (I) above (component A), a benzotriazole derivative (component B), and an imidazole derivative or a pyrazole derivative (component C).

[0012] Although the details of the mechanism of action by which the effects of the present disclosure are realized are unclear, it is speculated as follows. Component B (a benzotriazole derivative) and Component C (an imidazole derivative or a pyrazole derivative), which are nitrogen-containing aromatic heterocyclic compounds, are capable of coordinating with metals via nitrogen atoms. It is believed that copper ions are generated by dissolution of the organic coating by Component A (a compound represented by Formula (I)), and the generated copper ions react with Component B and Component C to reform the organic coating. It is speculated that the presence of both Component B and Component C results in the formation of a dense organic coating with significantly superior corrosion resistance compared to when either component is present alone. As a result, it is believed that the present disclosure exhibits excellent flux residue removal properties while suppressing metal corrosion and damage to the organic coating. However, the present disclosure need not be interpreted as being limited to this mechanism.

[0013] In one or more embodiments, the term "flux" in the present disclosure refers to a flux used to bond two members together by a sintering step (e.g., a step of maintaining 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 its main component. In one or more embodiments, the term "cleaning composition for removing flux residue" in the present disclosure refers to a cleaning composition for removing flux residue remaining after two members are bonded together by a sintering step.

[0014] [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)

[0015] 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, which 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, 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.

[0016] 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 flux residue removability, 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).

[0017] The content of Component A during use of 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 during use of 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, 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 types, the content of Component A refers to the total content of those components.

[0018] [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 suppressing damage to organic coatings, the compound represented by formula (III) is preferred. Component B may be used alone or in combination of two or more types.

[0019] <Compound represented by formula (II)>

[0020] In the above formula (II), R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 8 carbon atoms, a carboxy group, an amino group, or a nitro group. 3 R is preferably a hydrogen atom from the viewpoint of inhibiting metal corrosion and inhibiting damage to the organic coating. 4 From 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.

[0021] Examples of the compound represented by the formula (II) include benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, and tolyltriazole (a mixture of 4-methylbenzotriazole and 5-methylbenzotriazole).

[0022] <Compound represented by formula (III)>

[0023] In the above formula (III), R 5 and R 6 are each independently an alkyl group having 1 to 8 carbon atoms, and R 7 represents a hydrogen atom or a methyl group. 5 and R 6 From the viewpoint 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.

[0024] Examples of the compound represented by 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.

[0025] The content of component B during use of 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 inhibiting metal corrosion and inhibiting 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 during use of 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.

[0026] 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 even 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 1,000 or less, preferably 500 or less, preferably 300 or less, or even 250 or less. More specifically, the mass ratio A / B is preferably 50 or more and 1,000 or less, more preferably 100 or more and 500 or less, and still more preferably 150 or more and 300 or less.

[0027] [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.

[0028] <Imidazole Derivatives> Examples of imidazole derivatives include compounds represented by the following formula (IV).

[0029] In the above formula (IV), R 8 , R 9 , R 10 and R 11 are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and R 10 and R 11 may form a benzene ring together with the carbon atoms a and b. 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.

[0030] The compounds 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 ... Examples of the compound represented by formula (IV) include at least one selected from 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. Among these, the compound represented by 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 suppressing damage to organic coatings.

[0031] <Pyrazole Derivative> Examples of the pyrazole derivative include compounds represented by the following formula (V).

[0032] In the above formula (V), R 12 , R 13 , R 14 and R 15 are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and R 14 and R 15 may be bonded to each other to form a ring. 12 , R 13 , R 14 and R 15is preferably a hydrogen atom from the viewpoints of improving flux residue removal, inhibiting metal corrosion, and inhibiting damage to the organic coating.

[0033] Examples of the compound represented by the following formula (V) include pyrazole and 3,5-dimethylpyrazole.

[0034] The content of component C during use of 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 inhibiting metal corrosion and inhibiting 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 during use of 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.

[0035] In the cleaning composition of the present disclosure, the mass ratio B / C of Component B to Component C (B content / C content) 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 organic coatings, 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.

[0036] In the cleaning composition of the present disclosure, the mass ratio A / C of Component A to Component C (content of Component A / content of Component C) is preferably 20 or more, preferably 50 or more, or 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, or preferably 200 or less from the viewpoints of preventing 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.

[0037] 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 even more preferably 85% by mass or more, from the viewpoint of improving flux residue removability. Furthermore, from the viewpoint of lowering the flash point, it is preferably 100% by mass or less, more preferably 95% by mass or less, and even 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.

[0038] [Component D: Water] In one or more embodiments, the cleaning 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 by 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% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more from the viewpoint of lowering the flash point, and is preferably 15% by mass or less, more preferably 14% by mass or less, and even more preferably 13% by 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% by mass or more and 15% by mass or less, more preferably 5% by mass or more and 14% by mass or less, and even more preferably 8% by mass or more and 13% by mass or less.

[0039] [Other Components] The cleaning composition of the present disclosure may contain, as needed, within the scope that does not impair the effects of the present disclosure, any of the following components typically used in cleaning agents: a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 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 bactericide, an antibacterial agent, an antifoaming agent, an antioxidant, and an organic carboxylate (e.g., stannous octoate, etc.). The content of such other components in the cleaning composition of the present disclosure is preferably 0% by mass or more and 10% by mass or less, more preferably 0% by mass or more and 8% by mass or less, and even more preferably 0% by mass or more and 6% by mass or less.

[0040] [Method for producing detergent composition] The detergent composition of the present disclosure can be produced, for example, by blending component A, component B, component C, and, as needed, optional components (component D and other components) using a known method. In one or more embodiments, the detergent composition of the present disclosure can be produced by blending at least component A, component B, and component C. Accordingly, in one aspect, the present disclosure relates to a method for producing a detergent composition, the method including a step of blending at least component A, component B, and component C. In the present disclosure, the term "blending" includes mixing component A, component B, component C, and, as needed, optional components (component D and other components) simultaneously or in any order. In the method for producing a detergent composition of the present disclosure, the blended amount of each component can be the same as the content of each component when the detergent composition of the present disclosure is used as described above. In the present disclosure, the "content of each component when the detergent composition is used" refers to the content of each component at the time of cleaning, i.e., at the time when the detergent composition is first used for cleaning.

[0041] In one or more embodiments, the cleaning composition of the present disclosure is used to clean an object having flux residue, particularly an object having flux residue remaining after joining two components 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 having flux residue. Therefore, in one aspect, the present disclosure relates to the 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 flux residue remover for removing flux residue from an object having flux residue. Therefore, 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 the use of the cleaning composition or the flux residue cleaning remover composition of the present disclosure as a flux residue remover.

[0042] [Object to be cleaned] In one or more embodiments, the object to be cleaned may be a substrate having flux residue that has undergone a step of heating to 200°C or higher. In one or more embodiments, the object may have a copper-containing metal component on the substrate having flux residue that has undergone 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 that has flux residue. In one or more embodiments, the object to be cleaned that has flux residue may be a substrate having flux residue that has undergone a step of applying a flux-containing slurry between the substrate and the metal component or between two metal components on the substrate and then heating to 200°C or higher (sintering step). Therefore, in one aspect, the present disclosure relates to use of the cleaning composition of the present disclosure in cleaning a substrate having flux residue, which has been subjected to a step 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 (sintering step). In the sintering step, 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 exhibiting cleaning properties against thermal denaturation of the flux, the object to be cleaned is preferably an object to be cleaned that has been heated for 1 hour or more. In one or more 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, i.e., 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 that has been in contact 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 the metal member, and is formed by a water-soluble preflux (OSP, Organic Solderability Preservative) treatment.In one or more embodiments, an example of a method for forming an organic coating is a method in which the surface of a substrate and / or the surface of a metal member is immersed 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 containing an imidazole derivative as a main component. 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 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 which includes an organic coating containing an imidazole derivative. In one or more embodiments, the flux contains an acid as a main component. Examples of the acid include organic acids 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 with 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 a substrate and a metal member or two metal members on a substrate. In one or more embodiments, the flux-containing slurry can be used as a die attach paste. When the flux-containing slurry further contains metal particles, the slurry can be used as a conductive die attach paste. In one or more embodiments, the metal member is fixed on a substrate. In one or more embodiments, the metal of the metal member includes copper, iron, or another metal. Examples of the metal member include a heat sink, an electrical circuit, and the like. In one or more embodiments, the substrate includes 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 includes copper.

[0043] [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. Examples of the object to be cleaned include the objects described above. In one or more embodiments, the cleaning step includes contacting the object having flux residue with the cleaning composition of the present disclosure. The cleaning method of the present disclosure can efficiently remove flux residue while suppressing metal corrosion and damage to organic coatings. Examples of methods for cleaning an object to be cleaned with the cleaning composition of the present disclosure or contacting the object to be cleaned with the cleaning composition of the present disclosure include a method of contacting the object in a bathtub of an ultrasonic cleaning device and a method of contacting the object by spraying the cleaning composition (shower method). In one or more embodiments, the cleaning composition of the present disclosure can be used for cleaning as 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 suppressing damage to the 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 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 rinsing the object to be cleaned with water and / or an alcohol such as methanol and drying it after contacting the object to be cleaned with the cleaning composition. In the cleaning method of the present disclosure, it is preferable to irradiate the cleaning composition of the present disclosure with ultrasonic waves when the cleaning composition comes into contact with the object to be cleaned, and it is more preferable that the ultrasonic waves be relatively strong, from the viewpoint of making it easier for the cleaning power of the cleaning composition of the present disclosure to be exerted. From the same viewpoint, the ultrasonic frequencies are preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

[0044] 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. The flux residue remover used in the removal step can be 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 flux residue cleaning and removal method that 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).

[0045] [Method for Manufacturing Electronic Components] In one aspect, the present disclosure relates to a method for manufacturing electronic components (hereinafter also referred to as the "method for manufacturing electronic components of the present disclosure") using the cleaning method of the present disclosure. In one or more embodiments, the method for manufacturing electronic components of 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 using 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 the object to be cleaned having flux residue with the cleaning composition of the present disclosure. Examples of cleaning methods in the cleaning step include methods similar to the cleaning method of the present disclosure described above. Examples of objects to be cleaned include the objects to be cleaned described above.

[0046] In one or more embodiments, the present disclosure further relates to the following cleaning composition for removing flux residue, cleaning method, and method for manufacturing semiconductor electronic components. <1> 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): 1 -O-(AO) n -R 2 (I) In the above formula (I), R 1is a phenyl group or an alkyl group having 1 to 8 carbon atoms, and R 2represents a hydrogen atom or an alkyl group having from 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 from 1 to 3. <2> The cleaning composition according to <1>, in which the content of component A is from 35 to 99.5% by mass. <3> The cleaning composition according to <1>, in which the content of component A is from 35 to 99.5% by mass, or from 50 to 95% by mass, or from 75 to 90% by mass. <4> The cleaning composition according to any one of <1> to <3>, in which the content of component B is from 0.05 to 5% by mass. <5> The cleaning composition according to any one of <1> to <4>, in which the content of component B is from 0.05 to 5% by mass, or from 0.1 to 3% by mass, or from 0.3 to 1% by mass. <6> The cleaning composition according to any one of <1> to <5>, wherein the mass ratio B / C of component B to component C is 0.01 or more and 100 or less. <7> The cleaning composition according to any one of <1> to <6>, wherein the mass ratio B / C of component B to component C is 0.01 or more and 100 or less, or 0.1 or more and 10 or less, or 0.5 or more and 5 or less. <8> The cleaning composition according to any one of <1> to <7>, wherein the mass ratio A / B of component A to component B (content of A / content of B) is 50 or more and 1,000 or less, or 100 or more and 500 or less, or 150 or more and 300 or less. <9> The cleaning composition according to any one of <1> to <8>, wherein the mass ratio A / C of component A to component C (content of component A / content of component C) is 20 or more and 500 or less, or 50 or more and 300 or less, or 70 or more and 200 or less. <10> The cleaning composition according to any one of <1> to <9>, further comprising water (component D). <11> The cleaning composition according to <10>, in which the content of component D is 15% by mass or less. <12> The cleaning composition according to <10>, in which the content of component D is 1% by mass or more and 15% by mass or less, or 5% by mass or more and 14% by mass or less, or 8% by mass or more and 13% by mass or less.<13> The cleaning composition according to any one of <1> to <12>, wherein the total content of Component A, Component B, and Component C is 50% by mass or more and 100% by mass or less, or 70% by mass or more and 95% by mass or less, or 80% by mass or more and 90% by mass or less, or 85% by mass or more and 90% by mass or less. <14> A cleaning method comprising a cleaning step of cleaning an object to be cleaned having flux residue with the cleaning composition according to any one of <1> to <13>. <15> The cleaning method according to <14>, wherein the object to be cleaned having flux residue is a substrate having flux residue that has been subjected to 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. <16> The cleaning method according to <14> or <15>, wherein the substrate surface and / or the metal member of the object to be cleaned includes an organic coating containing an imidazole derivative. <17> The cleaning method according to any one of <14> to <16>, wherein the substrate surface and / or metal member of the object to be cleaned contains an organic coating that has been in contact with an agent containing an imidazole derivative. <18> The cleaning method according to any one of <14> to <17>, wherein the cleaning step is a step of immersing the object to be cleaned in the flux cleaning agent composition at 80°C or less. <19> The cleaning method according to any one of <14> to <18>, wherein the substrate surface and / or metal member of the object to be cleaned contains copper. <20> A method for producing a semiconductor electronic component using the cleaning method according to any one of <14> to <19>.

[0047] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples in any way.

[0048] 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 following conditions to prepare the cleaning compositions of Examples 1 to 18 and Comparative Examples 1 to 9. Unless otherwise specified, the numerical value for each component in the tables indicates the content (mass%) in the prepared cleaning composition. <Mixing Conditions> Liquid temperature: 25°C Stirrer: Magnetic stirrer (50 mm rotor) Rotation speed: 300 rpm Stirring time: 10 minutes

[0049] 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-Component A) Benzyl alcohol [manufactured by Lanxess K.K.] (Component B) Benzotriazole [manufactured by Tokyo Chemical Industry Co., Ltd.] 5-methylbenzotriazole [manufactured by 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 [manufactured by Tokyo Chemical Industry Co., Ltd.] 1-methylimidazole [manufactured by Tokyo Chemical Industry Co., Ltd.] Imidazole [manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.] Benzimidazole [manufactured by Tokyo Chemical Industry Co., Ltd.] Pyrazole [manufactured by Tokyo Chemical Industry Co., Ltd.] (Non-Component C) 1,2,3-triazole [manufactured by Tokyo Chemical Industry Co., Ltd.] Tetrazole [manufactured by Tokyo Chemical Industry Co., Ltd.] (Component D) Water [pure water of 1 μS / cm or less produced using Organo Corporation's G-10DSTSET water purification system] (Other ingredients) Dibutylaminoethanol [manufactured by Nippon Nyukazai Co., Ltd.] (basic substance) Diisopropanolamine [manufactured by Nippon Nyukazai Co., Ltd.] (basic substance) 1-hydroxyethylidene-1,1-diphosphonic acid [manufactured by Italmatch Japan Co., Ltd., Dequest 2010] (chelating agent) Stannous octoate (stannous octanoate) [manufactured by Tokyo Chemical Industry Co., Ltd.] (organic carboxylic acid metal salt)

[0050] 2. Evaluation of Cleaning Compositions The prepared cleaning compositions of Examples 1 to 18 and Comparative Examples 1 to 9 were subjected to the following tests to evaluate damage to organic coatings, metal corrosion ability (corrosion prevention), and flux residue removal ability.

[0051] [Test Substrate 1 (Evaluation of Damage to Organic Coating and Corrosion Prevention)] Test substrate 1 used to evaluate damage to organic coating and corrosion prevention was prepared as follows. <Preflux Treatment of Substrate (Formation of Organic Coating)> The test substrate was subjected to preflux treatment (Cu-OSP treatment) using the following steps and conditions. [Test Substrate] A tough pitch copper plate (50 mm x 20 mm) was used as the test substrate. [Preflux Treatment] The preflux treatment was carried out using a procedure including the following steps (a) to (d). (a) Degreasing Step The test substrate was immersed in a degreasing solution (manufactured by Shikoku Chemicals Corporation, product name: Tough Cleaner W40G) at 20 to 30°C for 30 seconds, then the substrate was removed and washed with water for 1 minute. (b) Soft Etching Process: The 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, then removed and rinsed with water for 1 minute. (c) Acid Cleaning Process: The substrate was immersed in an acid cleaning solution (5% aqueous sulfuric acid solution) at 20-30°C for 30 seconds, then removed and rinsed with water for 1 minute. The substrate was then drained with an air knife. (d) Prefluxing Process: The substrate was immersed in a metal treatment agent A (water-soluble preflux, manufactured by Shikoku Chemical Industry Co., Ltd., trade name: Tough Ace F2 (LX) PK) containing an imidazole compound at 40°C for 30-90 seconds, then removed and rinsed with water for 1 minute. The substrate was then drained with an air knife and dried at 100°C for 1 minute. A test substrate 1 was prepared by forming an organic coating (OSP film) having a thickness of about 0.1 to 0.3 μm on the copper surface.

[0052] Test Substrate 2 (Evaluation of Cleanability) 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 × 15 mm). 300 μm solder balls with a composition of Sn-3Ag-0.5Cu (each value is by mass %) were placed on the flux-printed areas. Using a reflow furnace, the temperature was increased at a rate of 2.5 ° C / sec, and the peak temperature was increased to 250 ° C for 30 seconds (oxygen concentration was 100 ppm). Test Substrate 2 was produced. Test Substrate 2 produced here is a model that simulates the joining of metals on a substrate based on 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 included a holding time at 250 ° C (30 seconds), a heating time, and a cooling time).

[0053] [Cleaning Test] The cleaning test was performed according to the following procedure. First, an ultrasonic cleaning tank, a first rinse tank, and a second rinse tank were prepared under the following conditions. The ultrasonic cleaning tank was set to a frequency of 40 kHz and an output of 400 W. 100 g of each cleaning composition was added to a 500 mL glass beaker, which was then placed in an ultrasonic cleaning bath and heated to 60°C. The first rinse tank and the second rinse tank 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 100 rpm. Next, a test substrate was held with tweezers and inserted into the ultrasonic cleaning tank, where it was immersed for 5 minutes at 60°C (ultrasonic cleaning, 40 kHz, 400 W). Next, the test substrate was held with tweezers and inserted into the first rinse tank, where it was immersed for 1 minute at 40°C while stirring at 100 rpm (water rinse). The test substrate is then held with tweezers and inserted into a second rinse tank, where it is immersed for 1 minute at 40° C. while being stirred at a rotation speed of 100 rpm (water rinse). Finally, the test substrate is purged with nitrogen and dried.

[0054] [Evaluation of Damage to Organic Coating] After the above cleaning test, the contact angle of water with the surface of test substrate 1 was measured by the drop method. Using a contact angle meter (DMo-501, manufactured by Kyowa Interface Science Co., Ltd.), 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 cleaned 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 remnant properties of the organic coating were evaluated by subtracting Y from X. The results are shown in Tables 1 and 2. The larger the value of X-Y, the more the organic coating remains and the more damage to the organic coating is suppressed.

[0055]

[0056]

[0057] 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.

[0058] [Evaluation of Corrosion Prevention] After the evaluation of the organic coating, the test substrate 1 was observed using an optical microscope (VHX-2000, manufactured by Keyence Corporation). The test substrate 1 was placed in a thermo-hygrostat (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 prevention was evaluated according to the following criteria. The results are shown in Tables 1 and 2. <Evaluation Criteria> A: No color unevenness and no discoloration. B: No color unevenness and discoloration observed. C: Discoloration observed, with partial browning. D: Entire surface browning. The cleaning composition of Example 1, which contained Components B and C, was superior in inhibiting copper discoloration (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). Cleaning compositions that have a large X-Y value in the evaluation of water contact angle after cleaning and that can leave an organic coating were superior in anticorrosion properties, and Examples 2 to 18 also showed excellent anticorrosion properties.

[0059] [Evaluation of cleaning performance (flux residue removal)] After the above cleaning test, the test substrate 2 was observed with an optical microscope (Keyence Corporation, VHX-2000), and the areas of the flux residue before and after cleaning were measured using an attached area calculation mode based on color identification to calculate the flux residue removal rate. The cleaning composition of Example 1 containing Component A achieved a flux residue removal rate of 100% (complete cleaning), demonstrating excellent flux residue removal ability. Examples 2 to 18 containing Component A also showed excellent flux residue removal ability.

[0060] Use of 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 devices, thereby improving the productivity of semiconductor devices.

Claims

1. A cleaning composition for removing flux residue, 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). 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. A cleaning composition according to claim 1 or 2, wherein the content of component B is 0.05% by mass or more and 5% by mass or less.

4. A cleaning composition according to any one of claims 1 to 3, wherein the mass ratio B / C of component B to component C is 0.01 or more and 100 or less.

5. A cleaning composition according to any one of claims 1 to 4, wherein the mass ratio B / C of component B to component C is 0.01 or more and 10 or less.

6. A cleaning composition according to any one of claims 1 to 5, further comprising water (component D).

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

8. A cleaning method comprising a cleaning step of cleaning an object having flux residue with a cleaning composition according to any one of claims 1 to 7.

9. The cleaning method according to claim 8, wherein the object 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.

10. The cleaning method according to claim 8 or 9, wherein the substrate surface and / or metal member of the object to be cleaned contains an organic coating containing an imidazole derivative.

11. A cleaning method according to any one of claims 8 to 10, wherein the substrate surface and / or metal member to be cleaned includes an organic coating in contact with an agent containing an imidazole derivative.

12. A cleaning method according to any one of claims 8 to 11, wherein the cleaning step is a step of immersing the object to be cleaned in the cleaning composition for removing flux residue at a temperature of 80°C or less.

13. A cleaning method according to any one of claims 8 to 12, wherein the substrate surface and / or metal member of the object to be cleaned contains copper.

14. A method for manufacturing electronic parts using the cleaning method according to any one of claims 8 to 13.

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