CN113165027A

CN113165027A - Cleaning of flux residue

Info

Publication number: CN113165027A
Application number: CN201980080692.6A
Authority: CN
Inventors: 长沼纯; 司马宽也
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2018-12-05
Filing date: 2019-12-04
Publication date: 2021-07-23
Anticipated expiration: 2039-12-04
Also published as: KR20210099006A; JPWO2020116534A1; TW202031884A; JP7370339B2; CN113165027B; WO2020116534A1

Abstract

The present disclosure provides, in one embodiment, a cleaning method having excellent flux removability. The present disclosure relates, in one aspect, to a cleaning method including a step of cleaning an object to be cleaned having flux residue with a cleaning agent composition containing an organic solvent (component a) and a compound (component B) having an alkyl group having 1 to 4 carbon atoms on a nitrogen atom of an imidazole ring or a piperazine ring.

Description

Cleaning of flux residue

Technical Field

The present disclosure relates to a cleaning agent composition for cleaning flux residue, a cleaning method using the cleaning agent composition, and a method for manufacturing an electronic component.

Background

In recent years, in mounting electronic components on printed wiring boards and ceramic substrates, the components have been miniaturized from the viewpoint of low power consumption and high-speed processing, and the gap to be cleaned in cleaning the solder flux has become narrow. In addition, lead-free solder has come to be used from the viewpoint of environmental safety, and rosin-based flux has come to be used in association therewith.

International publication No. 2012/005068 (patent document 1) discloses a stock solution for a detergent composition, which is used in combination with water and which cleans an object to be cleaned in a cloudy state with a specific amount of water added, and which contains 1 st and 2 nd organic solvents as organic solvents, wherein the 1 st organic solvent is a predetermined hydrophobic glycol ether compound or the like, the 2 nd organic solvent is a predetermined hydrophilic amine compound, the amount of the 2 nd organic solvent is in the range of 0.3 to 30 parts by weight relative to 100 parts by weight of the 1 st organic solvent, and the amount of the organic solvent having a boiling point exceeding 190 ℃.

International publication No. 2005/021700 (patent document 2) discloses a cleaning agent for removing solder flux, which is characterized in that: the content of benzyl alcohol is set to be 70-99.9 wt% and the content of amino alcohol is set to be 0.1-30 wt% when the content of diol compound is less than 1 wt% relative to the total amount, and the content of benzyl alcohol is set to be 15-99 wt% and the content of amino alcohol is set to be 0.1-30 wt% when the content of diol compound is 1-40 wt%.

Japanese patent laid-open publication No. 7-179893 (patent document 3) discloses a cleaning composition comprising: comprises 0-30 wt% of N-methyl-2-pyrrolidone containing water and at least one compound selected from phosphines, phenols, imidazolidinones, imidazoles and fluorenes.

Disclosure of Invention

The present disclosure relates, in one aspect, to a cleaning method including a step of cleaning an object to be cleaned having flux residue with a cleaning agent composition containing an organic solvent (component a) and a compound (component B) having an alkyl group having 1 to 4 carbon atoms on a nitrogen atom of an imidazole ring or a piperazine ring.

In one embodiment, the present disclosure relates to a method for manufacturing an electronic component, including the steps of: at least one step selected from a step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board on the circuit board by soldering using a flux, and a step of forming a solder bump for connecting the component and the like on the circuit board; and a step of cleaning at least one selected from a circuit board on which the component is mounted and a circuit board on which the solder bump is formed by the cleaning method of the present disclosure.

The present disclosure relates, in one aspect, to a composition for use as a cleaning agent in cleaning an object to be cleaned having flux residue, the composition comprising an organic solvent (component a) and a compound (component B) having an alkyl group having 1 to 4 carbon atoms on a nitrogen atom of an imidazole ring or a piperazine ring.

Detailed Description

In recent years, the size of a semiconductor package substrate has been reduced, solder bumps have been miniaturized, and a gap between the solder bumps and a component to be connected has been narrowed. Further, since the solder bumps are miniaturized and the gap between the solder bumps and the members to be connected is narrowed, the cleaning agent composition disclosed in the above patent document is insufficient in removability of flux residue (flux removability) and is not satisfactory in cleanability.

Accordingly, the present disclosure provides a cleaning agent composition having excellent flux removability, a cleaning method using the same, and a method for manufacturing an electronic component.

According to one embodiment of the present disclosure, a cleaning agent composition and a cleaning method having excellent flux removability can be provided.

The present disclosure is based on the following recognition: the removal of flux residue is improved compared to the conventional methods by using a cleaning agent composition containing a specific solvent and a specific amine for the removal of flux residue.

That is, the present disclosure relates, in one aspect, to a cleaning method (hereinafter, also referred to as a "cleaning method of the present disclosure") including a step of cleaning an object to be cleaned having flux residue with a cleaning agent composition containing an organic solvent (component a) and a compound (component B) having an alkyl group having 1 to 4 carbon atoms on a nitrogen atom of an imidazole ring or a piperazine ring. According to the present disclosure, in one or more embodiments, flux residue of a cleaning object can be efficiently removed.

In another embodiment, the present disclosure relates to a composition (hereinafter, also referred to as "the cleaning agent composition of the present disclosure") for use as a cleaning agent in cleaning an object to be cleaned having flux residue, the composition comprising an organic solvent (component a) and a compound (component B) having an alkyl group having 1 to 4 carbon atoms at a nitrogen atom of an imidazole ring or a piperazine ring. According to the present disclosure, in one or more embodiments, a cleaning agent composition excellent in flux removability can be obtained. Further, according to the present disclosure, in one or more embodiments, a cleaning agent composition that can suppress the influence of corrosion or the like on a solder metal can be obtained.

The details of the action mechanism of the effect of the cleaning method of the present disclosure and the cleaning agent composition of the present disclosure are not yet clarified, but are presumed as follows.

That is, in the cleaning method of the present disclosure and the cleaning agent composition of the present disclosure, the component a penetrates the flux and the flux residue deteriorated by reflow or the like to reduce the viscosity and make the flux easily flowable, and the component B functions to form a salt with the flux to decompose or hydrophilize the flux and the flux residue and make the flux and the flux residue easily soluble in the cleaning agent composition.

It is also presumed that the solubility in water in the washing step after washing of the flux and flux residue is increased by the component B, the removability by washing is improved, and the residue after washing and washing can be reduced.

Further, it is presumed that the component B acts on the solder metal in the solvent containing the component a, and the cleaning property is improved as described above without corroding the solder metal, and therefore, a cleaning agent composition for removing flux residue capable of suppressing the influence of corrosion or the like on the solder metal is obtained.

However, the present disclosure is not limited to this mechanism and can be explained.

The "flux" in the present disclosure refers to a rosin-based flux containing rosin or rosin derivatives used for soldering, a water-soluble flux containing no rosin, or the like for removing oxides that inhibit the connection between metals such as electrodes and wiring and solder metals to promote the connection, and the "soldering" in the present disclosure includes soldering by a reflow method and a flow soldering method. By "solder flux" in this disclosure is meant a mixture of solder and flux. In the present disclosure, "flux residue" refers to residue derived from a flux remaining on a substrate after solder bumps are formed using the flux and/or a substrate after soldering is performed using the flux. For example, when other components (e.g., a semiconductor chip, a chip capacitor, another circuit board, 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 mounting may remain in the gap as flux residue after soldering by reflow soldering or the like.

[ cleaning method ]

In one or more embodiments, the cleaning method of the present disclosure is a cleaning method for removing flux residue, which includes a step of cleaning an object to be cleaned having flux residue with the cleaning agent composition of the present disclosure. The cleaning method of the present disclosure, in one or more embodiments, includes contacting an object to be cleaned having flux residue with the cleaning agent composition of the present disclosure. Examples of the method for cleaning an object to be cleaned with the cleaning agent composition of the present disclosure or the method for bringing the cleaning agent composition of the present disclosure into contact with an object to be cleaned include a method of bringing into contact in a bath of an ultrasonic cleaning apparatus, a method of ejecting and bringing into contact the cleaning agent composition in a spray form (shower system), and the like. The cleaning agent composition of the present disclosure can be used directly for cleaning without dilution. The cleaning method of the present disclosure preferably includes a step of rinsing with water and drying after the object to be cleaned is brought into contact with the cleaning agent composition. With the cleaning method of the present disclosure, flux residue remaining in the gap between the soldered components can be efficiently cleaned. In terms of the remarkable effects of the cleanability and the permeability into narrow gaps of the cleaning method of the present disclosure, the solder is preferably a lead (Pb) -free solder. From the same viewpoint, the cleaning method of the present disclosure is preferably used for electronic components that are soldered using the flux described in international publication No. 2006/025224, japanese patent publication No. 6-75796, japanese patent laid-open publication No. 2014-144473, japanese patent laid-open publication No. 2004-230426, japanese patent laid-open publication No. 2013-188761, and japanese patent laid-open publication No. 2013-173184. In the cleaning method of the present disclosure, in terms of easily exerting the cleaning power of the cleaning agent composition of the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning agent composition of the present disclosure is in contact with an object to be cleaned, and it is more preferable that the ultrasonic waves be strong. From the same viewpoint, the frequency of the ultrasonic wave is preferably 26 to 72Hz and 80 to 1500W, more preferably 36 to 72Hz and 80 to 1500W.

[ cleaning agent composition ]

The cleaning agent composition of the present disclosure is a composition used as a cleaning agent in cleaning an object to be cleaned having flux residue, and in one or more embodiments, is a cleaning agent composition for removing flux residue. In the present disclosure, the term "cleaning agent composition for removing flux residue" refers to a cleaning agent composition for removing a flux residue after forming a solder bump and/or soldering using a flux or a solder flux in one or more embodiments. In terms of the remarkable effect of the cleanability of the cleaner composition of the present disclosure being exhibited, the solder is preferably a tin-containing lead (Pb) -free solder.

Accordingly, the present disclosure relates, in one aspect, to a composition for use as a cleaning agent in cleaning an object to be cleaned having flux residue, the composition comprising an organic solvent (component a) and a compound (component B) having an alkyl group having 1 to 4 carbon atoms on a nitrogen atom of an imidazole ring or a piperazine ring.

In one embodiment, the present disclosure relates to a cleaning agent composition for removing flux residue, including: at least one solvent (component A) 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); and at least one amine (component B) selected from the group consisting of 1-methylimidazole, 1, 2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1- (2-dimethylaminoethyl) -4-methylpiperazine.

The present disclosure relates, in one embodiment, to the use of a composition containing an organic solvent (component a) and a compound (component B) having an alkyl group having 1 to 4 carbon atoms on a nitrogen atom of an imidazole ring or a piperazine ring for cleaning an object to be cleaned having flux residue.

(component A: organic solvent)

The component a in the detergent composition of the present disclosure is an organic solvent. In one or more embodiments, the component a is preferably at least one solvent 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), from the viewpoint of improving the flux removability. The component A may be a combination of 1 type, 2 types, or a combination of 2 or more types.

R¹-O-(AO)_n-R² (I)

In the formula (I), R is preferably R from the viewpoint of improving the flux removability¹Is phenyl or alkyl with more than 1 and less than 8 carbon atoms, R²Is 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 an integer of 1 to 3 inclusive which is the number of moles of AO added.

In the above formula (I), R is R from the viewpoint of improving the flux removability¹Preferably 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, and still more preferably an alkyl group having 4 to 6 carbon atoms. From the viewpoint of improving the flux removability, R²Preferably 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 still more preferably a hydrogen atom or an n-butyl group. In addition, from the viewpoint of improving the flux removability, R is preferable¹Is an alkyl group having 1 to 3 carbon atoms, R²An alkyl group having 1 to 3 carbon atoms. From the viewpoint of improving the flux removability,AO is preferably an ethylene oxide group or a propylene oxide group, and more preferably an ethylene oxide group. From the viewpoint of improving the flux removability, n is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and even more preferably 2.

Examples of the compound represented by the formula (I) include: monophenyl ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether and the like; monoalkyl ethers such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and triethylene glycol monoalkyl ether having an alkyl group of 1 to 8 carbon atoms; dialkyl ethers such as ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, and triethylene glycol dialkyl ether having an alkyl group of 1 to 8 carbon atoms and an alkyl group of 1 to 4 carbon atoms; and phenylalkyl ethers such as ethylene glycol phenylalkyl ethers, diethylene glycol phenylalkyl ethers, and triethylene glycol phenylalkyl ethers having a phenyl group and an alkyl group having 1 to 4 carbon atoms. The compound represented by the formula (I) is preferably selected from the group consisting of 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, and dipropylene glycol monobutyl ether from the viewpoint of improving the flux removability, tripropylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, and triethylene glycol dimethyl ether, more preferably at least one selected from the group consisting of diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, dipropylene glycol monobutyl ether, and diethylene glycol dibutyl ether, still more preferably at least one selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, and diethylene glycol dimethyl ether, and still more preferably diethylene glycol dimethyl ether.

R³-CH₂OH(II)

In the above formula (II), R is R from the viewpoint of improving the flux removability³Preferably, the phenyl group is a phenyl group, a benzyl group, a cyclohexyl group, a furyl group, a tetrahydrofurfuryl group, a furfuryl group, or a tetrahydrofurfuryl group, more preferably a phenyl group, a cyclohexyl group, or a tetrahydrofurfuryl group, still more preferably a phenyl group.

Examples of the compound represented by the formula (II) include: benzyl alcohol, phenethyl alcohol, cyclohexane methanol, furfuryl alcohol and tetrahydrofurfuryl alcohol. The compound represented by the 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, from the viewpoint of improving the flux removability.

[ chemical formula 1]

In the above formula (III), R is R from the viewpoint of improving the flux removability⁴、R⁵、R⁶、R⁷Preferably each independently represents 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, more preferably R⁴、R⁵、R⁶、R⁷Any of these is a hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably any of a methyl group, an ethyl group, and a vinyl group.

Examples of the compound represented by the formula (III) include: 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, 5-methyl-2-pyrrolidone, and the like. The compound represented by the formula (III) is preferably selected from the group consisting of 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, and 1-vinyl-2-pyrrolidone, from the viewpoint of improving the flux removability, at least one of 1-phenyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone, more preferably at least one selected from 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, and 1-vinyl-2-pyrrolidone, and still more preferably 1-methyl-2-pyrrolidone.

The component A may be a combination of 1 or 2 or a combination of 2 or more. When the component a is a combination of 2 kinds, examples of the component a include a combination of a compound represented by the formula (I) and a compound represented by the formula (II).

As the component a, at least one selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, benzyl alcohol, and 1-methyl-2-pyrrolidone is preferable, and at least one selected from the group consisting of diethylene glycol monobutyl ether, benzyl alcohol, and 1-methyl-2-pyrrolidone is more preferable, from the viewpoint of improving the flux removability. 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 the component a in the cleaner 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, and is preferably 99.5% by mass or less, more preferably 99.3% by mass or less, and even more preferably 99% by mass or less, from the viewpoint of improving the flux removability. More specifically, the content of the component a in the detergent 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 99.3% by mass or less, and further preferably 75% by mass or more and 99% by mass or less. When the component a is a combination of 2 or more, the content of the component a means the total content thereof.

(ingredient B: amine)

The component B in the detergent composition of the present disclosure is a compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the imidazole ring or piperazine ring. From the viewpoint of improving the flux removability, the component B is preferably at least one amine selected from the group consisting of 1-methylimidazole, 1, 2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1- (2-dimethylaminoethyl) -4-methylpiperazine. The component B may be a combination of 1 type, 2 types, or a combination of 2 or more types. The component B is preferably a compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the imidazole ring, preferably at least one amine selected from 1-methylimidazole, 1, 2-dimethylimidazole, and 1-isobutyl-2-methylimidazole, and more preferably at least one amine selected from 1-methylimidazole and 1, 2-dimethylimidazole, from the viewpoint of improving the removability of the rosin-based flux.

The content of the component B in the cleaner composition of the present disclosure is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.4% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of improving the flux removability, and is preferably 15% by mass or less, more preferably 12% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of suppressing corrosion of the solder metal. More specifically, the content of the component B in the detergent composition of the present disclosure 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, still 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. When the component B is a combination of 2 or more, the content of the component B means the total content thereof.

In the cleaning agent composition of the present disclosure, the mass ratio of the component a to the component B (component a/component B) is preferably 8 or more, more preferably 10 or more, and even more preferably 15 or more, and is preferably 200 or less, more preferably 100 or less, and even more preferably 25 or less, from the viewpoint of improving the flux removability. 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 further preferably 15 or more and 25 or less.

(ingredient C: water)

The cleaner compositions of the present disclosure, in one or more embodiments, may further comprise water (component C). As the component C, ion-exchanged water, RO water, distilled water, pure water, ultrapure water, or the like can be used. The content of the component C in the cleaning agent composition of the present disclosure is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more from the viewpoint of reducing the ignition point, and is preferably 55% by mass or less, more preferably 15% by mass or less, further preferably 12% by mass or less, and further preferably 10% by mass or less from the viewpoint of improving the flux removability. More specifically, the content of the component C in the detergent composition of the present disclosure is preferably 1 mass% or more and 55 mass% or less, more preferably 1 mass% or more and 15 mass% or less, further preferably 5 mass% or more and 12 mass% or less, and further preferably 8 mass% or more and 10 mass% or less.

When the detergent composition of the present disclosure contains the component C, it is preferable to use diethylene glycol monobutyl ether in combination with the component a other than the diethylene glycol monobutyl ether in the component a contained in the detergent composition of the present disclosure from the viewpoint of improving stability.

(other Components)

The cleaning agent composition of the present disclosure may contain other components as necessary in addition to the components a to C described above. The content of the other components in the detergent composition of the present disclosure is preferably 0 mass% or more and 10 mass% or less, more preferably 0 mass% or more and 8 mass% or less, further preferably 0 mass% or more and 5 mass% or less, and further preferably 0 mass% or more and 2 mass% or less.

As other components in the detergent composition of the present disclosure, a surfactant can be mentioned, for example, from the viewpoint of improving stability. The surfactant is preferably a nonionic surfactant such as a polyoxyalkylene alkyl ether, a polyoxyalkylene alkylamine, a glycerin fatty acid ester, a sorbitan fatty acid ester, a sucrose fatty acid ester, an alkyl glucoside, or an alkyl glycerin ether, more preferably a polyoxyalkylene alkyl ether or an alkyl glycerin ether, and still more preferably an alkyl glycerin ether. Specific examples of the surfactant include 2-ethylhexyl glyceryl ether. The content of the surfactant in the detergent composition of the present disclosure is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and is preferably 7% by mass or less, more preferably 5% by mass or less, from the viewpoint of improving stability. More specifically, the content of the surfactant is preferably 0.5% by mass or more and 7% by mass or less, and more preferably 0.8% by mass or more and 5% by mass or less.

As further other components, the cleaning agent composition of the present disclosure may contain, as necessary, a compound having chelating ability such as amino carboxylate such as hydroxyethylglycine, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid or the like, a rust preventive such as benzotriazole, a thickener, a dispersant, a basic substance other than the component B, a polymer compound, a solubilizer, a preservative, a bactericide, an antibacterial agent, an antifoaming agent, and an antioxidant, as far as the effects of the present disclosure are not impaired.

[ method for producing detergent composition ]

The cleaning agent composition of the present disclosure can be produced, for example, by blending the component a and the component B, and the component C and other components as necessary by a known method. In one or more embodiments, the cleaning agent composition of the present disclosure may be prepared by blending at least component a and component B. Accordingly, the present disclosure relates, in one aspect, to a method for producing a cleaning agent composition, including a step of blending at least a component a and a component B. In the present disclosure, "blending" includes mixing the component a, the component B, and, if necessary, the component C and other components simultaneously or in any order. In the method for producing the detergent composition of the present disclosure, the amount of each component to be blended may be the same as the content of each component of the detergent composition of the present disclosure. In the present disclosure, the "content of each component in the detergent composition" refers to the content of each component at the time of cleaning, that is, at the time when the detergent composition is used for cleaning.

The cleaning agent composition of the present disclosure can be produced and stored in the form of a concentrate from the viewpoint of addition operation, storage and transportation. The dilution ratio of the concentrate of the detergent composition of the present disclosure is, for example, 3 times or more and 30 times or less. The concentrate of the detergent composition of the present disclosure can be diluted with water (component C) at the time of use so that the content of the component a, the component B, and, if necessary, the component C and other components becomes the above content (that is, the content at the time of cleaning).

[ pH value of detergent composition ]

The cleaning agent composition of the present disclosure is preferably alkaline in terms of improving the flux removability, and for example, preferably has a pH of 8 or more and a pH of 14 or less. The pH can be adjusted by appropriately compounding the following substances in the required amounts as required: inorganic acids such as nitric acid and sulfuric acid; organic acids such as hydroxycarboxylic acids, polycarboxylic acids, aminopolycarboxylic acids, and amino acids; and basic substances other than component B, such as metal salts or ammonium salts thereof, ammonia, sodium hydroxide, potassium hydroxide, and amines. The pH of the detergent composition in the present disclosure is the pH at 25 ℃ at the time of use (after dilution) of the detergent composition.

[ subject to be cleaned ]

The cleaning agent composition of the present disclosure is used in one or more embodiments for cleaning an object to be cleaned having flux residue. Examples of the object to be cleaned having flux residue include an object to be cleaned having solder reflowed. Specific examples of the object to be cleaned include, for example, electronic components and manufacturing intermediates thereof, specifically, soldered electronic components and manufacturing intermediates thereof, and more specifically, include: an electronic component to which a component is soldered with solder and an intermediate product for manufacturing the same, an electronic component to which a component is connected with solder and an intermediate product for manufacturing the same, an electronic component including flux residue in a gap between soldered components and an intermediate product for manufacturing the same, an electronic component including flux residue in a gap between components connected with solder and an intermediate product for manufacturing the same, and the like. The manufacturing intermediate product is an intermediate product in a manufacturing process of an electronic component including a semiconductor package or a semiconductor device, and includes, for example, a circuit board on which at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board is mounted by soldering using a flux, and/or a circuit board on which a solder bump for solder-connecting the components is formed. The gap in the object to be cleaned is, for example, a space formed between the circuit board and a component (semiconductor chip, chip capacitor, circuit board, etc.) mounted on the circuit board by soldering, and the height (distance between components) thereof is, for example, 5 to 500 μm, 10 to 250 μm, or 20 to 100 μm. The width and depth of the gap depend on the size and spacing of the components to be mounted and the electrodes (pads) on the circuit board.

[ method for producing electronic component ]

In one embodiment, the present disclosure relates to a method for manufacturing an electronic component (hereinafter, also referred to as "method for manufacturing an electronic component of the present disclosure"), including the steps of: at least one step selected from a step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board on the circuit board by soldering using a flux, and a step of forming a solder bump for connecting the component and the like on the circuit board; and a step of cleaning at least one selected from a circuit board on which the component is mounted and a circuit board on which the solder bump is formed by the cleaning method of the present disclosure. Soldering using the flux is performed, for example, by using a lead-free solder, and may be a reflow soldering method or a flow soldering method. The electronic component includes a semiconductor package not mounted with a semiconductor chip, a semiconductor package mounted with a semiconductor chip, and a semiconductor device. In the method for manufacturing an electronic component according to the present disclosure, by performing the cleaning method according to the present disclosure, flux residue remaining in the gaps between soldered components, the periphery of solder bumps, and the like is reduced, and short-circuiting and poor adhesion between electrodes due to the remaining flux residue are suppressed, so that an electronic component having high reliability can be manufactured. Further, by performing the cleaning method of the present disclosure, cleaning of flux residue remaining in a gap or the like of a soldered component becomes easy, so that the cleaning time can be shortened, and the manufacturing efficiency of an electronic component can be improved.

[ set ]

The present disclosure relates, in one aspect, to a kit (hereinafter, also referred to as "kit of the present disclosure") for use in a cleaning method of the present disclosure and/or a manufacturing method of an electronic component of the present disclosure. The kit of the present disclosure, in one or more embodiments, is a kit for manufacturing the cleaner composition of the present disclosure.

One embodiment of the kit of the present disclosure includes a kit (two-liquid type cleaning agent composition) in which a solution containing the component a (1 st liquid) and a solution containing the component B (2 nd liquid) are contained in an unmixed state, and the 1 st liquid and the 2 nd liquid are mixed at the time of use. Accordingly, the cleaning method of the present disclosure may include, in one or more embodiments, the following processes: the cleaning agent composition is prepared by mixing the solution 1 and the solution 2 at the time of use in a state where the solution containing the component A (the solution 1) and the solution containing the component B (the solution 2) are not mixed with each other. In addition, the cleaning method of the present disclosure may include, in one or more embodiments, the following processes: and a step of mixing the 1 st liquid and the 2 nd liquid at the time of use to prepare a cleaning agent composition by using a kit containing a solution containing the component A (1 st liquid) and a solution containing the component B (2 nd liquid) in an unmixed state.

The liquid 1 and the liquid 2 may contain the component C and other components, respectively, as required. At least one of the above-mentioned solution 1 and solution 2 may contain a part or all of the component C (water) in one or more embodiments. In one or more embodiments, the 1 st liquid and the 2 nd liquid may be mixed and then diluted with the component C (water) as necessary.

The present disclosure also relates to one or more of the following embodiments.

< 1 > a cleaning agent composition for removing flux residue, which comprises: at least one solvent (component A) 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); and

at least one amine selected from the group consisting of 1-methylimidazole, 1, 2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1- (2-dimethylaminoethyl) -4-methylpiperazine (component B).

R¹-O-(AO)_n-R² (I)

In the above formula (I), R¹Is phenyl or alkyl with more than 1 and less than 8 carbon atoms, R²Is 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 an integer of 1 to 3 inclusive which is the number of moles of AO added.

R³-CH₂OH (II)

In the above formula (II), R³Is phenyl, benzyl, cyclohexyl, furyl, tetrahydrofuryl, furfuryl or tetrahydrofurfuryl.

[ chemical formula 2]

In the above formula (III), R⁴、R⁵、R⁶、R⁷Each independently represents 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.

< 2 > the cleaning agent composition according to < 1 >, wherein, in the above formula (I), R¹Is 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, more preferably an alkyl group having 4 to 6 carbon atoms.

< 3 > the detergent composition according to < 1 > or < 2 >, wherein R in the formula (I) is²Is 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, more preferably a hydrogen atom or an n-butyl group.

< 4 > the cleaning agent composition according to any one of < 1 > to < 3 >, wherein AO in the above formula (I) is an ethylene oxide group or a propylene oxide group, preferably an ethylene oxide group.

< 5 > the cleaning agent composition according to any one of < 1 > to < 4 >, wherein n in the above formula (I) is an integer of 1 or more and 3 or less, preferably 1 or 2, more preferably 2.

< 6 > the cleaning agent composition according to any one of < 1 > to < 5 >, wherein R in the above formula (II)³Represents a phenyl group, a benzyl group, a cyclohexyl group, a furyl group, a tetrahydrofurfuryl group, a furfuryl group or a tetrahydrofurfuryl group, preferably a phenyl group, a cyclohexyl group or a tetrahydrofurfuryl group, more preferably a phenyl group or a tetrahydrofurfuryl group, and still more preferably a phenyl group.

< 7 > the cleaning agent composition according to any one of < 1 > to < 6 >, wherein R in the above formula (III)⁴、R⁵、R⁶、R⁷Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 or 1 carbon atomA hydroxyalkyl group or a hydroxyl group of 3 or less, preferably R⁴、R⁵、R⁶、R⁷Any of these is a hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still 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 the component A is preferably at least one selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, benzyl alcohol and 1-methyl-2-pyrrolidone, and 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 according to any one of < 1 > to < 8 >, wherein the content of the 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 according to any one of < 1 > to < 9 >, wherein the content of the component A is preferably 99.5% by mass or less, more preferably 99.3% by mass or less, and still more preferably 99% by mass or less.

< 11 > the detergent composition according to any one of < 1 > to < 10 >, wherein the content of the component A 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 further preferably 75% by mass or more and 99% by mass or less.

< 12 > the cleaning agent composition according to any one of < 1 > to < 11 >, wherein the content of the component B is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, further preferably 0.4% by mass or more, and further preferably 0.5% by mass or more.

< 13 > the cleaning agent composition according to any one of < 1 > to < 12 >, wherein the content of the component B is preferably 15% by mass or less, more preferably 12% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, and further preferably 5% by mass or less.

< 14 > the cleaning agent composition according to any one of < 1 > to < 13 >, wherein the content of the component B 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, further preferably 0.4% by mass or more and 8% by mass or less, and further 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 the component A to the component B (component A/component B) is preferably 8 or more, more preferably 10 or more, and still more preferably 15 or more.

< 16 > the cleaning agent composition according to any one of < 1 > to < 15 >, wherein the mass ratio of the component A to the component B (component A/component B) is preferably 200 or less, more preferably 100 or less, and still more preferably 25 or less.

< 17 > the cleaning agent composition according to any one of < 1 > to < 16 >, wherein the mass ratio of the component A to the component B (component A/component B) is preferably 8 or more and 200 or less, more preferably 10 or more and 100 or less, and further preferably 15 or more and 25 or less.

< 18 > the cleaning agent composition according to any one of < 1 > to < 17 > further comprising water (component C).

< 19 > the detergent composition of < 18 > wherein the content of the 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 cleaning agent composition according to < 18 > or < 19 >, wherein the content of the component C is preferably 55% by mass or less, more preferably 15% by mass or less, further preferably 12% by mass or less, and further preferably 10% by mass or less.

< 21 > the cleaning agent composition according to any one of < 18 > to < 20 >, wherein the content of the component C 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, further preferably 5% by mass or more and 12% by mass or less, and further preferably 8% by mass or more and 10% by mass or less.

< 22 > the detergent composition according to any one of < 1 > to < 21 > further comprising a surfactant.

< 23 > the detergent composition according to any one of < 1 > to < 22 > further comprising at least one selected from the group consisting of a compound having chelating ability, a rust inhibitor such as benzotriazole, a thickener, a dispersant, a basic substance other than the component B, a polymer compound, a solubilizer, an antiseptic, a bactericide, an antibacterial agent, an antifoaming agent, and an antioxidant.

< 24 > a cleaning method comprising a step of cleaning an object to be cleaned having flux residue with the cleaning agent composition according to any one of < 1 > to < 23 >.

< 25 > the cleaning method according to < 24 > wherein the object to be cleaned is a manufacturing intermediate for soldering electronic parts.

< 26 > a method for producing an electronic component, comprising the steps of: at least one step selected from a step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board on the circuit board by soldering using a flux, and a step of forming a solder bump for connecting the component and the like on the circuit board; and a step of cleaning at least one selected from the group consisting of a circuit board on which the component is mounted and a circuit board on which the solder bump is formed by the cleaning method described in < 24 > or < 25 >.

< 27 > a kit for use in the cleaning method < 24 > or < 25 > and/or the electronic component manufacturing method < 26 > comprising a solution containing component A (solution 1) and a solution containing component B (solution 2) in an unmixed state, the solution 1 and the solution 2 being mixed at the time of use.

< 28 > a cleaning method comprising a step of cleaning an object to be cleaned having flux residue with a cleaning agent composition,

the cleaning agent composition contains an organic solvent (component A) and a compound (component B) having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the imidazole ring or piperazine ring.

< 29 > the cleaning method according to < 28 > wherein the component B is at least one amine selected from the group consisting of 1-methylimidazole, 1, 2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1- (2-dimethylaminoethyl) -4-methylpiperazine.

< 30 > the cleaning method according to < 28 > or < 29 >, wherein the component A is at least one solvent 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).

R¹-O-(AO)_n-R²(I)

R³-CH₂OH(II)

[ chemical formula 3]

< 31 > the cleaning method according to any one of < 28 > to < 30 >, wherein the content of the component A in the cleaning agent composition is 35% by mass or more and 99.5% by mass or less.

< 32 > the cleaning method according to any one of < 28 > to < 31 >, wherein the mass ratio of the component A to the component B in the cleaning agent composition (component A/component B) is 8 or more and 200 or less.

< 33 > the cleaning method according to any one of < 28 > to < 32 >, wherein the above-mentioned cleaning agent composition further contains water (component C).

< 34 > the cleaning method according to < 33 >, wherein the content of the component C in the cleaning agent 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 cleaning agent composition is 0.2 mass% or more and 15 mass% or less.

< 36 > the cleaning method according to any one of < 28 > to < 35 >, wherein the component A is at least one selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol 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 the other components than the components A to C in the cleaning agent composition is 0% by mass or more and 10% by mass or less.

< 38 > the cleaning method according to any one of < 28 > to < 37 >, wherein the object to be cleaned is a manufacturing intermediate for soldering electronic parts.

< 39 > the cleaning method according to any one of < 28 > to < 38 > comprising the steps of: the cleaning agent composition is prepared by mixing the solution 1 and the solution 2 at the time of use in a state where the solution containing the component A (the solution 1) and the solution containing the component B (the solution 2) are not mixed with each other.

< 40 > the cleaning method according to any one of < 28 > to < 39 > wherein the object to be cleaned is cleaned with the cleaning agent composition by a method of contacting in a bath of an ultrasonic cleaning apparatus or a method of contacting by spraying the cleaning agent composition.

< 41 > a method for producing an electronic component, comprising the steps of: at least one step selected from a step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board on the circuit board by soldering using a flux, and a step of forming a solder bump for connecting the component and the like on the circuit board; and a step of cleaning at least one selected from the group consisting of a circuit board on which the component is mounted and a circuit board on which the solder bump is formed by the cleaning method described in any one of < 28 > to < 40 >.

< 42 > a composition for use as a cleaning agent in cleaning an object to be cleaned having flux residue, comprising an organic solvent (component A) and a compound (component B) having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the imidazole ring or piperazine ring.

< 43 > use of a composition comprising an organic solvent (component A) and a compound having an alkyl group having 1 to 4 carbon atoms at a nitrogen atom in an imidazole ring or a piperazine ring (component B) for cleaning an object to be cleaned having flux residue.

Examples

The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples at all.

1. Preparation of cleaning agent composition (examples 1 to 16, comparative examples 1 to 9)

The cleaning agent compositions of examples 1 to 16 and comparative examples 1 to 9 were prepared by mixing the respective components in a 100mL glass beaker so as to have the composition shown in table 1 below and mixing them under the following conditions. The numerical values of the respective components in table 1 indicate the contents (mass%) of the prepared cleaning agent compositions unless otherwise specified.

< mixing Condition >

Liquid temperature: 25 deg.C

The stirrer: magnetic force mixer (50mm rotor)

Rotating speed: 300rpm

Stirring time: 10 minutes

The following were used as components of the detergent composition.

(component A)

A1: benzyl alcohol [ Lanxess Co., Ltd ]

A2: diethylene glycol monobutyl ether [ diethylene glycol monobutyl ether (BDG) manufactured by Nippon emulsifier Co., Ltd ]

A3: dipropylene glycol monobutyl ether [ manufactured by Nippon emulsifier Co., Ltd., dipropylene glycol butyl ether (BFDG) ]

A4: diethylene glycol dimethyl ether [ diethylene glycol dimethyl ether (DMDG) manufactured by Nippon emulsifier Co., Ltd ]

A5: 1-methyl-2-pyrrolidone [ Fuji films and Wako pure chemical industries, Ltd ]

(component B)

B1: 1-methylimidazole [ Kaolizer No.110, manufactured by Kaowang Co., Ltd ]

B2: 1, 2-Dimethylimidazole [ manufactured by Tokyo chemical industry Co., Ltd ]

B3: 1-isobutyl-2-methylimidazole [ Kaolizer No.120, manufactured by Kaowang Co., Ltd ]

B4: 1- (2-dimethylaminoethyl) -4-methylpiperazine [ Kaolizer No.8, manufactured by KaiWang corporation ]

(not component B)

B5: triethanolamine [ manufactured by Japan catalyst Co., Ltd ]

B6: methyldiethanolamine [ aminoalcohol MDA manufactured by Nippon emulsifier Co., Ltd ]

B7: 2-Ethyl-4-methylimidazole [ Fuji film and Wako pure chemical industries, Ltd ]

B8: 1, 5-dimethyl-2-pyrrolidone

(component C)

Water [ purified water of 1. mu.S/cm or less produced by Water purifier G-10DSTSET, manufactured by Organo corporation ]

(other Components: surfactant)

2-ethylhexyl glyceryl ether [ produced by the following production method ]

130g of 2-ethylhexanol and 2.84g of boron trifluoride ether complex were cooled to 0 ℃ with stirring. 138.8g of epichlorohydrin was added dropwise over 1 hour while maintaining the temperature at 0 ℃. After the end of the dropwise addition, the remaining alcohol is distilled off under reduced pressure (13 to 26Pa) at 100 ℃. The reaction mixture was cooled to 50 ℃, while maintaining the temperature at 50 ℃, 125g of a 48% aqueous sodium hydroxide solution was added dropwise over 1 hour, and after stirring for 3 hours, 200mL of water was added to separate the layers. After removing the aqueous layer, the reaction solution was further washed 2 times with 100mL of water to obtain 208g of crude 2-ethylhexyl glycidyl ether. 208g of the crude 2-ethylhexyl glycidyl ether, 104.8g of water, 5.82g of lauric acid, and 18.5g of potassium hydroxide were charged into an autoclave, and stirred at 140 ℃ for 5 hours. After dehydration under reduced pressure (6.67kPa) at 100 ℃, 9.7g of lauric acid and 2.72g of potassium hydroxide were added, and the mixture was reacted at 160 ℃ for 15 hours, followed by purification by distillation under reduced pressure (53 to 67Pa, 120 to 123 ℃) to obtain 110.2g of 2-ethylhexyl glyceryl ether.

(other Components: Rust preventive)

Benzotriazole [ 1,2, 3-benzotriazole manufactured by Tokyo chemical industry Co., Ltd ]

2. Evaluation of cleaning agent composition

The cleaning agent compositions of examples 1 to 16 and comparative examples 1 to 9 were tested for cleaning performance and corrosion resistance and evaluated.

< test substrate >

On a copper wiring printed board (10mm × 15mm), the following solder paste was applied using a screen printing plate. The test substrate was fabricated by performing reflow soldering at 250 ℃ under a nitrogen atmosphere.

< composition of flux >

Total hydrogenated rosin (manufactured by Eastman Chemical Co., Ltd., Foral AX-E)58.0 mass%

N, N' -diphenylguanidine hydrobromide (manufactured by Kyowa chemical Co., Ltd.) in an amount of 0.5% by mass

Adipic acid (manufactured by Wako pure chemical industries, Ltd.) 0.5 mass%

Hydrogenated castor oil (manufactured by Fengkou oil Co., Ltd.) 6.0% by mass

Hexylene glycol (Japanese text: ヘキシルグリコール) (manufactured by Nippon emulsifier Co., Ltd.) 35.0 mass%

< method for producing flux >

The flux having the above composition is obtained by adding and dissolving the remaining other components to hexylene glycol as a solvent.

< method for producing solder paste >

The flux (11.0 g) was kneaded with solder powder (M705 (Sn/Ag/Cu: 96.5/3/0.5) manufactured by sumo metal industries, ltd.) (89.0 g) for 1 hour.

< cleaning test >

The cleaning test was carried out in the following manner.

First, an ultrasonic cleaning tank, a1 st rinsing tank, and a2 nd rinsing tank were prepared under the following conditions. The ultrasonic cleaning tank set the frequency to 40kHz and the output to 200W. Obtained by adding 50g of each detergent composition to a 50mL glass beaker, placing the mixture in an ultrasonic cleaning layer, and heating the mixture to 60 ℃. The 1 st and 2 nd flushing tanks are obtained by: two 100mL glass beakers each having a 50mm rotor were prepared, and 100g of pure water was added thereto, and the mixture was put into a warm bath and heated to 40 ℃ while stirring at 100 rpm.

Next, the test substrate was held by tweezers, inserted into the ultrasonic cleaning tank, and immersed for 5 minutes. Next, the test substrate was held by tweezers, inserted into the 1 st rinse tank, and immersed for 3 minutes while being stirred at 100 rpm.

Further, the test substrate was held by tweezers, inserted into the 2 nd rinse tank, and immersed for 3 minutes while being stirred at 100 rpm.

Finally, the test substrate was dried by purging with nitrogen.

[ evaluation of cleaning Property (flux removing Property) ]

After the cleaning, the test substrate was observed with a microscope Miniscope TM3030 (manufactured by Hitachi Kagaku K.K.) on a desk, and the presence or absence of flux residue remaining on any 10 solder bumps was visually checked to count the number of flux residues. The results are shown in Table 1.

Further, the test substrate was observed with an optical microscope VHX-2000 (manufactured by KEYENCE corporation), and the presence or absence of flux residue remaining in the vicinity of the solder bump was visually checked, and the number of solder bumps in which flux residue remained in the vicinity of the solder bump was counted. The results are shown in Table 1.

[ evaluation of Corrosion resistance ]

The solder metal on the test substrate after evaluation of the cleaning property (flux removing property) was visually observed using an optical microscope VHX-2000 (manufactured by KEYENCE corporation) and a desktop microscope Miniscope TM3030 (manufactured by hitachi new technologies), and the influence on the solder metal was evaluated based on the following evaluation criteria. The evaluation results are shown in table 1.

< evaluation Standard >

A: has no influence on solder metal

B: having an influence on the solder metal due to corrosion or the like

[ evaluation of detergency (rosin acid solubility) ]

In order to confirm the affinity of the flux, the solubility of rosin acid used as a component of the flux was evaluated by the following method. The evaluation results are shown in table 1.

100g of the detergent composition and 1g of abietic acid were added to a 50mL glass beaker, and ultrasonic treatment was performed at 25 ℃ for 1 hour using an ultrasonic cleaning tank under conditions of a frequency of 40kHz and an output of 200W. When the rosin acid was dissolved, 1g of rosin acid was further added, and the same operation was performed. This operation was repeated until the abietic acid was not dissolved, thereby estimating the solubility. The higher the solubility, the more excellent the rosin-based flux removability was evaluated. From the viewpoint of improving the removability of the rosin-based flux, the solubility is evaluated to be preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more.

< evaluation Standard >

A: a solubility of 60 mass% or more

B: the solubility is 50 to less than 60% by mass

C: the solubility is 40 to less than 50% by mass

D: solubility less than 40% by mass

[ Table 1]

As shown in Table 1, the cleaning agent compositions of examples 1 to 16 containing the component A and the component B are superior in flux removability to those of comparative examples 1 to 9 containing neither the component A nor the component B. Furthermore, the cleaning agent compositions of examples 1 to 16 were suppressed in their effect on the solder metal. Further, the rosin acid solubility of the cleaning agent compositions of examples 2 to 3, 6, 9 to 11, 13 to 14 and 16 was as high as 50 mass% or more, and it was found that the rosin-based flux removing property was excellent as compared with examples 1, 4 to 5, 7 to 8, 12 and 15.

Industrial applicability

By using the present disclosure, the flux residue can be cleaned satisfactorily, and therefore, for example, in the manufacturing process of electronic components, shortening of the cleaning process of the flux residue and improvement of the performance and reliability of the manufactured electronic components become possible, and the productivity of the electronic components can be improved.

Claims

1. A cleaning method comprising a step of cleaning an object to be cleaned having flux residue with a cleaning agent composition,

the cleaning agent composition contains a component A which is an organic solvent, and a component B which is a compound having an alkyl group having 1 to 4 carbon atoms on a nitrogen atom of an imidazole ring or a piperazine ring.

2. The cleaning method according to claim 1, wherein the component B is at least one amine selected from the group consisting of 1-methylimidazole, 1, 2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1- (2-dimethylaminoethyl) -4-methylpiperazine.

3. The cleaning method according to claim 1 or 2, wherein the component A is at least one solvent 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),

R¹-O-(AO)_n-R² (I)

in the formula (I), R¹Is phenyl or alkyl with more than 1 and less than 8 carbon atoms, R²Is hydrogen or alkyl of 1 to 4 carbon atoms, AO is ethylene oxide or propylene oxide, and n is the addition mole number of AO and is 1 to 1And an integer of 3 or less is used,

R³-CH₂OH (II)

in the formula (II), R³Is phenyl, benzyl, cyclohexyl, furyl, tetrahydrofuryl, furfuryl or tetrahydrofurfuryl,

in the formula (III), R⁴、R⁵、R⁶、R⁷Each independently represents 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.

4. The cleaning method according to any one of claims 1 to 3, wherein a content of the component A in the cleaning agent composition is 35% by mass or more and 99.5% by mass or less.

5. The cleaning method according to any one of claims 1 to 4, wherein a mass ratio of component A to component B in the cleaning agent composition, that is, component A/component B, is 8 or more and 200 or less.

6. The cleaning method according to any one of claims 1 to 5, wherein the cleaning agent composition further contains water, i.e., component C.

7. The cleaning method according to claim 6, wherein a content of the component C in the cleaning agent composition is 15% by mass or less.

8. The cleaning method according to any one of claims 1 to 7, wherein a content of the component B in the cleaning agent composition is 0.2% by mass or more and 15% by mass or less.

9. The cleaning method according to any one of claims 1 to 8, wherein component A is at least one selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, benzyl alcohol, and 1-methyl-2-pyrrolidone.

10. The cleaning method according to any one of claims 1 to 9, wherein a content of the other components than the components a to C in the cleaning agent composition is 0% by mass or more and 10% by mass or less.

11. The cleaning method according to any one of claims 1 to 10, wherein the object to be cleaned is a manufacturing intermediate for soldering an electronic component.

12. The cleaning method according to any one of claims 1 to 11, comprising the steps of: the cleaning agent composition is prepared by mixing the 1 st liquid and the 2 nd liquid at the time of use in a state where the 1 st liquid, which is a solution containing the component A, and the 2 nd liquid, which is a solution containing the component B, are not mixed with each other.

13. The cleaning method according to any one of claims 1 to 12, wherein the object to be cleaned is cleaned with the cleaning agent composition by a method of performing contact in a bath of an ultrasonic cleaning apparatus or a method of performing contact by spraying the cleaning agent composition.

14. A method of manufacturing an electronic component, comprising:

at least one process step selected from: a step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board on the circuit board by soldering using a flux, and a step of forming a solder bump for connecting the component and the like on the circuit board; and

a step of cleaning at least one selected from a circuit board on which the component is mounted and a circuit board on which the solder bump is formed by the cleaning method according to any one of claims 1 to 13.

15. A composition for use as a cleaning agent in cleaning an object to be cleaned having flux residue,

contains a component A which is an organic solvent and a component B which is a compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the imidazole ring or piperazine ring.

16. A use of a composition containing a component A which is an organic solvent and a component B which is a compound having an alkyl group having 1 to 4 carbon atoms on a nitrogen atom of an imidazole ring or a piperazine ring, for cleaning an object to be cleaned having a flux residue.