TW202031884A - Cleaning of flux residues - Google Patents

Abstract

One embodiment of the present disclosure provides a cleaning method exhibiting excellent flux removal performance. One embodiment of the present disclosure pertains to a cleaning method including a step for cleaning, with a detergent composition, a to-be-cleaned object having flux residues thereon, wherein the detergent composition contains an organic solvent (component A), and a compound (component B) that has an alkyl group having 1-4 carbon atoms attached to a nitrogen atom of a imidazole ring or a piperazine ring.

Description

Cleaning of flux residue

The present invention relates to a cleaning agent composition for cleaning flux residues, a cleaning method using the cleaning agent composition, and a manufacturing method of electronic parts.

In recent years, with regard to the mounting of electronic components on printed wiring boards or ceramic substrates, from the viewpoints of low power consumption and high-speed processing, the miniaturization of components has narrowed the gap that should be cleaned when cleaning with solder flux. In terms of environmental safety, lead-free solders have been used, and rosin-based fluxes have been used along with this.

International Publication No. 2012/005068 (Patent Document 1) discloses the following detergent composition stock solution, which is used to mix with water and add a certain amount of water to the cleaned object in a cloudy state A stock solution for cleaning composition for cleaning, etc., which contains the first and second organic solvents as organic solvents, the first organic solvent is a specific hydrophobic glycol ether compound, etc., and the second organic solvent is a specific hydrophilic amine For the compound, the compounding amount of the second organic solvent is set to a value in the range of 0.3-30 parts by weight relative to 100 parts by weight of the first organic solvent, and the compounding amount of the organic solvent with a boiling point exceeding 190°C is set It is a value within a specific range. International Publication No. 2005/021700 (Patent Document 2) discloses the following cleaning agent for removing solder flux, which is characterized in that when the content of the glycol compound is less than 1% by weight relative to the total amount, benzyl The content of the alcohol is set in the range of 70 to 99.9% by weight and the content of the amino alcohol is set in the range of 0.1 to 30% by weight. When the content of the diol compound is 1 to 40% by weight, the content of benzyl alcohol The range is 15 to 99% by weight, and the content of the amino alcohol is 0.1 to 30% by weight. Japanese Patent Laid-Open No. 7-179893 (Patent Document 3) discloses a cleaning composition containing 0-30% by weight of water N-methyl-2-pyrrolidone and selected from phosphines, phenols, One or more compounds among imidazolones, imidazoles, or stilbene compounds.

In one aspect, the present invention relates to a cleaning method, which includes the step of using a cleaning agent composition to clean an object to be cleaned with flux residues, the cleaning agent composition containing an organic solvent (component A), And a compound having an alkyl group with 1 to 4 carbon atoms on the nitrogen atom of the imidazole ring or the piperidine ring (component B).

In one aspect, the present invention relates to a method of manufacturing an electronic component, which includes the steps of: mounting at least one component selected from the group consisting of semiconductor chips, chip-type capacitors, and circuit substrates by soldering using flux At least one of the steps on the circuit board and the step of forming solder bumps for connecting the above-mentioned components on the circuit board; and the cleaning method of the present invention is used to select from the circuit boards equipped with the above-mentioned components and those formed with The step of cleaning at least one of the circuit substrates of the solder bumps.

In one aspect, the present invention relates to a composition which is used as a cleaning agent when cleaning objects to be cleaned with flux residues, and contains an organic solvent (component A) and an imidazole ring or pipette A compound having an alkyl group with 1 to 4 carbon atoms on the ring nitrogen (component B).

In recent years, due to the miniaturization of semiconductor package substrates, the solder bumps have been miniaturized or the gap between the solder bumps and the parts to be connected has narrowed. In addition, due to the miniaturization of solder bumps or the narrowing of the gap between the solder bumps and the parts to be connected, the cleaning agent composition disclosed in the above-mentioned patent documents has insufficient removability of flux residues (flux removal properties) and poor cleaning performance. It can be said to be sufficient.

Therefore, the present invention provides a cleaning agent composition having excellent flux removal properties, a cleaning method using the cleaning agent composition, and a manufacturing method of electronic parts.

According to the present invention, in one aspect, it is possible to provide a cleaning agent composition and cleaning method with excellent flux removability.

The present invention is based on the insight that by using a cleaning agent composition containing a specific solvent and a specific amine to remove flux residues, the removal of flux residues is improved compared to the previous ones.

That is, in one aspect, the present invention relates to a cleaning method (hereinafter, also referred to as "the cleaning method of the present invention"), which includes cleaning the object to be cleaned with flux residues using a cleaning agent composition Steps, and the above-mentioned detergent composition contains an organic solvent (component A) and a compound (component B) having an alkyl group with a carbon number of 1 to 4 on the nitrogen atom of the imidazole ring or piperidine ring. According to the present invention, in one or more embodiments, the flux residue of the cleaning object can be efficiently removed. In addition, the present invention relates to a composition (hereinafter, also referred to as "the cleaning agent composition of the present invention") in other aspects, which is used as a cleaning agent when cleaning objects to be cleaned with flux residues It contains an organic solvent (component A) and a compound (component B) having an alkyl group with 1 to 4 carbon atoms on the nitrogen atom of the imidazole ring or piperidine ring. According to the present invention, in one or a plurality of embodiments, a cleaning agent composition having excellent flux removal properties can be obtained. Furthermore, according to the present invention, in one or more embodiments, it is possible to obtain a cleaning agent composition capable of suppressing influences such as corrosion on solder metal.

Although the details of the action mechanism of the cleaning method of the present invention and the effect of the cleaning composition of the present invention are unclear, they are presumed to be as follows. That is, in the cleaning method of the present invention and the cleaning agent composition of the present invention, component A penetrates into the flux and flux residues that are degraded by reflow, etc., so that the viscosity decreases and becomes easy to flow, and component B functions , It forms a salt with the flux, which decomposes or hydrophilizes the flux and flux residues and makes them easily soluble in the cleaning agent composition. In addition, it is presumed that the flux and flux residues are more soluble in water in the rinse step after cleaning by the component B, and the removal of the rinse can be improved, thereby reducing the residue after cleaning and rinse. Furthermore, it is presumed that the component B acts on the solder metal in the solvent containing the component A so that it does not corrode. As described above, the cleanability can be improved, and therefore, the flux residue removal can suppress the influence of the corrosion on the solder metal. Cleaner composition. However, the present invention may be interpreted without being limited to this mechanism.

In the present invention, the "solder flux" refers to a rosin-based flux containing rosin or rosin derivatives used for soldering or not containing oxides that interfere with the connection of metals such as electrodes or wiring and solder metals to promote the connection. For the water-soluble flux of rosin, etc., the "welding" in the present invention includes reflow welding and flow welding. The "solder flux" in the present invention refers to a mixture of solder and flux. In the present invention, the "flux residue" refers to the residue of self-service flux remaining on the substrate after the solder bumps are formed with flux and/or the substrate after soldering with flux. For example, if other components (for example, semiconductor wafers, chip capacitors, other circuit boards, etc.) are stacked and mounted on a circuit board, a space (gap) is formed between the circuit board and the other components. The flux used for the above mounting will also remain in the gap in the form of flux residue after soldering by reflow or the like.

[Cleaning method] The cleaning method of the present invention is a cleaning method for removing flux residues in one or more embodiments, and it includes the step of using the cleaning agent composition of the present invention to clean the object to be cleaned with flux residues. The cleaning method of the present invention, in one or more embodiments, includes contacting an object to be cleaned with flux residues with the cleaning agent composition of the present invention. As a method of cleaning an object to be cleaned using the detergent composition of the present invention, or a method of contacting the cleaning agent composition of the present invention with the object to be cleaned, for example, contact in the bath of an ultrasonic cleaning device can be cited Method, the method of spraying and contacting the detergent composition (spray method), etc. The detergent composition of the present invention can be directly used for cleaning without dilution. The cleaning method of the present invention preferably includes a step of rinsing with water and drying after contacting the object to be cleaned with the detergent composition. According to the cleaning method of the present invention, the flux residue remaining in the gap of the welded parts can be cleaned efficiently. The solder is preferably lead-free (Pb) solder in terms of the obvious effect of the cleaning performance and the permeability into the narrow gap of the cleaning method of the present invention. Furthermore, from the same point of view, the cleaning method of the present invention is preferably used for the use of International Publication No. 2006/025224, Japanese Patent Publication No. 6-75796, Japanese Patent Application Publication No. 2014-144473, and Japanese Patent Electronic components connected with flux described in JP 2004-230426, JP 2013-188761, JP 2013-173184, etc. In the cleaning method of the present invention, in terms of easily exerting the cleaning power of the detergent composition of the present invention, it is preferable to irradiate ultrasonic waves when the detergent composition of the present invention is in contact with the object to be cleaned, more preferably the super The sound wave is relatively strong. From the same viewpoint, the frequency of the ultrasonic wave is preferably 26 to 72 Hz, 80 to 1500 W, and more preferably 36 to 72 Hz, and 80 to 1500 W.

[Cleaning agent composition] The cleaning agent composition of the present invention is a composition used as a cleaning agent when cleaning objects to be cleaned with flux residues. In one or more embodiments, it is a cleaning agent composition for removing flux residues . In the present invention, the "cleaner composition for removing flux residues" refers to the removal of flux residues after solder bumps and/or after soldering using flux or solder flux in one or more embodiments. The cleaning agent composition. In terms of the manifestation of the significant effect of the cleaning agent composition of the present invention, the solder is preferably a lead (Pb)-free solder containing tin.

Therefore, in one aspect, the present invention relates to a composition that is used as a cleaning agent when cleaning objects to be cleaned with flux residues, and contains an organic solvent (component A), and an imidazole ring or A compound having an alkyl group with 1 to 4 carbon atoms on the nitrogen atom of the piperidine ring (component B). In one aspect, the present invention relates to a cleaning composition for removing flux residues, which contains: a compound selected from the group consisting of a compound represented by the following formula (I), a compound represented by the following formula (II), and the following At least one solvent (component A) in the compound represented by formula (III); and selected from 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1- At least one amine among (2-dimethylaminoethyl)-4-methylpiperidine (ingredient B). In one aspect, the present invention relates to the use of a composition for cleaning objects to be cleaned with flux residues. The composition contains an organic solvent (component A) and an imidazole ring or piper ring. A compound having an alkyl group with 1 to 4 carbon atoms on the nitrogen atom (component B).

(Component A: organic solvent) The component A in the detergent composition of the present invention is an organic solvent. From the viewpoint of improving the flux removal property, the component A is preferably selected from the compound represented by the following formula (I), the compound represented by the following formula (II), and the following in one or more embodiments At least one solvent in the compound represented by formula (III). Component A may be one type, a combination of two types, or a combination of two or more types.

R ¹ -O-(AO) _n -R ² (I)

In the above formula (I), from the viewpoint of improving the flux removal property, R ¹ is preferably a phenyl group or an alkyl group having 1 to 8 carbons, and R ² is a hydrogen atom or a carbon number of 1 to 4 Alkyl, AO is ethylene oxide or propylene oxide, n is the number of AO added moles and is an integer of 1 to 3.

In the above formula (I), from the viewpoint of improving flux removal properties, R ^{1 is} preferably a phenyl group or an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group or an alkyl group having 4 to 6 carbon atoms. The group is more preferably an alkyl group having 4 to 6 carbon atoms. From the viewpoint of improving flux removal properties, R ^{2 is} preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 2 to 4 carbon atoms, and more preferably hydrogen. Atom or n-butyl. In addition, from the viewpoint of improving flux removal properties, R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and R ² is an alkyl group having 1 to 3 carbon atoms. From the viewpoint of improving flux removal properties, AO is preferably an ethylene oxide group or a propylene oxide group, and more preferably an ethylene oxide group. From the viewpoint of improving flux removal properties, n is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 2.

The compound represented by the above formula (I) includes, for example, monophenyl ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether; those having a carbon number of 1 to 8 Alkyl glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, triethylene glycol monoalkyl ethers and other monoalkyl ethers; alkyl groups with carbon numbers 1 to 8 and carbon numbers from 1 to 4 Dialkyl ethers such as ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, and triethylene glycol dialkyl ether of the following alkyl groups; those with a phenyl group and an alkyl group with 1 to 4 carbon atoms Phenyl alkyl ethers such as ethylene glycol phenyl alkyl ether, diethylene glycol phenyl alkyl ether, and triethylene glycol phenyl alkyl ether. The compound represented by the above formula (I) is preferably selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, from the viewpoint of improving flux removability. 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 At least one of dibutyl ether, diethylene glycol dibutyl ether, diethylene glycol dibutyl ether and triethylene glycol dimethyl ether, more preferably selected from diethylene glycol monobutyl ether, diethylene glycol mono At least one of hexyl ether, diethylene glycol monophenyl ether, dipropylene glycol monobutyl ether and diethylene glycol dibutyl ether, and more preferably selected from diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol monobutyl ether At least one of ethylene glycol dibutyl ether and diethylene glycol dimethyl ether, and more preferably diethylene glycol dimethyl ether.

R ³ -CH ₂ OH (II)

In the above formula (II), from the viewpoint of improving flux removal properties, R ^{3 is} preferably phenyl, benzyl, cyclohexyl, furanyl, tetrahydrofuryl, furyl methyl or tetrahydrofuryl methyl, more preferably benzene Group, cyclohexyl or tetrahydrofuranyl, more preferably phenyl or tetrahydrofuranyl, still more preferably phenyl.

Examples of the compound represented by the formula (II) include benzyl alcohol, phenethyl alcohol, cyclohexane methanol, furan methanol, and tetrahydrofuran methanol. The compound represented by the above formula (II) is preferably at least one selected from benzyl alcohol, furanmethanol, and tetrahydrofuranmethanol, and more preferably selected from benzyl alcohol and tetrahydrofuranmethanol, from the viewpoint of improving flux removability At least one of them is more preferably benzyl alcohol.

[化1]

In the above formula (III), from the viewpoint of improving the flux removability, R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, and 1 carbon atom. A hydroxyalkyl group or a hydroxy group of 3 or less, more preferably any one of R ⁴ , R ⁵ , R ⁶ , and R ⁷ is a hydrocarbon group with 1 to 8 carbon atoms, and more preferably a hydrocarbon group with 1 to 6 carbon atoms , And more preferably any of methyl, ethyl, and vinyl.

As the compound represented by the above formula (III), for example, 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-vinyl-2- Pyrrolidone, 1-phenyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone, 3-hydroxypropyl-2-pyrrolidone, 4 -Hydroxy-2-pyrrolidone, 4-phenyl-2-pyrrolidone and 5-methyl-2-pyrrolidone, etc. The compound represented by the above formula (III) is preferably selected from the group consisting of 2-pyrrolidone, 1-methyl-2-pyrrolidone, and 1-ethyl-2 from the viewpoint of improving flux removability. -Pyrrolidone, 1-vinyl-2-pyrrolidone, 1-phenyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone and 5 -At least one of methyl-2-pyrrolidone, more preferably selected from 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone and 1-vinyl-2-pyrrolidine At least one of the ketones is more preferably 1-methyl-2-pyrrolidone.

Component A may also be a combination of one type, two types, or a combination of two or more types. When component A is a combination of two types, as component A, for example, a combination of a compound represented by formula (I) and a compound represented by formula (II) can be cited.

As component A, it is preferably selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, from the viewpoint of improving flux removability. At least one of benzyl alcohol and 1-methyl-2-pyrrolidone, more preferably at least one selected from diethylene glycol monobutyl ether, benzyl alcohol, and 1-methyl-2-pyrrolidone. From the viewpoint of improving the removability of the rosin-based flux, the component A is preferably diethylene glycol dimethyl ether, benzyl alcohol, and 1-methyl-2-pyrrolidone.

The content of component A in the detergent composition of the present invention is preferably 35% by mass or more, more preferably 50% by mass or more, and still more preferably 75% by mass or more from the viewpoint of improving flux removability, and , Preferably 99.5% by mass or less, more preferably 99.3% by mass or less, and still more preferably 99% by mass or less. More specifically, the content of component A in the detergent composition of the present invention is preferably 35% by mass or more and 99.5% by mass or less, more preferably 50% by mass or more and 99.3% by mass or less, and more preferably 75% by mass or more 99% 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 these.

(Component B: Amine) The component B in the detergent composition of the present invention is a compound having an alkyl group with a carbon number of 1 to 4 on the nitrogen atom of the imidazole ring or the piperidine ring. From the standpoint of improving flux removal properties, component B is preferably selected from 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1-(2- At least one amine among dimethylaminoethyl)-4-methylpiperidine. Component B may be one type, a combination of two types, or a combination of two or more types. From the viewpoint of improving the removability of rosin-based fluxes, component B is preferably a compound having an alkyl group with a carbon number of 1 to 4 on the nitrogen atom of the imidazole ring, and is preferably selected from 1-methylimidazole, 1 At least one amine selected from the group consisting of 2-dimethylimidazole and 1-isobutyl-2-methylimidazole, more preferably at least one amine selected from 1-methylimidazole and 1,2-dimethylimidazole .

The content of component B in the detergent composition of the present invention is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.4% by mass or more, from the viewpoint of improving flux removability. More preferably, it is 0.5% by mass or more, and from the viewpoint of suppressing corrosion of the solder metal, it is preferably 15% by mass or less, more preferably 12% by mass or less, more preferably 10% by mass or less, and even more preferably 8 Mass% or less, more preferably 5 mass% or less. More specifically, the content of component B in the detergent composition of the present invention is preferably 0.2% by mass or more and 15% by mass or less, more preferably 0.3% by mass or more and 10% by mass or less, and still more preferably 0.4% by mass or more 8 mass% or less, more preferably 0.5 mass% or more and 5 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 these.

In the detergent composition of the present invention, the mass ratio of component A to component B (component A/component B) is preferably 8 or more, more preferably 10 or more, and more preferably, from the viewpoint of improving flux removability It is 15 or more, and is preferably 200 or less, more preferably 100 or less, and still more preferably 25 or less. More specifically, the mass ratio (component A/component B) is preferably 8 or more and 200 or less, more preferably 10 or more and 100 or less, and still more preferably 15 or more and 25 or less.

(Component C: Water) The cleanser composition of the present invention may further contain water (component C) in one or more embodiments. As the component C, ion exchange water, RO (reverse osmosis) water, distilled water, pure water, ultrapure water, etc. can be used. The content of Component C in the detergent composition of the present invention 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 reducing the ignition point. From the viewpoint of improving the flux removability, it is preferably 55% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, and still more preferably 10% by mass or less. More specifically, the content of Component C in the detergent composition of the present invention is preferably 1% by mass or more and 55% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and still more preferably 5% by mass or more 12% by mass or less, more preferably 8% by mass or more and 10% by mass or less.

When the detergent composition of the present invention contains component C, from the viewpoint of improving stability, the component A contained in the detergent composition of the present invention is preferably a combination of diethylene glycol monobutyl ether and the Component A other than diethylene glycol monobutyl ether.

(Other ingredients) In addition to the above-mentioned components A to C, the detergent composition of the present invention may contain other components as necessary. The content of other components in the detergent composition of the present invention is preferably 0 mass% or more and 10 mass% or less, more preferably 0 mass% or more and 8 mass% or less, and still more preferably 0 mass% or more and 5 mass% or less, Furthermore, it is more preferable that it is 0 mass% or more and 2 mass% or less.

As other components in the detergent composition of the present invention, from the viewpoint of improving stability, for example, surfactants can be cited. As the surfactant, for example, polyoxyalkylene alkyl ether, polyoxyalkylene alkylamine, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkyl glucoside, alkyl Nonionic surfactants such as glyceryl ethers are more preferably polyoxyalkylene alkyl ethers and alkyl glycerol ethers, and even more preferably alkyl glycerol ethers. Specific examples of the surfactant include 2-ethylhexyl glyceryl ether and the like. From the viewpoint of improving stability, the content of the surfactant in the detergent composition of the present invention is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and more preferably 7% by mass or less, more Preferably, it is 5 mass% or less. More specifically, the content of the surfactant is preferably from 0.5% by mass to 7% by mass, and more preferably from 0.8% by mass to 5% by mass.

As still other ingredients, the detergent composition of the present invention may contain hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, and ethylene that are commonly used in detergents as needed within a range that does not impair the effects of the present invention. Chelating compounds such as amino carboxylates such as diaminetetraacetic acid, rust inhibitors such as benzotriazole, thickeners, dispersants, alkaline substances other than component B, polymer compounds, cosolvents, preservatives , Bactericide, antibacterial agent, defoamer, antioxidant.

[Manufacturing method of detergent composition] The detergent composition of the present invention can be produced by, for example, blending component A and component B, and optionally the above-mentioned component C and other components using a known method. The cleanser composition of the present invention can be obtained by blending at least component A and component B in one or more embodiments. Therefore, in one aspect, the present invention relates to a method for manufacturing a detergent composition including the steps of at least blending component A and component B. The "preparation" in the present invention includes mixing component A, component B, and optionally component C and other components simultaneously or in any order. In the manufacturing method of the detergent composition of the present invention, the blending amount of each component can be the same as the content of each component of the detergent composition of the present invention. In the present invention, the "content of each component in the detergent composition" refers to the content of the above-mentioned components at the time of cleaning, that is, at the point in time when the detergent composition is used for cleaning.

The detergent composition of the present invention can also be manufactured and stored in the form of a concentrate from the viewpoint of addition operation, storage and transportation. As the dilution ratio of the concentrate of the detergent composition of the present invention, for example, 3 times or more and 30 times or less can be cited. The concentrate of the detergent composition of the present invention can utilize water (ingredient C) in such a way that component A, component B, and optionally blended component C and other components become the above-mentioned content (ie, the content during cleaning) during use. Dilute and use.

[PH value of detergent composition] The detergent composition of the present invention is preferably alkaline in terms of improving the flux removability, and for example, the pH value is 8 or more and pH value is 14 or less. The pH value can be adjusted by appropriately blending the following as needed, namely: inorganic acids such as nitric acid and sulfuric acid; organic acids such as hydroxycarboxylic acids, polycarboxylic acids, amino polycarboxylic acids, and amino acids; and These metal salts or ammonium salts, ammonia, sodium hydroxide, potassium hydroxide, amines and other alkaline substances other than component B. The pH value of the detergent composition in the present invention is the pH value when the detergent composition is used (after dilution) at 25°C.

[Object to be cleaned] The cleaning agent composition of the present invention is used in one or more embodiments for cleaning objects to be cleaned with flux residues. As an object to be cleaned with flux residue, for example, an object to be cleaned with reflowed solder can be cited. As a specific example of the object to be cleaned, for example, electronic parts and their manufacturing intermediates can be cited, specifically, soldered electronic parts and manufacturing intermediates thereof can be cited, and more specifically, include: electronic parts with parts soldered with solder And its manufacturing intermediates, electronic parts with parts connected via solder and their manufacturing intermediates, electronic parts containing flux residues in the gaps between soldered parts and their manufacturing intermediates, between parts connected via solder Electronic parts and manufacturing intermediates containing flux residue in the gap. The above-mentioned manufacturing intermediate is the intermediate manufacturing in the manufacturing steps of electronic parts including semiconductor packages or semiconductor devices. For example, it includes mounting at least selected from the group consisting of semiconductor chips, chip capacitors, and circuit substrates by soldering using flux A circuit substrate of a component, and/or a circuit substrate formed with solder bumps for soldering the above components. The so-called gap in the object to be cleaned refers to, for example, the space formed between the circuit board and the parts (semiconductor chip, chip capacitor, circuit board, etc.) soldered and mounted on the circuit board, and is the height (the distance between the parts) For example, it is a space of 5 to 500 μm, 10 to 250 μm, or 20 to 100 μm. The width and depth of the gap depend on the size or spacing of the mounted parts or electrodes (pads) on the circuit board.

[Method of manufacturing electronic parts] In one aspect, the present invention relates to a method of manufacturing electronic components (hereinafter, also referred to as "the manufacturing method of electronic components of the present invention"), which includes the following steps: selected from semiconductor chips, chip capacitors and At least one of the steps of mounting at least one component in the circuit board on the circuit board by soldering using flux and the step of forming solder bumps for connecting the above-mentioned components on the circuit board; and by this The cleaning method of the invention is a step of cleaning at least one selected from a circuit board on which the above-mentioned components are mounted and a circuit board on which the solder bumps are formed. The soldering using flux is, for example, a lead-free solder, which may be a reflow method or a flow soldering method. Electronic parts include semiconductor packages without semiconductor chips, semiconductor packages with semiconductor chips, and semiconductor devices. The manufacturing method of the electronic component of the present invention reduces the flux residue remaining in the gap of the soldered component or the periphery of the solder bump by performing the cleaning method of the present invention, thereby suppressing the residue caused by the flux residue There is a short circuit between the electrodes or poor connection, so it is possible to manufacture electronic parts with higher reliability. Furthermore, by performing the cleaning method of the present invention, the cleaning of the flux residue remaining in the gap of the soldered parts, etc. becomes easy, so the cleaning time can be shortened, and the manufacturing efficiency of electronic parts can be improved.

[Set] In one aspect, the present invention relates to a kit used in the cleaning method of the present invention and/or the manufacturing method of the electronic component of the present invention (hereinafter, also referred to as "the kit of the present invention"). The kit of the present invention is used in one or more embodiments to manufacture the kit of the detergent composition of the present invention.

As an embodiment of the kit of the present invention, a solution containing the aforementioned component A (first solution) and a solution containing component B (second solution) in a non-mixed state can be cited, and the second solution is mixed during use. A set of one-component and second-component (two-component detergent composition). Therefore, the cleaning method of the present invention may include the following steps in one or more embodiments: the second solution is not mixed with the solution containing component A (first solution) and the solution containing component B (second solution). The first liquid and the second liquid are mixed at the time of use to prepare a detergent composition. In addition, the cleaning method of the present invention may include the following steps in one or more embodiments: using a solution containing component A (first solution) and a solution containing component B (second solution) in an immiscible state The set is to mix the first liquid and the second liquid during use to prepare a detergent composition. The said 1st liquid and the said 2nd liquid may contain the said component C and other components, respectively as needed. At least one of the above-mentioned first liquid and second liquid may contain part or all of component C (water) in one or more embodiments. In one or more embodiments, after mixing the above-mentioned first liquid and second liquid, it may be diluted with component C (water) as necessary.

上述式(III)中，R⁴ 、R⁵ 、R⁶ 、R⁷ 分別獨立為氫原子、碳數1以上8以下之烴基、碳數1以上3以下之羥烷基或羥基。The present invention further relates to one or more of the following embodiments. <1> A cleaning composition for removing flux residues, comprising: selected from the group consisting of compounds represented by the following formula (I), compounds represented by the following formula (II), and those represented by the following formula (III) At least one solvent (component A) in the compound; and selected from 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1-(2-dimethylimidazole At least one amine of (aminoethyl)-4-methylpiperidine (component B). R ¹ -O-(AO) _n -R ² (I) In the above formula (I), R ¹ is a phenyl group or an alkyl group with a carbon number of 1 to 8 and R ² is a hydrogen atom or a carbon number of 1 to 4 The alkyl group, AO is an ethylene oxide group or a propylene oxide group, n is the number of AO added moles and is an integer of 1 to 3. R ³ -CH ₂ OH (II) In the above formula (II), R ³ is phenyl, benzyl, cyclohexyl, furanyl, tetrahydrofuranyl, furyl methyl or tetrahydrofuryl methyl. [化2]

In the above formula (III), R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydroxyl group.

上述式(III)中，R⁴ 、R⁵ 、R⁶ 、R⁷ 分別獨立為氫原子、碳數1以上8以下之烴基、碳數1以上3以下之羥烷基或羥基。 ＜31＞如＜28＞至＜30＞中任一項之清潔方法，其中上述清潔劑組合物中之成分A之含量為35質量%以上99.5質量%以下。 ＜32＞如＜28＞至＜31＞中任一項之清潔方法，其中上述清潔劑組合物中之成分A與成分B之質量比(成分A/成分B)為8以上200以下。 ＜33＞如＜28＞至＜32＞中任一項之清潔方法，其中上述清潔劑組合物進而含有水(成分C)。 ＜34＞如＜33＞之清潔方法，其中上述清潔劑組合物中之成分C之含量為15質量%以下。 ＜35＞如＜28＞至＜34＞中任一項之清潔方法，其中上述清潔劑組合物中之成分B之含量為0.2質量%以上15質量%以下。 ＜36＞如＜28＞至＜35＞中任一項之清潔方法，其中成分A為選自二乙二醇單丁醚、二丙二醇單丁醚、二乙二醇二丁醚、二乙二醇二甲醚、苄醇及1-甲基-2-吡咯啶酮中之至少一種。 ＜37＞如＜28＞至＜36＞中任一項之清潔方法，其中上述清潔劑組合物中之成分A～C以外之其他成分之含量為0質量%以上10質量%以下。 ＜38＞如＜28＞至＜37＞中任一項之清潔方法，其中被清潔物為焊接電子零件之製造中間物。 ＜39＞如＜28＞至＜38＞中任一項之清潔方法，其包括如下步驟：於含有成分A之溶液(第1液)與含有成分B之溶液(第2液)互不混合之狀態下將第1液與第2液於使用時混合而製備清潔劑組合物。 ＜40＞如＜28＞至＜39＞中任一項之清潔方法，其係使用在超音波清潔裝置之浴槽內進行接觸之方法、或將清潔劑組合物呈噴霧狀射出而進行接觸之方法，利用上述清潔劑組合物對被清潔物進行清潔。 ＜41＞一種電子零件之製造方法，其包括如下步驟：選自將選自半導體晶片、晶片型電容器及電路基板中之至少一種零件藉由使用助焊劑之焊接而搭載於電路基板上之步驟以及將用於連接上述零件等之焊料凸塊形成於電路基板上之步驟中的至少一個步驟；及藉由如＜28＞至＜40＞中任一項之清潔方法對選自搭載有上述零件之電路基板及形成有上述焊料凸塊之電路基板中之至少一種進行清潔之步驟。 ＜42＞一種組合物，其係用以於具有助焊劑殘餘物之被清潔物之清潔時用作清潔劑者，且含有有機溶劑(成分A)、及於咪唑環或哌𠯤環之氮原子上具有碳數1以上4以下之烷基之化合物(成分B)。 ＜43＞一種組合物之用途，其係用於具有助焊劑殘餘物之被清潔物之清潔，該組合物含有有機溶劑(成分A)、及於咪唑環或哌𠯤環之氮原子具有碳數1以上4以下之烷基之化合物(成分B)。 [實施例]<2> The detergent composition as in <1>, wherein in the above formula (I), R ¹ is a phenyl group or an alkyl group having 1 to 8 carbon atoms, preferably a phenyl group or a carbon number of 4 to 6 The alkyl group is more preferably an alkyl group having 4 to 6 carbon atoms. <3> The detergent composition of <1> or <2>, wherein in the above formula (I), R ² is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, preferably a hydrogen atom or 2 carbon atoms The alkyl group of 4 or less is more preferably a hydrogen atom or an n-butyl group. <4> The detergent composition according to any one of <1> to <3>, wherein in the above formula (I), AO is an ethylene oxide group or a propylene oxide group, preferably an ethylene oxide group . <5> The detergent composition according to any one of <1> to <4>, wherein 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. <6> The detergent composition of any one of <1> to <5>, wherein in the above formula (II), R ³ represents phenyl, benzyl, cyclohexyl, furanyl, tetrahydrofuranyl, furanmethyl Or tetrahydrofuryl methyl, preferably phenyl, cyclohexyl or tetrahydrofuryl, more preferably phenyl or tetrahydrofuryl, and still more preferably phenyl. <7> The detergent composition according to any one of <1> to <6>, wherein in the above formula (III), R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom with a carbon number of 1 or more A hydrocarbon group of 8 or less, a hydroxyalkyl group or a hydroxy group having a carbon number of 1 to 3, preferably any of R ⁴ , R ⁵ , R ⁶ , and R ⁷ is a hydrocarbon group of 1 to 8 carbons, more preferably carbon The hydrocarbon group having a number of 1 to 6 is more preferably any of a methyl group, an ethyl group, and a vinyl group. <8> The detergent composition according to any one of <1> to <7>, wherein component A is preferably selected from diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and diethylene glycol dibutyl ether , At least one of benzyl alcohol and 1-methyl-2-pyrrolidone, more preferably at least one selected from the group consisting of diethylene glycol monobutyl ether, benzyl alcohol and 1-methyl-2-pyrrolidone. <9> The detergent composition of any one of <1> to <8>, wherein the content of component A is preferably 35% by mass or more, more preferably 50% by mass or more, and still more preferably 75% by mass or more . <10> The detergent composition of any one of <1> to <9>, wherein the content of component A is preferably 99.5 mass% or less, more preferably 99.3 mass% or less, and still more preferably 99 mass% or less . <11> The detergent composition of any one of <1> to <10>, wherein the content of component A is preferably 35% by mass to 99.5% by mass, more preferably 50% by mass to 99.3% by mass, More preferably, it is 75% by mass or more and 99% by mass or less. <12> The detergent composition of any one of <1> to <11>, wherein the content of component B is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.4% by mass or more , And more preferably 0.5% by mass or more. <13> The detergent composition of any one of <1> to <12>, wherein the content of component B is preferably 15% by mass or less, more preferably 12% by mass or less, and more preferably 10% by mass or less, It is more preferably 8% by mass or less, and still more preferably 5% by mass or less. <14> The detergent composition of any one of <1> to <13>, wherein the content of component B is preferably 0.2% by mass to 15% by mass, more preferably 0.3% by mass to 10% by mass, It is more preferably 0.4% by mass or more and 8% by mass or less, and still more preferably 0.5% by mass or more and 5% by mass or less. <15> The detergent composition according to any one of <1> to <14>, wherein the mass ratio of component A to component B (component A/component B) is preferably 8 or more, more preferably 10 or more, and further Preferably it is 15 or more. <16> The detergent composition of any one of <1> to <15>, wherein the mass ratio of component A to component B (component A/component B) is preferably 200 or less, more preferably 100 or less, and further Preferably it is 25 or less. <17> The detergent composition of any one of <1> to <16>, wherein the mass ratio of component A to component B (component A/component B) is preferably 8 or more and 200 or less, more preferably 10 or more 100 or less, more preferably 15 or more and 25 or less. <18> The detergent composition of any one of <1> to <17>, which further contains water (component C). <19> The detergent composition according to <18>, wherein the content of component C is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more. <20> The detergent composition as in <18> or <19>, wherein the content of component C is preferably 55% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, and still more preferably It is 10% by mass or less. <21> The detergent composition of any one of <18> to <20>, wherein the content of component C is preferably 1% by mass to 55% by mass, more preferably 1% by mass to 15% by mass, It is more preferably 5 mass% or more and 12 mass% or less, and still more preferably 8 mass% or more and 10 mass% or less. <22> The detergent composition of any one of <1> to <21>, which further contains a surfactant. <23> The detergent composition of any one of <1> to <22>, which further contains a compound selected from chelating power, rust inhibitors such as benzotriazole, thickener, dispersant, and component B At least one of other alkaline substances, polymer compounds, cosolvents, preservatives, bactericides, antibacterial agents, defoamers, and antioxidants. <24> A cleaning method, which includes the step of using the cleaning agent composition of any one of <1> to <23> to clean the object to be cleaned with flux residue. <25> The cleaning method such as <24>, wherein the object to be cleaned is the manufacturing intermediate for welding electronic parts. <26> A method of manufacturing electronic components, comprising the steps of: mounting at least one component selected from the group consisting of semiconductor chips, chip capacitors, and circuit substrates on the circuit substrate by soldering using flux, and At least one of the steps of forming solder bumps for connecting the above-mentioned parts on the circuit board; and forming a circuit board selected from the above-mentioned parts by a cleaning method such as <24> or <25> The step of cleaning at least one of the circuit substrates with the above-mentioned solder bumps. <27> A kit used for cleaning methods such as <24> or <25> and/or manufacturing methods of electronic parts such as <26>, and contains a solution containing component A in an immiscible state (The first liquid) and the solution containing the component B (the second liquid), and the first liquid and the second liquid are mixed during use. <28> A cleaning method, which includes the step of using a cleaning agent composition to clean the object to be cleaned with flux residues, and the cleaning agent composition contains an organic solvent (component A), and an imidazole ring or A compound having an alkyl group with 1 to 4 carbon atoms on the nitrogen atom of the piperidine ring (component B). <29> The cleaning method such as <28>, wherein component B is selected from 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1-(2-di At least one amine of methylaminoethyl)-4-methylpiperidine. <30> The cleaning method such as <28> or <29>, wherein component A is selected from the compound represented by the following formula (I), the compound represented by the following formula (II), and the following formula (III) At least one solvent in the indicated compound. R ¹ -O-(AO) _n -R ² (I) In the above formula (I), R ¹ is a phenyl group or an alkyl group with a carbon number of 1 to 8 and R ² is a hydrogen atom or a carbon number of 1 to 4 The alkyl group, AO is an ethylene oxide group or a propylene oxide group, n is the number of AO added moles and is an integer of 1 to 3. R ³ -CH ₂ OH (II) In the above formula (II), R ³ is phenyl, benzyl, cyclohexyl, furanyl, tetrahydrofuranyl, furyl methyl or tetrahydrofuryl methyl. [化3]

In the above formula (III), R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydroxyl group. <31> The cleaning method according to any one of <28> to <30>, wherein the content of component A in the detergent composition is 35% by mass or more and 99.5% by mass or less. <32> The cleaning method of any one of <28> to <31>, wherein the mass ratio of component A to component B (component A/component B) in the detergent composition is 8 or more and 200 or less. <33> The cleaning method of any one of <28> to <32>, wherein the detergent composition further contains water (component C). <34> The cleaning method as in <33>, wherein the content of component C in the detergent composition is 15% by mass or less. <35> The cleaning method according to any one of <28> to <34>, wherein the content of the component B in the detergent composition is 0.2% by mass or more and 15% by mass or less. <36> The cleaning method such as any one of <28> to <35>, wherein component A is selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, and diethylene two At least one of dimethyl ether, benzyl alcohol and 1-methyl-2-pyrrolidone. <37> The cleaning method according to any one of <28> to <36>, wherein the content of other components other than components A to C in the detergent composition is 0% by mass to 10% by mass. <38> The cleaning method as in any one of <28> to <37>, wherein the object to be cleaned is an intermediate in the manufacture of welding electronic parts. <39> The cleaning method such as any one of <28> to <38>, which includes the following steps: the solution containing component A (first solution) and the solution containing component B (second solution) are not mixed with each other In the state, the first liquid and the second liquid are mixed at the time of use to prepare a detergent composition. <40> The cleaning method such as any one of <28> to <39>, which is a method of contacting in the bath of an ultrasonic cleaning device, or a method of spraying the detergent composition into a spray to contact , Use the above-mentioned detergent composition to clean the object to be cleaned. <41> A method of manufacturing electronic components, comprising the steps of: mounting at least one component selected from the group consisting of semiconductor chips, chip capacitors, and circuit substrates on the circuit substrate by soldering using flux; and At least one of the steps of forming solder bumps used to connect the above-mentioned parts on the circuit board; and by cleaning methods such as any one of <28> to <40> to select from those equipped with the above-mentioned parts At least one of the circuit substrate and the circuit substrate on which the solder bumps are formed is cleaned. <42> A composition used as a cleaning agent for cleaning objects with flux residues, and containing an organic solvent (component A) and nitrogen atoms in the imidazole ring or the piperidine ring A compound having an alkyl group with a carbon number of 1 to 4 (component B). <43> The use of a composition for cleaning objects to be cleaned with flux residues. The composition contains an organic solvent (component A) and the nitrogen atom of the imidazole ring or piperidine ring has carbon number Compounds of alkyl groups of 1 to 4 (component B). [Example]

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited by these examples.

1. Preparation of detergent composition (Examples 1-16, Comparative Examples 1-9) In a 100 mL glass beaker, the ingredients were blended so as to have the composition described in Table 1 below, and mixed under the following conditions to prepare the detergent combinations of Examples 1-16 and Comparative Examples 1-9 Things. Unless otherwise specified, the numerical value of each component in Table 1 indicates the content (mass%) in the prepared detergent composition. ＜Mixed conditions＞ Liquid temperature: 25℃ Stirrer: Magnetic stirrer (50 mm rotor) Speed: 300 rpm Stirring time: 10 minutes

The following are used as components of the detergent composition. (Ingredient A) A1: Benzyl alcohol [manufactured by Lanxess Co., Ltd.] A2: Diethylene glycol monobutyl ether [manufactured by Japan Emulsifier Co., Ltd., diethylene glycol butyl ether (BDG)] A3: Dipropylene glycol monobutyl ether [manufactured by Japan Emulsifier Co., Ltd., dipropylene glycol butyl ether (BFDG)] A4: Diethylene glycol dimethyl ether [manufactured by Japan Emulsifier Co., Ltd., diethylene glycol dimethyl ether (DMDG)] A5: 1-Methyl-2-pyrrolidone [manufactured by Fujifilm Wako Pure Chemical Co., Ltd.] (Ingredient B) B1: 1-Methylimidazole [manufactured by Kao Co., Ltd., Kaolizer No.110] B2: 1,2-Dimethylimidazole [manufactured by Tokyo Chemical Industry Co., Ltd.] B3: 1-isobutyl-2-methylimidazole [manufactured by Kao Co., Ltd., Kaolizer No.120] B4: 1-(2-Dimethylaminoethyl)-4-methylpiperidine [manufactured by Kao Co., Ltd., Kaolizer No. 8] (Non-component B) B5: Triethanolamine [manufactured by Nippon Shokubai Co., Ltd.] B6: Methyldiethanolamine [manufactured by Japan Emulsifier Co., Ltd., amino alcohol MDA] B7: 2-Ethyl-4-methylimidazole [manufactured by Fujifilm Wako Pure Chemical Co., Ltd.] B8: 1,5-Dimethyl-2-pyrrolidone (Ingredient C) Water [Pure water less than 1 μS/cm produced by G-10DSTSET, a pure water device manufactured by Organo Co., Ltd.] (Other ingredients: Surfactant) 2-Ethylhexyl glyceryl ether [manufactured by the following manufacturing method] 130 g of 2-ethylhexanol and 2.84 g of boron trifluoride ether complex were cooled to 0°C while stirring. While keeping the temperature at 0°C, 138.8 g of epichlorohydrin was dropped over 1 hour. After the dropping, the remaining alcohol was distilled off at 100°C under reduced pressure (13～26 Pa). The reaction mixture was cooled to 50°C, 125 g of 48% sodium hydroxide aqueous solution was dropped over 1 hour while maintaining 50°C, and after stirring for 3 hours, 200 mL of water was added to separate the layers. After removing the water layer, it was washed twice with 100 mL of water to obtain 208 g of crude 2-ethylhexyl glycidyl ether. 208 g of the crude 2-ethylhexyl glycidyl ether, 104.8 g of water, 5.82 g of lauric acid, and 18.5 g of potassium hydroxide were added to the autoclave and stirred at 140° C. for 5 hours. After dehydration at 100°C under reduced pressure (6.67 kPa), 9.7 g of lauric acid and 2.72 g of potassium hydroxide were added, and reacted at 160°C for 15 hours, and then vacuum distillation (53～67 Pa, 120～ 123° C.) was refined to obtain 110.2 g of 2-ethylhexyl glyceryl ether. (Other ingredients: rust inhibitor) Benzotriazole [manufactured by Tokyo Chemical Industry Co., Ltd., 1,2,3-benzotriazole]

2. Evaluation of detergent composition Using the prepared detergent compositions of Examples 1-16 and Comparative Examples 1-9, the cleaning properties and corrosion resistance were tested and evaluated.

＜Test board＞ On the copper wiring printed circuit board (10 mm×15 mm), use a screen to coat the following solder paste. The test substrate was produced by reflowing at 250°C in a nitrogen atmosphere.

＜The composition of flux＞ Fully hydrogenated rosin (manufactured by Eastman Chemical Company, Foral AX-E) 58.0% by mass N,N'-Diphenylguanidine hydrobromide (manufactured by Wako Chemical Co., Ltd.) 0.5% by mass Adipic acid (manufactured by Wako Pure Chemical Industry Co., Ltd.) 0.5% by mass Hydrogenated castor oil (manufactured by Feng Guo Oil Co., Ltd.) 6.0% by mass Hexyldiol (manufactured by Japan Emulsifier Co., Ltd.) 35.0% by mass

<The manufacturing method of flux> The flux of the above composition is obtained by adding and dissolving the remaining other components in the hexyl glycol of the solvent.

＜Method of manufacturing solder paste＞ 11.0 g of the above-mentioned flux and 89.0 g of solder powder [manufactured by Senju Metal Industry Co., Ltd., M705 (Sn/Ag/Cu=96.5/3/0.5)] were kneaded for 1 hour to prepare.

＜Cleaning test＞ The cleaning test is carried out in the following order. First, prepare the ultrasonic cleaning tank, the first washing tank, and the second washing tank under the following conditions. The ultrasonic cleaning tank sets the frequency to 40 kHz and the output to 200 W. It is obtained by adding 50 g of each detergent composition in a 50 mL glass beaker, putting it in the ultrasonic cleaning layer and heating it to 60°C. The first washing tank and the second washing tank are obtained by the following method: prepare two 100 mL glass beakers with a 50 mm rotor and add 100 g of pure water respectively, put them in the warm bath, and stir at 100 rpm. Heat to 40°C on one side. Secondly, the test substrate was held with tweezers and inserted into the above-mentioned ultrasonic cleaning tank for immersion for 5 minutes. Then, the test substrate was held with tweezers and inserted into the first washing tank, while stirring at 100 rpm, immersed for 3 minutes. Furthermore, the test substrate was held with tweezers and inserted into the second rinse tank, and immersed for 3 minutes while stirring at 100 rpm. Finally, the test substrate was flushed with nitrogen and dried.

[Evaluation of Cleanability (Flux Removability)] After cleaning, observe the test substrate with a desktop microscope Miniscope TM3030 (manufactured by Hitachi High-Tech Co., Ltd.) to visually confirm the presence or absence of residual flux residues on any 10-point solder bumps, and count the number of flux residues number. The results are shown in Table 1. Furthermore, the test substrate was observed with an optical microscope VHX-2000 (manufactured by KEYENCE Co., Ltd.) to visually confirm the presence or absence of flux residues remaining near the solder bumps, and count the solders with flux residues remaining near the solder bumps The number of bumps. The results are shown in Table 1.

[Evaluation of corrosion resistance] Using the optical microscope VHX-2000 (manufactured by KEYENCE Co., Ltd.) and the desktop microscope Miniscope TM3030 (manufactured by Hitachi High-Technologies Co., Ltd.), the solder metal on the test substrate was evaluated for cleanliness (flux removal). Visually observe, and evaluate the influence on solder metal based on the following evaluation criteria. The evaluation results are shown in Table 1. <Evaluation criteria> A: No influence on solder metal B: There is an impact on the solder metal due to corrosion, etc.

[Evaluation of cleanliness (solubility of rosinic acid)] In order to confirm the affinity of the flux, use the following method to evaluate the solubility of rosinic acid used as a component of the flux. The evaluation results are shown in Table 1. Add 100 g of the detergent composition and 1 g of rosinic acid to a 50 mL glass beaker, use an ultrasonic cleaning tank, set the frequency to 40 kHz and set the output to 200 W, and perform ultrasonic waves at 25°C for 1 hour deal with. When the rosinic acid is dissolved, add 1 g of rosinic acid and perform the same operation. This operation is repeated until the pinoresinic acid becomes undissolved, thereby estimating the solubility. The higher the solubility, the better the rosin-based flux removability can be evaluated. From the viewpoint of improving the removability of the rosin-based flux, it can be evaluated that the solubility is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. <Evaluation criteria> A: The solubility is 60% by mass or more B: The solubility is 50% by mass or more and less than 60% by mass C: The solubility is more than 40% by mass and less than 50% by mass D: The solubility is less than 40% by mass

[Table 1] Table 1 Example Detergent composition ingredient 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Ingredient A A1 Benzyl alcohol 99.0 80.0 80.0 80.0 80.0 85.0 80.0 70.0 80.0 30.0 80.0 A2 Diethylene glycol monobutyl ether 5.0 5.0 5.0 5.0 85.0 25.0 1.0 10.0 A3 Dipropylene glycol monobutyl ether 85.0 A4 Diethylene glycol dimethyl ether 85.0 A5 1-methyl-2-pyrrolidone 85.0 80.0 Ingredient B B1 1-methylimidazole 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 B2 1,2-Dimethylimidazole 5.0 B3 1-isobutyl-2-methylimidazole 5.0 B4 1-(2-Dimethylaminoethyl)-4-methylpiperidine 1.0 5.0 5.0 10.0 Ingredient C water 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 9.0 9.0 15.0 55.0 10.0 other Benzotriazole 1.0 2-ethylhexyl glyceryl ether 5.0 5.0 Mass ratio [component A/component B] 99.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 16.0 19.0 16.2 16.0 8.0 8.0 Evaluation Flux removal On solder bump (pcs) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 Near the solder bump (a) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Corrosion resistance Effect on solder metal A A A A A A A A A A A A A A A A Pinoleic acid solubility Solubility (mass%) 40 50 50 45 40 50 45 45 55 80 50 45 50 75 30 55 Evaluation C B B C C B C C B A B C B A D B Comparative example Detergent composition ingredient 1 2 3 4 5 6 7 8 9 Ingredient A A1 Benzyl alcohol 100.0 90.0 85.0 85.0 85.0 95.0 70.0 85.0 A2 Diethylene glycol monobutyl ether 25.0 Ingredient B B1 1-methylimidazole 100.0 Non-ingredient B B5 Triethanolamine 5.0 5.0 5.0 B6 Methyldiethanolamine 5.0 B7 2-ethyl-4-methylimidazole 5.0 B8 1,5-Dimethyl-2-pyrrolidone 5.0 Ingredient C water 10.0 10.0 10.0 10.0 10.0 Mass ratio [component A/component B] or mass ratio [component A/non-component B] - - - 17.0 17.0 17.0 19.0 19.0 17.0 Evaluation Flux removal On solder bump (pcs) 3 3 5 4 4 3 2 3 3 Near the solder bump (a) 2 2 6 1 1 1 2 1 2 Corrosion resistance Effect on solder metal A A B A A A A A A

As shown in Table 1 above, the detergent compositions of Examples 1 to 16 containing Component A and Component B are superior in flux removability compared to Comparative Examples 1 to 9 not containing Component A or Component B. Furthermore, the effect of the detergent compositions of Examples 1-16 on the solder metal was suppressed. In addition, the detergent compositions of Examples 2 to 3, 6, 9 to 11, 13 to 14, and 16 have a higher solubility of rosinic acid of 50% by mass or more, which is comparable to Examples 1, 4 to 5, and 7 to 8. Compared with, 12 and 15, rosin-based flux has excellent removability. Industrial availability

By using the present invention, the cleaning of flux residues can be performed well. Therefore, for example, the cleaning steps of the flux residues in the manufacturing process of electronic parts can be shortened and the performance and reliability of the manufactured electronic parts can be improved. , Which can improve the productivity of electronic parts.

Claims (16)

A cleaning method, which includes the step of using a cleaning agent composition to clean an object to be cleaned with flux residues, and The aforementioned detergent composition contains an organic solvent (component A) and a compound (component B) having an alkyl group with a carbon number of 1 to 4 on the nitrogen atom of the imidazole ring or the piperidine ring. The cleaning method of claim 1, wherein component B is selected from 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1-(2-dimethylamine (Ethyl)-4-methylpiperidine at least one amine. The cleaning method of claim 1 or 2, wherein component A is selected from the group consisting of a compound represented by the following formula (I), a compound represented by the following formula (II), and a compound represented by the following formula (III) At least one solvent, 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 carbon number An alkyl group of 1 to 4, AO is ethylene oxide or propylene oxide, n is the number of AO added and an integer of 1 to 3, R ³ -CH ₂ OH (II) The above formula In (II), R ³ is phenyl, benzyl, cyclohexyl, furanyl, tetrahydrofuranyl, furyl methyl or tetrahydrofuryl methyl, [化1]

In the above formula (III), R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydroxyl group. The cleaning method of claim 1 or 2, wherein the content of the component A in the detergent composition is 35% by mass or more and 99.5% by mass or less. The cleaning method of claim 1 or 2, wherein the mass ratio of component A to component B (component A/component B) in the detergent composition is 8 or more and 200 or less. The cleaning method of claim 1 or 2, wherein the above-mentioned detergent composition further contains water (component C). The cleaning method of claim 6, wherein the content of the component C in the cleaning agent composition is 15% by mass or less. The cleaning method of claim 1 or 2, wherein the content of component B in the detergent composition is 0.2% by mass or more and 15% by mass or less. The cleaning method of claim 1 or 2, wherein component A is selected from diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, benzyl alcohol and 1 -At least one of methyl-2-pyrrolidone. The cleaning method according to claim 1 or 2, wherein the content of other components other than components A to C in the detergent composition is 0% by mass or more and 10% by mass or less. Such as the cleaning method of claim 1 or 2, wherein the object to be cleaned is a manufacturing intermediate for welding electronic parts. For example, the cleaning method of claim 1 or 2, which includes the following steps: the first solution and the second solution are not mixed with the solution containing component A (first solution) and the solution containing component B (second solution). The liquid is mixed during use to prepare a detergent composition. For example, the cleaning method of claim 1 or 2, which uses the method of contacting in the bath of the ultrasonic cleaning device or the method of spraying the cleaning agent composition in the form of spray to contact, and the cleaning agent composition is used to clean The objects are cleaned. A method of manufacturing electronic components, comprising the steps of: mounting at least one component selected from the group consisting of semiconductor chips, chip-type capacitors and circuit substrates on the circuit substrate by soldering using flux, and using At least one of the steps of forming solder bumps that connect the above-mentioned components on the circuit board; and, by the cleaning method as in any one of claims 1 to 13, select from the circuit board mounted with the above-mentioned components and the The step of cleaning at least one of the circuit substrates of the solder bumps. A composition used as a cleaning agent when cleaning objects to be cleaned with flux residues, and A compound containing an organic solvent (component A) and a compound having an alkyl group with 1 to 4 carbon atoms on the nitrogen atom of the imidazole ring or piperidine ring (component B). The use of a composition for cleaning objects to be cleaned with flux residues. The composition contains an organic solvent (component A) and the nitrogen atom of the imidazole ring or the piperidine ring has a carbon number of 1 or more 4 or less alkyl compounds (component B).