Flux cleaning composition

Abstract

To provide, in one aspect, a flux detergent which can prevent elution of lead to the detergent in washing of electronic components mounted using lead-containing high-melting-point solder, and a washing method.SOLUTION: In one aspect, the present disclosure relates to a flux detergent composition containing the following component A, component B, and component C. Component A: an organic solvent; component B: aliphatic tertiary amine represented by the formula (III); and component C: phosphoric ester.SELECTED DRAWING: None

Description

[Technical Field]

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

[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 used as a mounting method for printed wiring boards. To improve mounting density, a known technique involves applying a nanometal paste between the wiring on the board and the terminals of the electronic device, melting and solidifying the nanometal by heating, and bonding the wiring on the board and the terminals of the electronic device.

[0004] On the other hand, there is known a technique for cleaning solder flux from electronic components after soldering. For example, Patent Document 1 proposes a cleaning composition for soldering flux, which contains a specific polycarboxylic acid compound, a phosphate ester surfactant, and an organic solvent. Patent Document 2 proposes a detergent composition containing a glycol ether compound, a hydrophobic tertiary amine compound, a hydrophilic carboxylic acid, and water. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-53198 [Patent Document 2] Japanese Patent Publication No. 2022-72721 Summary of the Invention [Problem to be solved by the invention]

[0006] When assembling electronic components, lead solder containing lead, particularly high-melting-point solder containing 90% or more by mass of lead, is sometimes used. When cleaning (removing) flux (flux residue) remaining on electronic components mounted using such high-melting-point solder containing lead, the flux residue can be effectively removed by using cleaning agents containing organic solvents, as proposed in Patent Documents 1 and 2. However, lead may leach from the lead solder into the cleaning agent during the cleaning process or the rinsing process after the cleaning process, causing lead corrosion. Furthermore, lead leaching into the cleaning agent may precipitate insoluble lead compounds during the drying process after the rinsing process. These precipitated insoluble lead compounds pose problems, such as reduced insulation resistance and reduced product performance, which can lead to reduced electrical reliability of electronic components. Therefore, when cleaning electronic components mounted with high-melting-point solder containing lead, there is a demand for a flux cleaner that maintains flux removal properties (cleaning ability, flux residue removal ability) while minimizing lead elution into the cleaner.

[0007] Therefore, the present disclosure provides a flux cleaning agent composition, a cleaning method, and a method for manufacturing electronic components that can suppress the elution of lead into the cleaning agent when cleaning electronic components mounted with high-melting-point solder containing lead. [Means for solving the problem]

[0008] In one aspect, the present disclosure relates to a flux cleaning composition containing the following components A, B, and C: Component A: Organic solvent Component B: an aliphatic tertiary amine represented by the following formula (III): Component C: Phosphate ester [ka] In the above formula (III), R 4 , R 5 and R 6 are the same or different and represent a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms; R 4 , R 5 and R6 The sum of the carbon numbers is 18 or more.

[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 flux cleaning composition of the present disclosure.

[0010] In one aspect, the present disclosure relates to a method for producing electronic components, including a cleaning step of cleaning an object having flux residue with the flux cleaning composition of the present disclosure.

[0011] In one aspect, the present disclosure relates to a flux cleaning composition comprising the following components A, B, and C: Component A: Organic solvent Component B: an aliphatic tertiary amine represented by the following formula (III): Component C: Phosphate ester [ka] In the above formula (III), R 4 , R 5 and R 6 are the same or different and represent a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms; R 4 , R 5 and R 6 The sum of the carbon numbers is 18 or more. [Effects of the Invention]

[0012] In one or more embodiments, the present disclosure can provide a flux cleaning agent composition, a cleaning method, and a method for manufacturing electronic components, which can suppress the elution of lead into a cleaning agent when cleaning electronic components mounted using high-melting-point solder containing lead. DETAILED DESCRIPTION OF THE INVENTION

[0013] The inventors discovered that the combined use of a specific aliphatic tertiary amine (ingredient B) and a phosphate ester (ingredient C) as a cleaning agent can suppress lead elution into the cleaning agent while maintaining flux removal (flux residue removal) when cleaning electronic components mounted with high-melting-point solder containing lead.

[0014] That is, in one aspect, the present disclosure relates to a flux cleaning composition (hereinafter also referred to as "the cleaning composition of the present disclosure") containing the following Components A, B, and C: Component A: Organic solvent Component B: an aliphatic tertiary amine represented by the following formula (III): Component C: Phosphate ester [ka] In the above formula (III), R 4 , R 5 and R 6 are the same or different and represent a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms; R 4 , R 5 and R 6 The sum of the carbon numbers is 18 or more.

[0015] According to the present disclosure, when cleaning electronic components mounted using high-melting-point solder containing lead, the elution of lead into the cleaning agent can be suppressed.

[0016] Although the details of the mechanism of action by which the effects of the present disclosure are manifested are still unclear, it is speculated as follows. The cleaning composition of the present disclosure contains two components: a specific aliphatic tertiary amine (component B) and a phosphate ester (component C). This is thought to promote the formation of an organic film on lead. It is also thought that components B and C interact with each other, for example, by forming a salt. As a result, the cleaning and rinsing processes maintain excellent flux removal (flux residue removal) while suppressing damage to the lead surface, i.e., inhibiting lead metal elution and corrosion. This is thought to suppress the precipitation of insoluble lead compounds in the drying process. However, the present disclosure need not be construed as being limited to this mechanism.

[0017] 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 a high temperature of 200°C or higher), and is used, for example, to bond a heat sink to a semiconductor element or 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 "flux" to be removed by cleaning in this disclosure is the flux used in a soldering process (joining) using a lead-containing solder, or the flux used in a soldering process (joining) using a high-melting-point solder (e.g., Pb-5Sn, Pb-10Sn, etc.), which is called "flux residue." In one or more embodiments, the term "flux residue" used in the present disclosure refers to flux remaining on an electronic component or a semi-finished product thereof that has been mounted using lead-containing solder or high-melting-point solder. Here, in one or more embodiments, the semi-finished product refers to an item in the manufacturing stage of the electronic component. In one or more embodiments, the term "flux residue" used in the present disclosure refers to flux remaining after joining two components together through a sintering process. In one or more embodiments, the "cleaning composition for flux" in the present disclosure is a cleaning composition for removing flux residue, which is used to remove flux residue on electronic components mounted by soldering or semi-finished products thereof. In one or more embodiments, the "flux cleaning composition" of the present disclosure is a cleaning composition for removing flux residue, which is used to remove flux residue on electronic components or semi-finished products thereof mounted with high-melting-point solder containing 90 mass % or more of lead. In one or more embodiments, the "cleaning composition for flux" in the present disclosure refers to a cleaning composition for removing flux residue remaining after joining two members by a sintering step (cleaning composition for removing flux residue).

[0018] [Component A: organic solvent] The organic solvent (hereinafter also referred to as "component A") contained in the cleaning composition of the present disclosure may be one type, or two or more types may be combined. In one or more embodiments, from the viewpoint of improving flux removability, Component A is preferably at least one selected from the group consisting of compounds represented by the following formula (I) and compounds represented by the following formula (II):

[0019] <Compound represented by formula (I)> 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 or a propylene oxide group, and n is the number of moles of AO added and is an integer of 1 to 3.

[0020] In the above formula (I), R 1 From the viewpoint of improving flux removability, represents a phenyl group or an alkyl group having 1 to 8 carbon atoms, preferably a phenyl group or an alkyl group having 4 to 6 carbon atoms, and more preferably an alkyl group having 4 to 6 carbon atoms. In the above formula (I), R 2From the viewpoint of improving flux removability, represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 2 to 4 carbon atoms, and more preferably a hydrogen atom. In the above formula (I), AO is an ethyleneoxy group (EO) or a propyleneoxy group (PO) from the viewpoint of improving flux removability, and an ethyleneoxy group is preferred. In the above formula (I), n is an integer of 1 or more and 3 or less, preferably 1 or 2, and more preferably 2, from the viewpoint of improving flux removability.

[0021] Examples of the compound represented by formula (I) above 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, and triethylene 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 viewpoint of improving flux removability, the compound represented by the above formula (I) is preferably at least one selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, diethylene glycol dibutyl ether and triethylene glycol dimethyl ether, more preferably at least one selected from diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, dipropylene glycol monobutyl ether and diethylene glycol dibutyl ether, and even more preferably at least one selected from diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and diethylene glycol monohexyl ether.

[0022] <Compound represented by formula (II)> R 3 -CH2OH (II) In the above formula (II), R 3 is a phenyl group, a benzyl group, a cyclohexyl group, a furyl group, a tetrahydrofuryl group, a furfuryl group, or a tetrahydrofurfuryl group.

[0023] In the above formula (II), R 3 is a phenyl group, a benzyl group, a cyclohexyl group, a furyl group, a tetrahydrofuryl group, a furfuryl group, or a tetrahydrofurfuryl group, preferably a phenyl group, a cyclohexyl group, or a tetrahydrofuryl group, more preferably a phenyl group or a tetrahydrofuryl group, and even more preferably a phenyl group, from the viewpoint of improving flux removability.

[0024] Examples of the compound represented by formula (II) include at least one selected from benzyl alcohol, phenethyl alcohol, cyclohexanemethanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol. Among these, from the viewpoint of improving flux removability, the compound represented by formula (II) is preferably at least one selected from benzyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol, more preferably at least one selected from benzyl alcohol and tetrahydrofurfuryl alcohol, and even more preferably benzyl alcohol.

[0025] From the viewpoint of improving flux removability, Component A is preferably at least one selected from diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, dipropylene glycol monobutyl ether, and benzyl alcohol.

[0026] 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 removability. Also, from the viewpoint of lowering the flash point, it is preferably 99.5% by mass or less, more preferably 97.5% by mass or less, and even more preferably 95.0% by mass or less or 90% by mass or less. 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 97.5% by mass or less, and even more preferably 75% by mass or more and 95.0% by mass or less or 75% by mass or more and 90% by mass or less. When Component A is a combination of two or more types, the content of Component A refers to the total content of those types.

[0027] [Component B: Aliphatic tertiary amine] In one or more embodiments, the aliphatic tertiary amine (hereinafter also referred to as "Component B") contained in the cleaning composition of the present disclosure is a compound represented by the following formula (III). Component B may be in the form of a salt of the compound. Component B may also form a salt with Component C in the cleaning composition. Component B may be one type, or two or more types may be combined. [ka] In the above formula (III), R 4 , R 5 and R 6 are the same or different and represent a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms; R 4 , R 5 and R 6 The sum of the carbon numbers is 18 or more.

[0028] In the above formula (III), R 4 , R 5 and R 6 are each independently a linear or branched alkyl or alkenyl group having from 1 to 24 carbon atoms, more preferably a linear alkyl group having from 1 to 24 carbon atoms, from the viewpoint of reducing the elution of lead into the cleaning agent. In the above formula (III), R 4, R 5 and R 6 From the viewpoint of reducing elution of lead into the cleaning agent, the sum of the carbon numbers of the above is 18 or more, preferably 20 or more, and more preferably 22 or more, and from the viewpoint of solubility in water at the time of blending, the sum of the carbon numbers of the above is preferably 30 or less, more preferably 28 or less, and even more preferably 26 or less. In the above formula (III), R 4 , R 5 and R 6 The number of carbon atoms in R is chosen to reduce the amount of lead eluted into the cleaning agent. 4 and R 5 Each of these is 1 and R 6 is 16 or more, or R 4 is 1 and R 5 and R 6 Each of these is 9 or more, or R 4 , R 5 and R 6 are preferably each 6 or more, and R 4 and R 5 Each of these is 1 and R 6 is 18 or above, or R 4 is 1 and R 5 and R 6 Each of these is 10 or more, or R 4 , R 5 and R 6 It is more preferable that each of these is 8 or more.

[0029] Examples of Component B include dimethylpalmitylamine, dimethylstearylamine, didecylmonomethylamine, trioctylamine, trilaurylamine, etc. Among these, from the viewpoint of reducing elution of lead into the cleaning agent and from the viewpoint of solubility in water at the time of blending, Component B is preferably at least one selected from dimethylstearylamine, didecylmonomethylamine, and trioctylamine, and more preferably trioctylamine.

[0030] The content of Component B during use of the cleaning composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of reducing lead elution into the cleaning agent. From the viewpoint of solubility in water during blending, the content is preferably 10% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5.0% by mass or less. More specifically, the content of Component B during use of the cleaning composition of the present disclosure is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 7.5% by mass or less, and even more preferably 0.5% by mass or more and 5.0% by mass or less. When Component B is a combination of two or more types, the content of Component B refers to the total content of those components.

[0031] [Component C: Phosphate ester] In one or more embodiments, the phosphate ester (hereinafter also referred to as "component C") contained in the cleaning composition of the present disclosure is a phosphate ester surfactant. In one or more embodiments, component C of the present disclosure includes a compound represented by the following formula (IV): Component C of the present disclosure may be one type or a combination of two or more types. Component C may be in the form of a salt of the compound. Furthermore, component C may form a salt with component B in the cleaning composition. [ka] In the above formula (IV), R 7 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 1 to 12 carbon atoms, p is an integer from 0 to 20, and X is a hydroxyl group or R 8 -O-(CH2CH2O) q - indicates R 8 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 1 to 12 carbon atoms; and q represents an integer of 0 to 20.

[0032] In the above formula (IV), R 7is a linear or branched alkyl group having from 1 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having from 1 to 12 carbon atoms, from the viewpoint of reducing the elution of lead into the cleaning agent, with a linear or branched alkyl group having from 1 to 20 carbon atoms being preferred, and a linear alkyl group having from 1 to 20 carbon atoms being more preferred. R 7 From the viewpoint of reducing the elution of lead into the detergent, the number of carbon atoms is preferably 4 or more, more preferably 8 or more, and from the same viewpoint, it is preferably 18 or less, more preferably 16 or less. R 7 From the viewpoint of reducing the elution of lead into the cleaning agent, the carbon number of the linear alkyl group is preferably 4 or more, more preferably 8 or more, and from the same viewpoint, the carbon number of the linear alkyl group is preferably 18 or less, more preferably 16 or less. In the above formula (IV), p is an integer of 0 to 20, preferably 10 or less, and more preferably 5 or less, from the viewpoint of reducing the elution of lead into the cleaning agent. In the above formula (IV), X is a hydroxyl group or R 8 -O-(CH2CH2O) q -(However, R 8 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 1 to 12 carbon atoms, and q represents an integer of 0 to 20), and preferably R 8 -O-(CH2CH2O) q -It is. In the above formula (IV), R 8 is a linear or branched alkyl group having from 1 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having from 1 to 12 carbon atoms, from the viewpoint of reducing the elution of lead into the cleaning agent, with a linear or branched alkyl group having from 1 to 20 carbon atoms being preferred, and a linear alkyl group having from 1 to 20 carbon atoms being more preferred. R 8From the viewpoint of reducing the elution of lead into the detergent, the number of carbon atoms is preferably 4 or more, more preferably 8 or more, and from the same viewpoint, it is preferably 18 or less, more preferably 16 or less. R 8 From the viewpoint of reducing the elution of lead into the cleaning agent, the carbon number of the linear alkyl group is preferably 4 or more, more preferably 8 or more, and from the same viewpoint, the carbon number of the linear alkyl group is preferably 18 or less, more preferably 16 or less. In the above formula (IV), q is an integer of 0 to 20, preferably 10 or less, more preferably 5 or less, and even more preferably 0, from the viewpoint of reducing the elution of lead into the cleaning agent.

[0033] Examples of Component C include at least one selected from methyl phosphate, monobutyl phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) acid phosphate, isotridecyl acid phosphate, laureth-2-phosphate, laureth-4-phosphate, and steareth-2-phosphate. Among these, from the viewpoint of reducing elution of lead into the detergent, Component C is preferably at least one selected from 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) acid phosphate, isotridecyl acid phosphate, laureth-2-phosphate, laureth-4-phosphate, and steareth-2-phosphate, and more preferably at least one selected from isotridecyl acid phosphate and steareth-2-phosphate.

[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 reducing lead elution into the cleaning agent. From the viewpoint of solubility in water during blending, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. More specifically, the content of component C during use of the cleaning composition of the present disclosure is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, and even more preferably 0.3% by mass or more and 3% 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 of those components.

[0035] In the cleaning composition of the present disclosure, the molar ratio B / C of component B to component C is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, from the viewpoint of reducing elution of lead into the cleaning agent, and from the same viewpoint, is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. More specifically, the molar ratio B / C is preferably 0.1 or more and 10 or less, more preferably 0.3 or more and 5 or less, and even more preferably 0.5 or more and 3 or less.

[0036] In the cleaning composition of the present disclosure, the mass ratio B / C of component B to component C is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 0.3 or more, from the viewpoint of reducing lead elution into the cleaning agent, and is preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less, from the viewpoint of reducing lead elution into the cleaning agent. More specifically, the mass ratio B / C is preferably 0.01 or more and 20 or less, more preferably 0.1 or more and 10 or less, and even more preferably 0.3 or more and 5 or less.

[0037] In the cleaning composition of the present disclosure, the mass ratio A / B of Component A to Component B is preferably 10 or more, more preferably 15 or more, and even more preferably 20 or more, from the viewpoint of reducing lead elution into the cleaning agent, and is preferably 500 or less, more preferably 200 or less, even more preferably 100 or less, and even more preferably 50 or less. More specifically, the mass ratio A / B is preferably 10 or more and 500 or less, more preferably 15 or more and 200 or less, even more preferably 20 or more and 100 or less, and even more preferably 20 or more and 50 or less.

[0038] In the cleaning composition of the present disclosure, the mass ratio A / C of Component A to Component C is preferably 10 or more, more preferably 25 or more, and even more preferably 50 or more, from the viewpoint of reducing lead elution into the cleaning agent, and is preferably 500 or less, more preferably 200 or less, and even more preferably 100 or less, from the viewpoint of reducing lead elution into the cleaning agent. More specifically, the mass ratio A / C is preferably 10 or more and 500 or less, more preferably 25 or more and 200 or less, and even more preferably 50 or more and 100 or less.

[0039] [Component D: Water] In one or more embodiments, the cleaning composition of the present disclosure does not contain water. In one or more embodiments, the cleaning composition of the present disclosure may further contain water (hereinafter also referred to as "component D") from the viewpoint of lowering the flash point. Examples of component D include deionized 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% by mass or more, more preferably 3% by mass or more, and even more preferably 5% 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 removability. More specifically, the content of Component D during use of the cleaning composition of the present disclosure is preferably 1% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 14% by mass or less, and even more preferably 5% by mass or more and 13% by mass or less.

[0040] In the cleaning composition of the present disclosure, the mass ratio A / D of Component A to Component D is preferably 1 or more, more preferably 5 or more, and even more preferably 7 or more from the viewpoint of improving flux removability, and is preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less from the viewpoint of lowering the flash point. More specifically, the mass ratio A / D is preferably 1 or more and 50 or less, more preferably 5 or more and 20 or less, and even more preferably 7 or more and 10 or less.

[0041] In the cleaning composition of the present disclosure, the mass ratio B / D of component B to component D is preferably 0.0001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and still more preferably 0.1 or more, from the viewpoint of reducing elution of lead into the cleaning agent, and from the viewpoint of solubility in water at the time of blending, is preferably 10 or less, more preferably 2 or less, and still more preferably 1 or less. More specifically, the mass ratio B / D is preferably 0.0001 or more and 10 or less, more preferably 0.005 or more and 2 or less, even more preferably 0.01 or more and 1 or less, and still more preferably 0.1 or more and 1 or less.

[0042] In the cleaning composition of the present disclosure, the mass ratio C / D of Component C to Component D is preferably 0.0001 or more, more preferably 0.005 or more, and even more preferably 0.01 or more from the viewpoint of reducing elution of lead into the cleaning agent, and from the viewpoint of solubility in water at the time of blending, it is preferably 5 or less, more preferably 1 or less, and even more preferably 0.5 or less. More specifically, the mass ratio C / D is preferably 0.0001 or more and 5 or less, more preferably 0.005 or more and 1 or less, and even more preferably 0.01 or more and 0.5 or less.

[0043] From the viewpoint of reducing lead elution into the cleaning agent, the total content of Components A, B, and C in the cleaning composition of the present disclosure is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. More specifically, the total content of Components A, B, and C in the cleaning composition of the present disclosure is preferably 40% by mass or more and 99% by mass or less, more preferably 60% by mass or more and 97% by mass or less, and even more preferably 80% by mass or more and 95% by mass or less.

[0044] [Other ingredients] The cleaning composition of the present disclosure may contain, as needed, appropriate additives typically used in cleaning agents, such as a chelating agent, an anti-rust agent, a thickener, a dispersant, a solvent other than Component A, a basic substance, a pH adjuster, a polymer compound, a surfactant other than Component C, a solubilizer, a preservative, a disinfectant, an antibacterial agent, an antifoaming agent, and an antioxidant, within the scope of not impairing the effects of the present disclosure. The content of other components in the cleaning composition of the present disclosure is preferably 0% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less.

[0045] In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of a water-insoluble polycarboxylic acid. For example, the content of the water-insoluble polycarboxylic acid in the cleaning composition of the present disclosure is preferably less than 0.05% by mass, more preferably 0.01% by mass or less, and even more preferably 0% by mass (i.e., no content). In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of a hydrophilic carboxylic acid. For example, the content of a hydrophilic carboxylic acid in the cleaning composition of the present disclosure is preferably less than 0.01% by mass, and more preferably 0% by mass (i.e., no hydrophilic carboxylic acid is contained). In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of a phosphonic acid compound. For example, the content of the phosphonic acid compound in the cleaning composition of the present disclosure is preferably less than 0.2% by mass, preferably 0.01% by mass or less, and more preferably 0% by mass (i.e., no phosphonic acid compound is contained).

[0046] [Method of manufacturing the cleaning composition] The cleaning 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 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, which includes blending at least component A, component B, and component C. In the present disclosure, "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 the cleaning composition of the present disclosure, the blending amount of each component can be the same as the content of each component when the above-described cleaning composition of the present disclosure is used. In the present disclosure, the "content of each component of the detergent 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 detergent composition starts to be used for cleaning. In one or more embodiments, the content of each component in the cleaning composition of the present disclosure during use can be considered to be the blended amount of each component in the cleaning composition of the present disclosure. However, if there is an effect of neutralization, the blended amount and the actual content may differ.

[0047] [pH of cleaning composition] The pH of the cleaning composition of the present disclosure is preferably 5 or higher, more preferably 6 or higher, from the viewpoint of reducing lead elution into the cleaning agent, and from the same viewpoint, is preferably 12 or lower, more preferably 11 or lower, and even more preferably 10 or lower. More specifically, the pH of the cleaning composition of the present disclosure is preferably 5 or higher and 12 or lower, more preferably 6 or higher and 11 or lower, and even more preferably 6 or higher and 10 or lower. If necessary, the pH can be adjusted using inorganic acids such as nitric acid and sulfuric acid, organic acids such as oxycarboxylic acids, polycarboxylic acids, aminopolycarboxylic acids, and amino acids, as well as metal salts or ammonium salts thereof, ammonia, sodium hydroxide, potassium hydroxide, amines, carboxylic acids having 8 or more carbon atoms, etc. The pH of the cleaning composition of the present disclosure is the pH at 25°C when the cleaning composition is in use, and can be measured by the method described in the Examples.

[0048] [Items to be cleaned] In one or more embodiments, the object to be cleaned is an object to be cleaned that has flux residue. In one or more embodiments, the object to be cleaned having flux residue is an electronic component having flux residue. In one or more embodiments, the electronic component may be an electronic component mounted by soldering or a semi-finished product thereof. Here, in one or more embodiments, the semi-finished product refers to an electronic component in the manufacturing stage. In one or more embodiments, the object to be cleaned having flux residue includes lead-containing solder and electronic components having flux residue, such as electronic components mounted using high-melting-point solder containing 90% or more by mass of lead, or semi-finished products thereof, to which flux residue adheres. Therefore, in one or more embodiments, the cleaning composition of the present disclosure is suitable for use in removing (cleaning) flux residue from electronic components mounted by soldering or their semi-finished products, particularly from electronic components mounted with high-melting-point solder containing 90% by mass or more of lead, or from their semi-finished products. That is, in one or more embodiments, the cleaning composition of the present disclosure is a cleaning agent for removing flux residue remaining on electronic components mounted with high-melting-point solder containing 90% by mass or more of lead, or from their semi-finished products.

[0049] 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 members by a sintering process. 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 substrate may have a metal member containing copper on it. In one or more embodiments, the step of heating to 200°C or higher is a step of maintaining the temperature at a high temperature of 200°C or higher (sintering step). In one or more embodiments, the object to be cleaned having flux residue is a substrate having flux residue, which has undergone 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 the slurry to 200° C. or higher (sintering step).Accordingly, in one aspect, the present disclosure relates to the use of the cleaning composition of the present disclosure in cleaning a substrate having flux residue, which has undergone 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 the slurry to 200° C. or higher (sintering step). 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 more embodiments, the substrate surface and / or the metal member of the object to be cleaned contains lead or a lead alloy. In one or more embodiments, the flux contains an acid as a main component, such as an organic acid such as abietic acid. In one or more embodiments, the flux-containing slurry may further contain metal particles. Examples of the metal particles include tin, lead, 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. 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, etc. Examples of the metal member include a heat sink, an electric circuit, etc. In one or more embodiments, the substrate may be a substrate having a metal surface, such as a copper plate, a steel plate, a stainless steel plate, or a copper-wiring printed circuit board.

[0050] [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") that includes a cleaning step of cleaning an object having flux residue with the cleaning composition of the present disclosure. Examples of the object 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 reduce lead elution into the cleaning agent while maintaining flux removability. In another aspect, the present disclosure relates to use of the cleaning agent composition of the present disclosure for suppressing elution of lead into a cleaning agent and removing flux residue. 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 immersing the object in a bath of an ultrasonic cleaning device, a method for spraying 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 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. The immersion temperature is preferably 20°C or higher, more preferably 30°C or higher, and even more preferably 40°C or higher from the viewpoint of improving flux removability. From the viewpoints of reducing lead elution into the cleaning agent, handling safety, and reducing equipment load, the immersion temperature is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower. From the same viewpoints, the immersion time is preferably 1 minute or longer, more preferably 3 minutes or longer, and even more preferably 5 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, after contacting the object to be cleaned with the cleaning composition (after the cleaning step), a step of rinsing the object with water and / or an alcohol such as methanol, a halogenated solvent, or the like (rinsing step), and a step of drying the object (drying step). 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, since this makes it easier for the cleaning power of the cleaning composition of the present disclosure to be exerted. It is more preferable that the ultrasonic waves be relatively strong.

[0051] [Electronic component manufacturing method] In one aspect, the present disclosure relates to a method for producing electronic components (hereinafter also referred to as the "method for producing electronic components of the present disclosure"), which includes a cleaning step of cleaning an object having flux residue with the flux cleaning composition of the present disclosure. The object to be cleaned may be any of the above-mentioned objects to be cleaned. 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. Examples of a cleaning method in the cleaning step include the same methods as the cleaning method of the present disclosure described above. In one or more embodiments, the cleaning step is a step of cleaning electronic components or semi-finished products thereof, which are mounted using high-melting-point solder containing 90 mass % or more of lead and have flux residue attached thereto, with the cleaning composition of the present disclosure. Here, in one or more embodiments, the semi-finished products refer to the electronic components in the manufacturing stage. [Example]

[0052] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples in any way.

[0053] 1. Preparation of Cleaning Compositions (Examples 1 to 14, Comparative Examples 1 and 2) The components shown in Table 1 were blended in a 100 mL glass beaker and mixed under the conditions below to prepare cleaning compositions (pH: 7.2) for Examples 1 to 14 and Comparative Examples 1 and 2. Unless otherwise specified, the numerical value for each component in the table indicates the content (mass%) of the component in the prepared cleaning composition. The molar ratio B / C for Comparative Example 1 was calculated assuming that polyoxyethylene stearylamine was component B. <Mixing conditions> Liquid temperature: 60℃ Stirrer: Magnetic stirrer (50 mm rotor) Rotation speed: 300 rpm Mixing time: 1 hour

[0054] 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.] Benzyl alcohol [Tokyo Chemical Industry Co., Ltd.] (Component B) Tri-n-octylamine [Tokyo Chemical Industry Co., Ltd.] Didecylmonomethylamine [Tokyo Chemical Industry Co., Ltd.] Dimethylstearylamine [Tokyo Chemical Industry Co., Ltd.] (Non-ingredient B) Polyoxyethylenestearylamine [Kao Corporation] (Component C) Methyl phosphate (mono- and di-mixture) [Tokyo Chemical Industry Co., Ltd.] Dibutyl phosphate [Tokyo Chemical Industry Co., Ltd.] 2-Ethylhexyl Acid Phosphate (Mono- and Di-mixture) [Johoku Chemical Industry Co., Ltd.] Isotridecyl acid phosphate (mono- and di-mixture) [Johoku Chemical Industry Co., Ltd.] Laureth-2-phosphate [Toho Chemical Industry Co., Ltd.] Laureth-4-phosphate [Toho Chemical Industry Co., Ltd.] Steareth-2-phosphate [Toho Chemical Industry Co., Ltd.] (Component D) Water [pure water of 1 μS / cm or less produced using the Organo Corporation G-10DSTSET water purification system]

[0055] [pH measurement] The pH of the cleaning composition was measured at 25°C, and the electrode of a pH meter (HM-30G, Toa Denpa Kogyo Co., Ltd.) was immersed in the cleaning composition and the value was measured 3 minutes later.

[0056] 2. Evaluation of cleaning composition The cleaning compositions of Examples 1 to 14 and Comparative Examples 1 and 2 were evaluated as follows.

[0057] [Evaluation of the amount of dissolved lead] The amount of dissolved lead was evaluated according to the following procedure. First, an ultrasonic cleaning tank was prepared under the following conditions. The ultrasonic cleaning tank was set to a frequency of 40 kHz and an output of 400 W, and 20 g of each cleaning composition was added to a 100 mL glass beaker, which was then placed in the ultrasonic cleaning tank and heated to 60°C. Next, 0.1 g of lead powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the beaker, which was then inserted into the ultrasonic bath and immersed at 60° C. for 1 hour. The cleaning compositions were collected from the beakers, filtered (ADVANTEC, 25HP020AN), and then diluted 100-fold with ultrapure water. The resulting samples were analyzed by ICP optical emission spectroscopy (Agilent Technologies, Agilent 5100 / 5110ICP-OES) to calculate the amount of dissolved lead in each cleaning composition. To calculate the amount of dissolved lead, a lead standard solution (Pb1000) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used and a calibration curve method was applied. The results are shown in Table 1. The values ​​in the table are converted values ​​before dilution, and the lower the value, the more the damage to lead (elution and corrosion) is suppressed.

[0058] [Evaluation of lead corrosion protection and precipitation] The evaluation of lead corrosion prevention was carried out according to the following procedure. First, an ultrasonic cleaning tank and a 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, and 20 g of each detergent composition was added to a 100 mL glass beaker, which was then placed in the ultrasonic cleaning tank and heated to 60°C. The rinse bath was prepared by setting the frequency to 40 kHz and the output to 400 W, adding 20 mL of ultrapure water to a 100 mL glass beaker, placing it in the rinse bath, and heating it to 40°C. Next, a 1 cm x 1 cm lead test piece (manufactured by Taiyu Kizai Co., Ltd.) was held with tweezers and placed in a beaker, which was then inserted into the ultrasonic bath and immersed at 60°C for 1 hour. Before use, the surface of the test piece was rubbed with Kimwipe (manufactured by Nippon Paper Crecia Co., Ltd.) coated with acetone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to remove the rust-preventing components. Next, the test piece is held with tweezers and inserted into the rinse bath, where it is immersed for 5 minutes. Finally, the test pieces were purged with nitrogen and dried. Before and after the above evaluation, the test pieces were observed using a scanning electron microscope (JEOL Ltd., JCM-7000NeoScope), visually inspected, and compared in appearance before and after storage under constant temperature and humidity conditions, and the corrosion resistance (corrosion of lead metal and precipitation of insoluble lead compounds) was evaluated according to the following criteria. The results are shown in Table 1. <Judgment criteria> A: There is no change in appearance before and after cleaning. B: After cleaning, pitting corrosion less than 1 μm in diameter is observed in some areas. C: After cleaning, pitting corrosion with a diameter of 1 μm or more is observed in some areas. D: After cleaning, pitting corrosion with a diameter of 1 μm or more and deposits of insoluble lead compounds are observed throughout the surface.

[0059] [Table 1]

[0060] As shown in Table 1 above, the cleaning compositions of Examples 1 to 14 were able to suppress lead metal elution and corrosion and insoluble lead compound deposition compared to Comparative Examples 1 and 2. Therefore, it is believed that the cleaning compositions of Examples 1 to 14 can suppress lead elution into the cleaning compositions when cleaning electronic components mounted with high-melting-point solder containing lead. [Industrial Applicability]

[0061] The cleaning composition of the present disclosure can, for example, 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. A flux cleaning composition comprising the following components A, B and C. Component A: organic solvent Component B: an aliphatic tertiary amine represented by the following formula (III): Component C: a compound represented by the following formula (IV): 【Chemistry 1】 In the above formula (III), R 4 , R 5 and R 6 are the same or different and represent a linear or branched alkyl or alkenyl group having from 1 to 24 carbon atoms; R 4 , R 5 and R 6 The sum of the carbon numbers of the above is 18 or more. 【Chemistry 2】 In the above formula (IV), R 7 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 1 to 12 carbon atoms, p is an integer from 0 to 20, X represents a hydroxyl group or R 8 -O-(CH 2 CH 2 O) q -, R 8 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 1 to 12 carbon atoms, and q is an integer from 0 to 20.

2. 2. The flux cleaning composition according to claim 1, wherein Component A is at least one compound selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II): 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 or a propylene oxide group; n is the number of moles of AO added and is an integer of 1 to 3. ( 3 . 2 H () In the above formula (II), R 3 is a phenyl group, a benzyl group, a cyclohexyl group, a furyl group, a tetrahydrofuryl group, a furfuryl group, or a tetrahydrofurfuryl group.

3. 2. The flux cleaning composition according to claim 1, wherein the molar ratio B / C of component B to component C is 0.1 or more and 10 or less.

4. A flux cleaning composition as described in claim 1, wherein the mass ratio A / B of component A to component B is 10 or more and 500 or less.

5. A flux cleaning composition as described in claim 1, wherein the mass ratio A / C of component A to component C is 10 or more and 500 or less.

6. The flux cleaning composition according to claim 1, further comprising water (component D).

7. A flux cleaning composition as described in claim 6, wherein the mass ratio A / D of component A to component D is 1 or more and 50 or less.

8. 2. The flux cleaning composition according to claim 1, which is a cleaning agent for removing flux residue remaining on electronic components mounted using high-melting-point solder containing 90 mass % or more of lead.

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

10. A method for producing electronic components, comprising a cleaning step of cleaning an object having flux residue with the flux cleaning composition according to any one of claims 1 to 8.

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