TWI850293B - Cleaning of flux residues - Google Patents

Abstract

The present invention provides a cleaning method with excellent flux removal performance in one embodiment. The present invention relates to a cleaning method in one embodiment, which includes a step of using a cleaning agent composition to clean an object having flux residues, wherein the cleaning agent composition contains an organic solvent (component A) and a compound having an alkyl group with a carbon number of 1 or more and a carbon number of 4 or less on the nitrogen atom of an imidazole ring or a piperidine ring (component B).

Description

Cleaning of flux residues

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

In recent years, when mounting electronic components on printed wiring boards or ceramic substrates, the components have been miniaturized from the perspectives of low power consumption and high-speed processing, and the gaps that need to be cleaned when cleaning solder flux have become narrower. In addition, lead-free solder has begun to be used from the perspective of environmental safety, and rosin-based flux has been used along with it.

International Publication No. 2012/005068 (Patent Document 1) discloses a cleaning agent composition stock solution, which is used to be mixed with water and to clean the object to be cleaned in a white and turbid state when a specific amount of water is added. It contains a first and a second organic solvent as organic solvents, and the first organic solvent is a specific hydrophobic glycol ether compound, etc., and the second organic solvent is a specific hydrophilic amine compound. The amount of the second organic solvent is set to a value within the range of 0.3 to 30 parts by weight relative to 100 parts by weight of the first organic solvent, and the amount of the organic solvent having a boiling point exceeding 190°C is set to a value within a specific range.

International Publication No. 2005/021700 (Patent Document 2) discloses the following solder flux removal cleaning agent, which is characterized in that: relative to the total amount, when the content of the diol compound is less than 1% by weight, the content of benzyl alcohol is set to a range of 70-99.9% by weight and the content of the amino alcohol is set to a range of 0.1-30% by weight; when the content of the diol compound is 1-40% by weight, the content of benzyl alcohol is set to a range of 15-99% by weight and the content of the amino alcohol is set to a range of 0.1-30% by weight.

Japanese Patent Publication No. 7-179893 (Patent Document 3) discloses the following cleaning composition: comprising N-methyl-2-pyrrolidone containing 0-30% by weight of water and one or more compounds selected from phosphines, phenols, imidazolones, imidazoles or fluorenes.

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)。 The present invention relates to a cleaning method in one embodiment, which comprises the steps of using a cleaning agent composition to clean an object having flux residues, wherein the cleaning agent composition comprises an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the ring (component B).

The present invention in one embodiment relates to a method for manufacturing electronic components, which includes the following steps: at least one step selected from the step of mounting at least one component selected from semiconductor chips, chip-type capacitors and circuit substrates on a circuit substrate by soldering using flux and the step of forming solder bumps for connecting the above components on the circuit substrate; and the step of cleaning at least one selected from the circuit substrate mounted with the above components and the circuit substrate formed with the above solder bumps by the cleaning method of the present invention.

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)。 The present invention relates in one aspect to a composition for use as a cleaning agent for cleaning an object having flux residues, and comprising an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the ring (component B).

In recent years, due to the miniaturization of semiconductor package substrates, solder bumps have become smaller or the gaps between them and the parts to be connected have become narrower. Moreover, due to the miniaturization of solder bumps or the narrowing of the gaps between them and the parts to be connected, the cleaning agent composition disclosed in the above patent document has insufficient removal of flux residues (flux removal), and the cleaning property cannot be considered sufficient.

Therefore, the present invention provides a cleaning agent composition with excellent flux removal performance, a cleaning method using the same, and a method for manufacturing electronic components.

According to the present invention, in one embodiment, a cleaning agent composition and a cleaning method having excellent flux removal performance can be provided.

The present invention is based on the following insight: by using a cleaning agent composition containing a specific solvent and a specific amine for removing flux residues, the removal of flux residues is improved compared to the past.

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)。根據本發明，於一個或複數個實施形態中，可效率良好地除去被清潔物之助焊劑殘餘物。 That is, the present invention in one aspect is related to a cleaning method (hereinafter, also referred to as "the cleaning method of the present invention"), which comprises the step of using a cleaning agent composition to clean an object having flux residues, and the cleaning agent composition contains an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound having an alkyl group with 1 or more and 4 or less carbon atoms on the nitrogen atom of the ring (component B). According to the present invention, in one or more embodiments, flux residues of the object to be cleaned can be removed efficiently.

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)。根據本發明，於一個或複數個實施形態中，可獲得助焊劑除去性優異之清潔劑組合物。進而，根據本發明，於一個或複數個實施形態中，可獲得能抑制對焊料金屬之腐蝕等影響之清潔劑組合物。 In another aspect, the present invention relates to a composition (hereinafter also referred to as "the cleaning agent composition of the present invention"), which is used as a cleaning agent when cleaning an object having flux residues, and contains an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound in which the nitrogen atom of the ring has an alkyl group with 1 or more and 4 carbon atoms (component B). According to the present invention, in one or more embodiments, a cleaning agent composition having excellent flux removal performance can be obtained. Furthermore, according to the present invention, in one or more embodiments, a cleaning agent composition capable of suppressing the effects of corrosion on solder metal can be obtained.

The cleaning method of the present invention and the cleaning agent composition of the present invention have effects. Although the details of the mechanism are unclear, they are presumed to be as follows.

That is, in the cleaning method and the cleaning agent composition of the present invention, component A penetrates into the flux and the flux residue deteriorated by reflow, etc., and reduces the viscosity, making it easy to flow, and component B works to form a salt with the flux, thereby decomposing the flux and the flux residue or hydrophilizing them so that they are easily soluble in the cleaning agent composition.

In addition, it is speculated that the solubility of flux and flux residue in water in the rinsing step after cleaning is increased by component B, which can improve the removability of rinsing, thereby reducing the residue after cleaning and rinsing.

Furthermore, it is speculated that component B acts on the solder metal in the solvent containing component A to prevent it from corroding, and the cleaning property can be improved as described above, thereby obtaining a cleaning agent composition for removing flux residues that can inhibit the effects of corrosion on solder metal.

However, the present invention may be interpreted without being limited to this mechanism.

The "flux" mentioned in the present invention refers to a rosin-based flux containing rosin or rosin derivatives for soldering or a water-soluble flux without rosin, etc., which is used to remove oxides that hinder the connection between metals such as electrodes or wiring and solder metals to promote the above connection. The "soldering" mentioned in the present invention includes soldering by reflow method and flow soldering method. The "solder flux" mentioned in the present invention refers to a mixture of solder and flux. The "flux residue" mentioned in the present invention refers to the residue from the flux remaining in the substrate after the solder bump is formed using the flux and/or the substrate after the soldering is performed using the flux. For example, if other parts (e.g., semiconductor chips, chip-type capacitors, other circuit boards, etc.) are stacked on a circuit board, a space (gap) will be formed between the circuit board and the other parts. The flux used for the above loading will also remain in the gap in the form of flux residues 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, which includes the step of using the cleaning agent composition of the present invention to clean the object to be cleaned having flux residues. The cleaning method of the present invention is a cleaning method for removing flux residues in one or more embodiments, which includes contacting the object to be cleaned having flux residues with the cleaning agent composition of the present invention. As a method of using the cleaning agent composition of the present invention to clean an object to be cleaned, or a method of bringing the cleaning agent composition of the present invention into contact with an object to be cleaned, for example, a method of bringing the cleaning agent composition into contact in a bath of an ultrasonic cleaning device, a method of bringing the cleaning agent composition into contact by spraying the cleaning agent composition (spraying method), etc. The cleaning agent composition of the present invention can be used directly for cleaning without dilution. The cleaning method of the present invention preferably includes the steps of rinsing with water and drying after bringing the cleaning agent composition into contact with the object to be cleaned. According to the cleaning method of the present invention, the flux residues remaining in the gaps of the soldered parts can be cleaned efficiently. In terms of the cleaning property of the cleaning method of the present invention and the significant effect of penetrating into narrow gaps, the solder is preferably lead (Pb)-free solder. Furthermore, from the same viewpoint, the cleaning method of the present invention is preferably used for electronic components connected by solder using the flux described in International Publication No. 2006/025224, Japanese Patent Publication No. 6-75796, Japanese Patent Publication No. 2014-144473, Japanese Patent Publication No. 2004-230426, Japanese Patent Publication No. 2013-188761, Japanese Patent Publication No. 2013-173184, etc. In terms of making it easier to exert the cleaning power of the cleaning agent composition of the present invention, the cleaning method of the present invention preferably irradiates the cleaning agent composition of the present invention with ultrasound when it is in contact with the object to be cleaned, and it is more preferred that the ultrasound is relatively strong. From the same point of view, the frequency of the above-mentioned ultrasound is preferably 26~72Hz, 80~1500W, and more preferably 36~72Hz, 80~1500W.

[Cleaning agent composition]

The cleaning agent composition of the present invention is a cleaning agent composition used for cleaning a cleaned object having flux residues, and in one or more embodiments, it is a cleaning agent composition for removing flux residues. The so-called "cleaning agent composition for removing flux residues" in the present invention refers to a cleaning agent composition used for removing flux residues after forming solder bumps and/or soldering using flux or solder flux in one or more embodiments. In terms of the significant cleaning effect of the cleaning agent composition of the present invention, the solder is preferably a lead (Pb)-free solder containing tin.

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)。 Therefore, the present invention relates to a composition in one aspect, which is used as a cleaning agent for cleaning a target having flux residues, and contains an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the ring (component B).

中之至少一種胺(成分B)。 The present invention relates to a cleaning agent composition for removing flux residues, which contains: 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 a solvent selected from the group consisting of 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-(2-dimethylaminoethyl)-4-methylpiperidinazole.

At least one amine (ingredient B) in the present invention.

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)。 The present invention relates to a composition for cleaning a material having flux residues. The composition comprises an organic solvent (component A), an imidazole ring or a piperidine ring.

A compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the ring (component B).

(Ingredient A: organic solvent)

Component A in the cleaning agent composition of the present invention is an organic solvent. From the perspective of improving the flux removal performance, component A in one or more embodiments is preferably at least one solvent selected from the compound represented by the following formula (I), the compound represented by the following formula (II), and the compound represented by the following formula (III). Component A may also be one, a combination of two, or a combination of two or more.

R ¹ -O-(AO) _n -R ² (I)

In the above formula (I), from the viewpoint of improving the flux removal property, it is preferred that ^R1 is a phenyl group or an alkyl group having 1 to 8 carbon atoms, ^R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an oxyethyl group or an oxypropyl group, and n is the addition molar number of AO and is an integer of 1 to 3.

In the above formula (I), from the viewpoint of improving the flux removability, ^R1 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, and further preferably an alkyl group having 4 to 6 carbon atoms. From the viewpoint of improving the flux removability, ^R2 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 further preferably a hydrogen atom or an n-butyl group. Furthermore, from the viewpoint of improving the flux removability, it is preferred that ^R1 is an alkyl group having 1 to 3 carbon atoms and ^R2 is an alkyl group having 1 to 3 carbon atoms. From the viewpoint of improving the flux removability, AO is preferably an oxyethylene group or an oxypropylene group, and further preferably an oxyethylene group. From the viewpoint of improving the flux removal property, n is preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 2.

Examples of the compound represented by the above formula (I) include monophenyl ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether; monoalkyl ethers such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and triethylene glycol monoalkyl ether having an alkyl group with a carbon number of 1 to 8; dialkyl ethers such as ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, and triethylene glycol dialkyl ether having an alkyl group with a carbon number of 1 to 8 and an alkyl group with a carbon number of 1 to 4; and phenyl alkyl ethers such as ethylene glycol phenyl alkyl ether, diethylene glycol phenyl alkyl ether, and triethylene glycol phenyl alkyl ether having a phenyl group and an alkyl group with a carbon number of 1 to 4. The compound represented by the above formula (I) is preferably selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, ethylene glycol dibutyl ether, di ...phenyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, At least one of glycol dibutyl ether and triethylene glycol dimethyl ether, more preferably at least one selected from diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, dipropylene glycol monobutyl ether and diethylene glycol dibutyl ether, further preferably at least one selected from diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether and diethylene glycol dimethyl ether, further preferably diethylene glycol dimethyl ether.

R ³ -CH ₂ OH (II)

In the above formula (II), from the viewpoint of improving the flux removability, ^R3 is preferably a phenyl group, a benzyl group, a cyclohexyl group, a furyl group, a tetrahydrofuranyl group, a furanyl group or a tetrahydrofuranyl group, more preferably a phenyl group, a cyclohexyl group or a tetrahydrofuranyl group, further preferably a phenyl group or a tetrahydrofuranyl group, further more preferably a phenyl group.

As the compound represented by the above formula (II), for example, benzyl alcohol, phenylethyl alcohol, cyclohexane methanol, furan methanol and tetrahydrofuran methanol can be listed. As the compound represented by the above formula (II), from the viewpoint of improving the flux removal performance, it is preferably at least one selected from benzyl alcohol, furan methanol and tetrahydrofuran methanol, more preferably at least one selected from benzyl alcohol and tetrahydrofuran methanol, and further preferably benzyl alcohol.

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

Examples of the compound represented by the above 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 and 5-methyl-2-pyrrolidone. As the compound represented by the above formula (III), from the viewpoint of improving the flux removal property, it is preferably at least one selected from 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 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 more preferably 1-methyl-2-pyrrolidone.

Component A may be one, a combination of two, or a combination of two or more. When component A is a combination of two, component A may include, for example, a combination of a compound represented by formula (I) and a compound represented by formula (II).

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

From the viewpoint of improving the flux removal performance, the content of component A in the cleaning agent composition of the present invention is preferably 35% by mass or more, more preferably 50% by mass or more, and further preferably 75% by mass or more, and further preferably 99.5% by mass or less, more preferably 99.3% by mass or less, and further preferably 99% by mass or less. More specifically, the content of component A in the cleaning agent 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 further preferably 75% by mass or more and 99% by mass or less. When component A is a combination of two or more components, the content of component A refers to the total content of the components.

(Component B: amine)

環之氮原子上具有碳數1以上4以下之烷基之化合物。就提高助焊劑除去性之觀點而言，成分B較佳為選自1-甲基咪唑、1,2-二甲基咪唑、1-異丁基-2-甲基咪唑及1-(2-二甲基胺基乙基)-4-甲基哌

中之至少一種胺。成分B亦可為1種、2種之組合、或2種以上之組合。就提高松香系助焊劑除去性之觀點而言，成分B較佳為於咪唑環之氮原子上具有碳數1以上4以下之烷基之化合物，較佳為選自1-甲基咪唑、1,2-二甲基咪唑、及1-異丁基-2-甲基咪唑中之至少一種胺，更佳為選自1-甲基咪唑及1,2-二甲基咪唑中之至少一種胺。 The component B in the cleaning agent composition of the present invention is an imidazole ring or a piperidine ring.

A compound having an alkyl group with 1 to 4 carbon atoms on the nitrogen atom of the ring. From the viewpoint of improving the flux removal performance, component B is preferably selected from 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1-(2-dimethylaminoethyl)-4-methylpiperidazole.

Component B may be one, a combination of two, or a combination of two or more. From the viewpoint of improving the removability of rosin-based flux, component B is preferably a compound having an alkyl group with 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.

The content of component B in the cleaning agent composition of the present invention is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, further preferably 0.4% by mass or more, further preferably 0.5% by mass or more from the viewpoint of improving flux removal performance, and is preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less, further preferably 8% by mass or less, further preferably 5% by mass or less from the viewpoint of suppressing solder metal corrosion. More specifically, the content of component B in the cleaning agent composition of the present invention is preferably 0.2 mass% to 15 mass%, more preferably 0.3 mass% to 10 mass%, further preferably 0.4 mass% to 8 mass%, further preferably 0.5 mass% to 5 mass%. When component B is a combination of two or more, the content of component B refers to the total content of such components.

In the cleaning agent 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 further preferably 15 or more, and preferably 200 or less, more preferably 100 or less, and further preferably 25 or less, from the perspective of improving flux removal performance. 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 cleaning agent composition of the present invention may further contain water (component C) in one or more embodiments. As component C, ion exchange water, RO (reverse osmosis) water, distilled water, pure water, ultrapure water, etc. can be used. From the viewpoint of reducing the flash point, the content of component C in the cleaning agent composition of the present invention is preferably 1 mass % or more, more preferably 5 mass % or more, and further preferably 8 mass % or more, and from the viewpoint of improving the flux removal property, it is preferably 55 mass % or less, more preferably 15 mass % or less, further preferably 12 mass % or less, and further preferably 10 mass % or less. More specifically, the content of component C in the cleaning agent composition of the present invention is preferably 1% by mass to 55% by mass, more preferably 1% by mass to 15% by mass, further preferably 5% by mass to 12% by mass, further preferably 8% by mass to 10% by mass.

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

(Other ingredients)

The cleaning agent composition of the present invention may contain other components as needed in addition to the above-mentioned components A to C. The content of other components in the cleaning agent composition of the present invention is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 8% by mass, further preferably 0% by mass to 5% by mass, further preferably 0% by mass to 2% by mass.

As other components in the cleaning agent composition of the present invention, from the viewpoint of improving stability, for example, a surfactant can be listed. As a surfactant, for example, non-ionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkylamines, glycerol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, alkyl glucosides, and alkyl glyceryl ethers are preferred, and polyoxyalkylene alkyl ethers and alkyl glyceryl ethers are more preferred, and alkyl glyceryl ethers are further preferred. As specific examples of surfactants, 2-ethylhexyl glyceryl ether and the like can be listed. From the viewpoint of improving stability, the content of the surfactant in the cleaning agent composition of the present invention is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and preferably 7% by mass or less, and more preferably 5% by mass or less. More specifically, the content of the surfactant is preferably 0.5 mass% to 7 mass%, and more preferably 0.8 mass% to 5 mass%.

As further other ingredients, the cleaning agent composition of the present invention may contain, as needed, chelating compounds such as aminocarboxylic acid salts such as hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, and ethylenediaminetetraacetic acid, antirust agents such as benzotriazole, thickeners, dispersants, alkaline substances other than component B, polymer compounds, solubilizers, preservatives, bactericides, antibacterial agents, defoaming agents, and antioxidants used in conventional cleaning agents within the scope of not damaging the effect of the present invention.

[Manufacturing method of cleaning agent composition]

The cleaning agent composition of the present invention can be prepared, for example, by mixing component A and component B, and optionally the above-mentioned component C and other components using a known method. The cleaning agent composition of the present invention can be prepared by mixing at least component A and component B in one or more embodiments. Therefore, the present invention, in one embodiment, is related to a method for preparing a cleaning agent composition including the step of mixing at least component A and component B. The so-called "mixing" in the present invention includes mixing component A, component B, and optionally component C and other components at the same time or in any order. In the method for preparing the cleaning agent composition of the present invention, the mixing amount of each component can be set to be the same as the content of each component of the cleaning agent composition of the present invention. The "content of each component in the cleaning agent composition" mentioned in the present invention refers to the content of the above-mentioned components at the time of cleaning, that is, at the time when the cleaning agent composition is used for cleaning.

The cleaning agent composition of the present invention can also be manufactured and stored in the form of a concentrate from the viewpoint of addition, storage and transportation. The dilution ratio of the concentrate of the cleaning agent composition of the present invention can be, for example, 3 times or more and 30 times or less. The concentrate of the cleaning agent composition of the present invention can be used by diluting it with water (ingredient C) in such a way that ingredient A, ingredient B, and ingredient C and other ingredients prepared as needed are in the above-mentioned content (i.e., the content during cleaning).

[pH value of cleaning agent composition]

The cleaning agent composition of the present invention is preferably alkaline in terms of improving the flux removal performance, for example, preferably having a pH value of 8 or more and a pH value of 14 or less. The pH value can be adjusted by appropriately mixing the following in the required amount as needed, namely: inorganic acids such as nitric acid and sulfuric acid; organic acids such as hydroxycarboxylic acids, polycarboxylic acids, aminopolycarboxylic acids, and amino acids; and alkaline substances other than component B such as metal salts or ammonium salts thereof, ammonia, sodium hydroxide, potassium hydroxide, and amines. The pH value of the cleaning agent composition in the present invention is the pH value of the cleaning agent composition at 25°C when it is used (after dilution).

[Things to be cleaned]

The cleaning agent composition of the present invention is used in one or more embodiments to clean an object having flux residues. An example of an object having flux residues is an object having reflowed solder. As specific examples of the objects to be cleaned, for example, electronic components and intermediate products thereof can be listed. Specifically, electronic components and intermediate products thereof can be listed. More specifically, electronic components and intermediate products thereof with components soldered together by solder, electronic components and intermediate products thereof with components connected by solder, electronic components and intermediate products thereof with flux residues in the gaps between soldered components, and electronic components and intermediate products thereof with flux residues in the gaps between components connected by solder, etc. can be listed. The above-mentioned intermediate manufacturing products are intermediate products in the manufacturing steps of electronic parts of semiconductor packages or semiconductor devices, for example, circuit substrates mounted with at least one component selected from semiconductor chips, chip capacitors and circuit substrates by soldering using flux, and/or circuit substrates formed with solder bumps for soldering the above-mentioned components. The so-called gap in the cleaned object refers to, for example, a space formed between the circuit substrate and the components (semiconductor chips, chip capacitors, circuit substrates, etc.) soldered and mounted on the circuit substrate, and the height (distance between components) is, for example, 5-500μm, 10-250μm, or 20-100μm. The width and depth of the gap depend on the size or spacing of the mounted parts or electrodes (pads) on the circuit board.

[Manufacturing method of electronic parts]

The present invention relates to a method for manufacturing an electronic component (hereinafter, also referred to as "the method for manufacturing an electronic component of the present invention") in one aspect, which comprises the following steps: at least one step selected from the step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit substrate on a circuit substrate by soldering using a flux and the step of forming a solder bump for connecting the above components on the circuit substrate; and the step of cleaning at least one selected from the circuit substrate on which the above components are mounted and the circuit substrate on which the above solder bumps are formed by the cleaning method of the present invention. The soldering using the flux is, for example, performed using lead-free solder, and can be a reflow method or a flow soldering method. Electronic components include semiconductor packages without semiconductor chips, semiconductor packages with semiconductor chips, and semiconductor devices. The manufacturing method of electronic components of the present invention can reduce the flux residues remaining in the gaps between soldered components or the periphery of solder bumps by performing the cleaning method of the present invention, thereby suppressing the short circuit or poor connection between electrodes caused by the residual flux residues, thereby manufacturing electronic components with higher reliability. Furthermore, by performing the cleaning method of the present invention, it becomes easier to clean the flux residues remaining in the gaps between soldered components, thereby shortening the cleaning time and improving the manufacturing efficiency of electronic components.

[Set]

The present invention, in one embodiment, relates to a kit for use in the cleaning method of the present invention and/or the method for manufacturing the electronic components of the present invention (hereinafter, also referred to as the "kit of the present invention"). The kit of the present invention, in one or more embodiments, is a kit for manufacturing the cleaning agent composition of the present invention.

As one embodiment of the kit of the present invention, a kit (two-liquid cleaning agent composition) can be cited that includes a solution containing the above-mentioned component A (first liquid) and a solution containing component B (second liquid) in a state that they do not mix with each other, and the first liquid and the second liquid are mixed when used. Therefore, the cleaning method of the present invention may include the following steps in one or more embodiments: the solution containing component A (first liquid) and the solution containing component B (second liquid) are mixed when used to prepare the cleaning agent composition. Furthermore, the cleaning method of the present invention may include the following steps in one or more embodiments: using a kit containing a solution containing component A (first liquid) and a solution containing component B (second liquid) in a non-mixed state, and mixing the first liquid and the second liquid when used to prepare a cleaning agent composition.

The first liquid and the second liquid may contain the component C and other components as needed. At least one of the first liquid and the second liquid may contain a part or all of the component C (water) in one or more embodiments. In one or more embodiments, after mixing the first liquid and the second liquid, the component C (water) may be used for dilution as needed.

The present invention further relates to one or more of the following embodiments.

中之至少一種胺(成分B)。 <1> A flux residue removal cleaning agent composition comprising: 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 a solvent selected from the group consisting of 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-(2-dimethylaminoethyl)-4-methylpiperidinazole.

At least one amine (ingredient B) in the present invention.

R ¹ -O-(AO) _n -R ² (I)

In the above formula (I), ^R1 is a phenyl group or an alkyl group having 1 to 8 carbon atoms, ^R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an oxyethyl group or an oxypropyl group, and n is the added molar number of AO 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, furyl, tetrahydrofuranyl, furanyl or tetrahydrofuranyl.

In the above formula (III), R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently a hydrogen atom, a alkyl 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 of <1>, wherein in the above formula (I), ^R1 is a phenyl group or an alkyl group having 1 to 8 carbon atoms, preferably a phenyl group or an alkyl group having 4 to 6 carbon atoms, and more preferably an alkyl group having 4 to 6 carbon atoms.

<3> The cleaning agent composition of <1> or <2>, wherein in the above formula (I), ^R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 2 to 4 carbon atoms, and more preferably a hydrogen atom or an n-butyl group.

<4> A cleaning agent composition as described in any one of <1> to <3>, wherein in the above formula (I), AO is an oxyethyl group or an oxypropyl group, preferably an oxyethyl group.

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

<6> The cleaning agent composition according to any one of <1> to <5>, wherein in the above formula (II), ^R3 represents phenyl, benzyl, cyclohexyl, furyl, tetrahydrofuranyl, furanyl or tetrahydrofuranyl, preferably phenyl, cyclohexyl or tetrahydrofuranyl, more preferably phenyl or tetrahydrofuranyl, and even more preferably phenyl.

<7> The cleaning agent composition of any one of <1> to <6>, wherein in the above formula (III), R ⁴ , R ⁵ , R ⁶ , and R ⁷ are independently a hydrogen atom, a alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydroxyl group. Preferably, any one of R ⁴ , R ⁵ , R ⁶ , and R ⁷ is a alkyl group having 1 to 8 carbon atoms, more preferably, a alkyl group having 1 to 6 carbon atoms, and further preferably, any one of methyl, ethyl, and vinyl.

<8> A cleaning agent composition as described in any one of <1> to <7>, wherein component A is preferably at least one selected from 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 diethylene glycol monobutyl ether, benzyl alcohol and 1-methyl-2-pyrrolidone.

<9> A cleaning agent composition as described in 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 further preferably 75% by mass or more.

<10> A cleaning agent composition as described in any one of <1> to <9>, wherein the content of component A 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.

<11> A cleaning agent composition as described in 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, and further preferably 75% by mass to 99% by mass.

<12> A cleaning agent composition as described in 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, further preferably 0.4% by mass or more, further preferably 0.5% by mass or more.

<13> A cleaning agent composition as described in 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, more preferably 10% by mass or less, further preferably 8% by mass or less, further preferably 5% by mass or less.

<14> A cleaning agent composition as described in any one of <1> to <13>, wherein the content of component B is preferably 0.2 mass % to 15 mass %, more preferably 0.3 mass % to 10 mass %, further preferably 0.4 mass % to 8 mass %, further preferably 0.5 mass % to 5 mass %.

<15> A cleaning agent composition as described in 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 even more preferably 15 or more.

<16> A cleaning agent composition as described in 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 25 or less.

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

<18> A cleaning agent composition as described in any one of <1> to <17>, further comprising water (ingredient C).

<19> The cleaning agent composition as described in <18>, wherein the content of component C is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more.

<20> The cleaning agent composition of <18> or <19>, wherein the content of component C is preferably 55% by mass or less, more preferably 15% by mass or less, further preferably 12% by mass or less, further preferably 10% by mass or less.

<21> A cleaning agent composition as described in 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, further preferably 5% by mass to 12% by mass, further preferably 8% by mass to 10% by mass.

<22> A cleaning agent composition as described in any one of <1> to <21>, further comprising a surfactant.

<23> A cleaning agent composition as described in any one of <1> to <22>, further comprising at least one selected from a compound having chelating power, a rust inhibitor such as benzotriazole, a thickener, a dispersant, an alkaline substance other than component B, a polymer compound, a solubilizer, a preservative, a bactericide, an antibacterial agent, a defoaming agent, and an antioxidant.

<24> A cleaning method, comprising the step of cleaning an object having flux residues using a cleaning agent composition as described in any one of <1> to <23>.

<25> A cleaning method as in <24>, wherein the object to be cleaned is an intermediate in the manufacturing process of soldering electronic parts.

<26> A method for manufacturing electronic components, comprising the following steps: at least one step selected from the step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit substrate on a circuit substrate by soldering using a flux and the step of forming solder bumps for connecting the above components on the circuit substrate; and the step of cleaning at least one of the circuit substrates mounted with the above components and the circuit substrates formed with the above solder bumps by a cleaning method such as <24> or <25>.

<27> A kit, which is used in the cleaning method of <24> or <25> and/or the method for manufacturing electronic parts of <26>, and contains a solution containing component A (first liquid) and a solution containing component B (second liquid) in a non-mixable state, and the first liquid and the second liquid are mixed during use.

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)。 <28> A cleaning method comprising the step of using a cleaning agent composition to clean an object having flux residues, wherein the cleaning agent composition comprises an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the ring (component B).

中之至少一種胺。 <29> The cleaning method of <28>, wherein component B is selected from 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole and 1-(2-dimethylaminoethyl)-4-methylpiperidazole.

At least one amine.

<30> A cleaning method as described in <28> or <29>, wherein 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).

R ¹ -O-(AO) _n -R ² (I)

In the above formula (I), ^R1 is a phenyl group or an alkyl group having 1 to 8 carbon atoms, ^R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an oxyethyl group or an oxypropyl group, and n is the added molar number of AO 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, furyl, tetrahydrofuranyl, furanyl or tetrahydrofuranyl.

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

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

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

<33> A cleaning method as described in any one of <28> to <32>, wherein the cleaning agent composition further contains water (ingredient C).

<34> A cleaning method as in <33>, wherein the content of component C in the cleaning agent composition is less than 15% by mass.

<35> A cleaning method as described in any one of <28> to <34>, wherein the content of component B in the cleaning agent composition is greater than 0.2 mass % and less than 15 mass %.

<36> A cleaning method as described in any one of <28> to <35>, wherein component A is at least one selected from diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, benzyl alcohol and 1-methyl-2-pyrrolidone.

<37> A cleaning method as described in any one of <28> to <36>, wherein the content of other components other than components A to C in the above-mentioned cleaning agent composition is greater than 0 mass % and less than 10 mass %.

<38> A cleaning method as described in any one of <28> to <37>, wherein the object to be cleaned is an intermediate in the manufacture of soldered electronic parts.

<39> A cleaning method as described in any one of <28> to <38>, comprising the following steps: mixing the first liquid and the second liquid when the solution containing component A (the first liquid) and the solution containing component B (the second liquid) are immiscible with each other to prepare a cleaning agent composition.

<40> A cleaning method as described in any one of <28> to <39>, wherein the cleaning agent composition is used to clean the object by contacting the object in a bath of an ultrasonic cleaning device or by spraying the cleaning agent composition in a spray form.

<41> A method for manufacturing an electronic component, comprising the following steps: at least one step selected from the step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit substrate on a circuit substrate by soldering using a flux and the step of forming solder bumps for connecting the above components on the circuit substrate; and the step of cleaning at least one selected from the circuit substrate on which the above components are mounted and the circuit substrate on which the above solder bumps are formed by a cleaning method as described in any one of <28> to <40>.

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)。 <42> A composition for use as a cleaning agent for cleaning an object having flux residues, comprising an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the ring (component B).

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)。 <43> A composition for cleaning an object having flux residues, the composition comprising an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound in which the nitrogen atom of the ring has an alkyl group having 1 to 4 carbon atoms (component B).

[Implementation example]

The present invention is described in detail below using examples, but the present invention is not limited to these examples.

1. Preparation of cleaning agent composition (Examples 1 to 16, Comparative Examples 1 to 9)

In a 100 mL glass beaker, each component was prepared in the manner of the composition described in Table 1 below, and mixed under the following conditions to prepare the cleaning agent compositions of Examples 1 to 16 and Comparative Examples 1 to 9. The numerical values of each component in Table 1 represent the content (mass %) in the prepared cleaning agent composition unless otherwise specified.

<Mixing conditions>

Liquid temperature: 25℃

Mixer: Magnetic stirrer (50mm rotor)

Speed: 300rpm

Stirring time: 10 minutes

Use the following as ingredients in the cleaning composition.

(Ingredient A)

A1: Benzyl alcohol [manufactured by Lanxess Co., Ltd.]

A2: Diethylene glycol monobutyl ether [manufactured by Japan Emulsifier Co., Ltd., diethylene glycol monobutyl ether (BDG)]

A3: Dipropylene glycol monobutyl ether [manufactured by Japan Emulsifier Co., Ltd., dipropylene glycol monobutyl 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 Fuji Film Wako Pure Chemical Industries, Ltd.]

(Ingredient B)

B1: 1-Methylimidazole [Kao Corporation, Kaolizer No.110]

B2: 1,2-dimethylimidazole [manufactured by Tokyo Chemical Industry Co., Ltd.]

B3: 1-isobutyl-2-methylimidazole [manufactured by Kao Corporation, Kaolizer No.120]

[花王股份有限公司製造，Kaolizer No.8] B4: 1-(2-dimethylaminoethyl)-4-methylpiperidin

[Manufactured by Kao Corporation, Kaolizer No.8]

(Non-ingredient B)

B5: Triethanolamine [manufactured by Japan Catalyst Co., Ltd.]

B6: Methyldiethanolamine [manufactured by Japan Emulsifier Co., Ltd., amino alcohol MDA]

B7: 2-ethyl-4-methylimidazole [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.]

B8: 1,5-dimethyl-2-pyrrolidone

(Ingredient C)

Water [pure water below 1μS/cm produced by the pure water device G-10DSTSET manufactured by Organo Co., Ltd.]

(Other ingredients: surfactant) 2-Ethylhexylglyceryl ether [produced by the following production method]

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

(Other ingredients: rust inhibitor)

Benzotriazole [manufactured by Tokyo Chemical Industry Co., Ltd., 1,2,3-benzotriazole]

2. Evaluation of cleaning agent composition

The cleaning agent compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 9 were used to test and evaluate the cleaning and anti-corrosion properties.

<Test substrate>

The following solder paste was applied on a copper wiring printed circuit board (10 mm × 15 mm) using a screen. The test board was produced by reflowing at 250°C in a nitrogen atmosphere.

<Composition of flux>

Fully hydrogenated rosin (manufactured by Eastman Chemical, Foral AX-E) 58.0 mass%

N,N'-Diphenylguanidine hydrobromide (manufactured by Wako Chemical Co., Ltd.) 0.5 mass%

Adipic acid (produced by Wako Pure Chemical Industries, Ltd.) 0.5 mass%

Hydrogenated castor oil (produced by Toyota Oil Corporation) 6.0 mass%

Hexyl glycol (manufactured by Japan Emulsifier Co., Ltd.) 35.0 mass%

<Method for manufacturing flux>

The flux of the above composition is obtained by adding the remaining other components to the hexyl glycol solvent and dissolving them.

<Method for manufacturing solder paste>

11.0 g of the above flux was mixed with 89.0 g of solder powder [M705 (Sn/Ag/Cu=96.5/3/0.5, manufactured by Senju Metal Industries, Ltd.] for 1 hour to prepare the soldering agent.

<Cleaning test>

The cleaning test is carried out in the following order.

First, prepare the ultrasonic cleaning tank, the first rinse tank, and the second rinse tank under the following conditions. The ultrasonic cleaning tank is set to 40kHz in frequency and 200W in output. It is obtained by adding 50g of each cleaning agent composition to a 50mL glass beaker, placing it in the ultrasonic cleaning layer and heating it to 60℃. The first rinse tank and the second rinse tank are obtained by preparing two 100mL glass beakers with a 50mm rotor, adding 100g of pure water respectively, placing them in a warm bath, and heating them to 40℃ while stirring at a rotation speed of 100rpm.

Next, hold the test substrate with tweezers and insert it into the ultrasonic cleaning tank for immersion for 5 minutes. Next, hold the test substrate with tweezers and insert it into the first rinse tank, and immerse it for 3 minutes while stirring at a speed of 100 rpm.

Then, the test substrate was held with tweezers and inserted into the second rinse tank, where it was immersed for 3 minutes while being stirred at 100 rpm.

Finally, the test substrates were nitrogen flushed and dried.

[Evaluation of cleanliness (flux removal)]

After cleaning, the test substrate was observed using a tabletop microscope Miniscope TM3030 (manufactured by Hitachi High-Technologies Co., Ltd.), and the presence of residual flux on any 10 solder bumps was visually checked, and the number of residual flux was counted. The results are shown in Table 1.

Furthermore, the test substrate was observed using an optical microscope VHX-2000 (manufactured by KEYENCE Co., Ltd.) to visually check whether there were residual flux residues near the solder bumps, and the number of solder bumps with residual flux residues near the solder bumps was counted. The results are shown in Table 1.

[Evaluation of corrosion resistance]

Using an optical microscope VHX-2000 (manufactured by KEYENCE Co., Ltd.) and a desktop microscope Miniscope TM3030 (manufactured by Hitachi High-Technologies Co., Ltd.), the solder metal on the test substrate after the evaluation of cleanliness (flux removal) was visually observed, and the impact on the solder metal was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

<Evaluation criteria>

A: No effect on solder metal

B: There are effects on solder metal caused by corrosion, etc.

[Evaluation of cleanliness (solubility of rosin acid)]

In order to confirm the affinity of the flux, the solubility of rosin acid, which is a component of the flux, was evaluated using the following method. The evaluation results are shown in Table 1.

Add 100g of the cleaning agent composition and 1g of rosin acid to a 50mL glass beaker, use an ultrasonic cleaning tank, set the frequency to 40kHz and the output to 200W, and perform ultrasonic treatment at 25°C for 1 hour. When the rosin acid is dissolved, add 1g of rosin acid and perform the same operation. Repeat this operation until the rosin acid becomes undissolved, and estimate the solubility. The higher the solubility, the better the removability of rosin-based flux. From the perspective of improving the removability of 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 more preferably 60% by mass or more.

<Evaluation criteria>

A: Solubility is 60% by mass or more

B: Solubility is 50% by mass or more and less than 60% by mass

C: Solubility is 40% by mass or more and less than 50% by mass

D: Solubility less than 40% by mass

As shown in Table 1 above, the cleaning agent compositions of Examples 1 to 16 containing component A and component B have superior flux removal properties compared to Comparative Examples 1 to 9 not containing component A or component B. Furthermore, the cleaning agent compositions of Examples 1 to 16 have suppressed effects on solder metal. In addition, the solubility of rosin acid in the cleaning agent compositions of Examples 2 to 3, 6, 9 to 11, 13 to 14, and 16 is higher than 50% by mass, and it can be seen that the rosin-based flux removal properties are superior compared to Examples 1, 4 to 5, 7 to 8, 12, and 15.

Industrial availability

By using the present invention, the flux residue can be cleaned well, so that, for example, the flux residue cleaning step in the manufacturing process of electronic components can be shortened and the performance and reliability of the manufactured electronic components can be improved, thereby improving the productivity of electronic components.

Claims (16)

A cleaning method includes the step of using a cleaning agent composition to clean an object having flux residues, wherein the cleaning agent composition contains component A and component B, component A is an organic solvent, and component B is an imidazole ring or a piperidine ring.

A compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the 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-dimethylaminoethyl)-4-methylpiperidazole.

At least one amine. The cleaning method of claim 1 or 2, wherein 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), R ¹ -O-(AO) _n -R ² (I) In the above formula (I), R ¹ is a phenyl group or an alkyl group having 1 to 8 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an oxyethyl group or an oxypropyl group, n is the added molar number of AO and is an integer of 1 to 3, R ³ -CH ₂ OH (II) In the above formula (II), R ³ is a phenyl group, a benzyl group, a cyclohexyl group, a furanyl group, a tetrahydrofuranyl group, a furanyl group, or a tetrahydrofuranyl group, [Chemical 1]

In the above formula (III), R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently a hydrogen atom, a alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms or a hydroxyl group. A cleaning method as claimed in claim 1 or 2, wherein the content of component A in the above-mentioned cleaning agent composition is greater than 35% by mass and less than 99.5% by mass. A cleaning method as claimed in claim 1 or 2, wherein the mass ratio of component A to component B in the above-mentioned cleaning agent composition (component A/component B) is greater than 8 and less than 200. A cleaning method as claimed in claim 1 or 2, wherein the cleaning agent composition further contains ingredient C, which is water. The cleaning method of claim 6, wherein the content of component C in the above-mentioned cleaning agent composition is less than 15% by mass. A cleaning method as claimed in claim 1 or 2, wherein the content of component B in the above-mentioned cleaning agent composition is greater than 0.2 mass % and less than 15 mass %. The cleaning method of claim 1 or 2, wherein component A is at least one selected from diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, benzyl alcohol and 1-methyl-2-pyrrolidone. For example, the cleaning method of claim 1 or 2, wherein the content of other components other than components A to C in the above-mentioned cleaning agent composition is greater than 0 mass % and less than 10 mass %. A cleaning method as claimed in claim 1 or 2, wherein the object to be cleaned is an intermediate in the manufacturing process of soldering electronic parts. The cleaning method of claim 1 or 2 includes the following steps: mixing the first liquid and the second liquid when the first liquid and the second liquid are immiscible with each other to prepare a cleaning agent composition, wherein the first liquid is a solution containing component A and the second liquid is a solution containing component B. The cleaning method of claim 1 or 2 uses a contact method in a bath of an ultrasonic cleaning device or a contact method by spraying the cleaning agent composition, and uses the cleaning agent composition to clean the object to be cleaned. A method for manufacturing electronic components, comprising the following steps: at least one step selected from the step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit substrate on a circuit substrate by soldering using a flux and the step of forming solder bumps for connecting the above components on the circuit substrate; and the step of cleaning at least one selected from the circuit substrate on which the above components are mounted and the circuit substrate on which the above solder bumps are formed by a cleaning method as described in any one of claims 1 to 13. A composition is used as a cleaning agent for cleaning an object having flux residues, and contains an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the ring (component B). A composition is used for cleaning a material with flux residues, the composition comprising an organic solvent (component A), and an imidazole ring or a piperidine ring.

A compound having an alkyl group having 1 to 4 carbon atoms on the nitrogen atom of the ring (component B).