JP2018053248A - Azeotropic cleaning agent and regeneration method thereof, cleaning method, and cleaning agent kit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an azeotropic cleaning agent and a regeneration method thereof, a cleaning method, and a cleaning agent kit.SOLUTION: An azeotropic cleaning agent contains an azeotropic mixture, the azeotropic mixture containing a glycol ether represented by general formula: R-O-CH-CHX-O-H (where when X is a hydrogen atom, R is a group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group; when X is a methyl group, R is a group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group) and water.SELECTED DRAWING: None

Description

  The present disclosure relates to an azeotropic cleaning agent, a regeneration method thereof, a cleaning method, and a cleaning agent kit.

  When an electronic component is joined to an electrode of a printed wiring board using solder paste, solder containing solder, or the like, flux is inevitably generated. Therefore, various cleaning agents are used in this field in order to remove the flux.

  As a cleaning agent for removing flux, once a chlorofluorocarbon-based cleaning agent has been the mainstream. However, as a result of considering adverse environmental impacts, non-fluorocarbon-based cleaning agents such as hydrocarbon-based cleaning agents and glycol-based cleaning agents have recently been used. A cleaning agent is used.

  Among non-fluorocarbon cleaners, glycol cleaners are composed of various glycol compounds and water, and are not only excellent in the removal of flux and ion residues, but are also non-hazardous hydrocarbon cleaners. Superior to agents (Patent Documents 1 to 3).

  For hydrocarbon cleaners consisting of a combination of specific hydrocarbon solvents, a technology that enables distillation regeneration by limiting the azeotropic composition for the purpose of recycling the waste liquid used for cleaning and rinsing. Have been proposed (Patent Documents 4 to 6).

Japanese Patent Laid-Open No. 3-152197 Japanese Patent Laid-Open No. 5-175541 Japanese Patent Laid-Open No. 10-046198 Japanese Patent Laid-Open No. 10-053797 JP 2004-307839 A JP 2008-024901 A

  When using a glycol-based cleaning agent, a large amount of cleaning agent waste fluid containing dirt such as flux and rinse agent waste fluid (rinsing water etc.) containing a rinsing agent used when rinsing the cleaning agent is rinsed. Therefore, appropriate equipment and cost are required for the processing. Therefore, it has been demanded to reduce the amount of cleaning agent waste liquid and waste water generated during cleaning.

  A main problem to be solved by the present disclosure is to provide an azeotropic cleaning agent that contains a glycol solvent and is recyclable, a regeneration method thereof, and a cleaning method.

  As a result of intensive studies, the inventors of the present invention obtained an azeotropic cleaning agent that can be regenerated by distillation and that can be easily dried by limiting the composition of a specific glycol ether and water to an azeotropic composition. I found out that

The present disclosure provides the following items.
(Item 1) General formula (1): R—O—CH ₂ —CHX—O—H
(In the formula, when X represents a hydrogen atom, R is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Represents the selected group,
When X represents a methyl group, R is a group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Represents a group selected from: An azeotropic cleaning agent comprising an azeotropic mixture containing glycol ether and water represented by:
(Item 2) The azeotropic cleaning agent according to the above item, comprising an azeotropic mixture of the glycol ether and water.
(Item 3) The glycol ether and the general formula (2): R ¹ R ² N— (CH ₂ ) _n —NR ³ R ⁴
(Wherein R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6)
The azeotropic cleaning agent according to the above item, comprising an azeotropic mixture comprising a diamine represented by
(Item 4) The azeotropic cleaning agent according to any one of the above items, wherein the azeotropic cleaning agent does not contain a surfactant.
(Item 5) The azeotropic cleaning agent according to any one of the above items, wherein the azeotropic cleaning agent includes only the azeotropic mixture.
(Item 6) The azeotropic cleaning agent according to any one of the above items, wherein the azeotropic cleaning agent does not have a cloud point.
(Item 7) The azeotropic cleaning agent according to any one of the above items, wherein the azeotropic cleaning agent is a rinse agent.
(Item 8) The azeotropic cleaning agent according to the above item, wherein the rinse agent is for a flux cleaning solution.
(Item 9) A method for regenerating an azeotropic cleaning agent, comprising a step of distilling a liquid containing the azeotropic cleaning agent according to any one of the above items to obtain the azeotropic mixture.
(Item 10) The method includes a step of bringing the azeotropic cleaning agent according to any one of the above items into contact with a cleaning agent and / or a contaminant adhering to an article. A cleaning method that is not an azeotropic cleaning agent according to any one of the above items.
(Item 11) General Formula (A): R ^A1 —O— (CH ₂ —CHR ^A2 —O) _a —R ^A3
(In the formula, R ^A1 represents an alkyl group having 1 to 6 carbon atoms or a benzyl group, R ^A2 represents a methyl group or a hydrogen atom, R ^A3 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, and a Represents an integer of 2 to 4.)
An organic solvent (A) represented by
Formula (B):
(In the formula, R ^B represents an alkyl group having 1 to 7 carbon atoms, B represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, b1 represents an integer of 1 to 15 and b2 represents 0 to 15) Represents an integer.)
An amine (B) represented by
And a step of bringing a non-azeotropic cleaning agent containing an amino group-free chelating agent (C) into contact with a contaminant attached to the article, and attaching the azeotropic cleaning agent according to any one of the above items to the article The cleaning method according to the above item, which comprises a step of contacting the non-azeotropic cleaning agent and / or contaminants.
(Item 12) The cleaning method according to any one of the above items, wherein the contaminant includes at least one of the group consisting of soldering flux, solder paste, and industrial oil.
(Item 13)
Formula (A): R ^A1 —O— (CH ₂ —CHR ^A2 —O) _a —R ^A3
(In the formula, R ^A1 represents an alkyl group having 1 to 6 carbon atoms or a benzyl group, R ^A2 represents a methyl group or a hydrogen atom, R ^A3 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, and a Represents an integer of 2 to 4.)
An organic solvent (A) represented by
Formula (B):
(In the formula, R ^B represents an alkyl group having 1 to 7 carbon atoms, B represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, b1 represents an integer of 1 to 15 and b2 represents 0 to 15) Represents an integer.)
An amine (B) represented by
And a non-azeotropic cleaning agent containing the amino group-free chelating agent (C) and the azeotropic cleaning agent according to any one of the above items.

  The azeotropic cleaning agent according to this embodiment can be regenerated by distillation operation even if the waste liquid after cleaning contains a flux or a cleaning agent other than the azeotropic cleaning agent according to this embodiment. The composition ratio and the cleaning power of the azeotropic cleaning agent after regeneration hardly change even when compared with the azeotropic cleaning agent before use. As a result, since the azeotropic cleaning agent can be recycled, it is possible to reduce the cleaning agent waste liquid generated during cleaning. Moreover, the azeotropic cleaning agent according to this embodiment is easily dried. As a result, since it does not remain on the surface of the object to be cleaned, it is possible to reduce the amount of the rinse agent and the rinse agent waste liquid generated after using the rinse agent. Furthermore, since the azeotropic cleaning agent according to this embodiment has good rinsing properties and good drying properties, it can also be used as a rinsing agent. In addition, when the azeotropic cleaning agent according to this embodiment is used as a rinse agent, depending on the cleaning agent, an azeotropic cleaning agent solution can be stably regenerated even by simple distillation.

FIG. 1 is a graph showing the results of a distillation experiment in Example 4-3.

(1. Azeotropic cleaning agent)
In one aspect, the present disclosure provides a general formula (1): R—O—CH ₂ —CHX—O—H.
(In the formula, when X represents a hydrogen atom, R is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Represents the selected group,
When X represents a methyl group, R is a group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Represents a group selected from: And an azeotropic mixture comprising water and a azeotropic detergent.

  In the present disclosure, an “azeotropic mixture” is a mixture having the same composition of the gas phase and the liquid phase.

  In the present disclosure, an “azeotropic detergent” is a detergent comprising an azeotropic mixture.

(1.1. An azeotropic detergent containing an azeotropic mixture of glycol ether and water)
In one embodiment, the azeotropic detergent comprises an azeotropic mixture of the glycol ether and water.

(Glycol ether (hereinafter also referred to as component (1)))
The glycol ether constituting the azeotropic cleaning agent according to this embodiment has a boiling point of about 120 to 180 ° C, preferably 145 to 165 ° C under normal pressure. “Normal pressure” means standard atmospheric pressure.

  In addition, from the viewpoint of safety, the component (1) has a flash point of preferably 30 ° C. or higher, more preferably 50 to 60 ° C. for the purpose of making the azeotropic cleaning agent according to the present embodiment non-hazardous. .

  Examples of component (1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-sec. -Butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol Mono-iso-butyl ether, propylene glycol mono-sec-butyl ether, pro Glycol monobutyl -tert- butyl ether, and the like. Two or more of these glycol ethers can be used in combination.

(water)
Examples of the water constituting the azeotropic cleaning agent according to this embodiment include ultrapure water, pure water, distilled water, ion exchange water, and tap water. The water may be soft water or hard water.

(1.2. An azeotropic detergent containing an azeotropic mixture of glycol ether, water and diamine)
In one embodiment, the azeotropic detergent comprises the glycol ether and the general formula (2): R ¹ R ² N— (CH ₂ ) _n —NR ³ R ⁴
(Wherein R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6)
An azeotrope composed of diamine and water represented by

  Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, and tert-butyl group. It is done.

(Diamine (hereinafter also referred to as component (2)))
Examples of the diamine represented by the general formula (2) include diaminomethane such as N, N, N ′, N′-tetramethyldiaminomethane;
Ethylenediamine (diaminoethane) such as N, N, N ′, N′-tetramethylethylenediamine;
Diaminopropane such as N, N, N ′, N′-tetramethyl-1,3-diaminopropane;
Diaminobutane such as N, N, N ′, N′-tetramethyl-1,4-diaminobutane;
Diaminopentane such as N, N, N ′, N′-tetramethyl-1,5-diaminopentane;
Examples thereof include diaminohexane such as N, N, N ′, N′-tetramethyl-1,6-diaminohexane.

(1.3. Physical properties of azeotropic detergents)
The azeotropic cleaning agent according to this embodiment preferably has an azeotropic point under normal pressure of about 90 to 100 ° C, more preferably about 95 to 99 ° C.

  In order to achieve the above azeotropic point and perform distillation regeneration easily, the above azeotropic mixture is [(1) component / [(1) component + water]] or [[(1) component + (2) component]. ] / [(1) component + (2) component + water]] is preferably about 25 to 45% by mass, more preferably about 30 to 40% by mass.

  In one embodiment, the azeotropic cleaning agent according to this embodiment does not have a cloud point. It has been known that a conventional cleaning agent having a cloud point has excellent cleaning properties. As a result of intensive studies, the present inventors have surprisingly found that even if an azeotropic cleaning agent does not have a cloud point, it has excellent cleaning properties and rinsing properties.

  In the present disclosure, the “cloud point” is a temperature at which a phase separation occurs due to a temperature change in a transparent or translucent liquid, resulting in an opaqueness. In the case of the azeotropic cleaning agent according to this embodiment, it means a temperature at which the hydrogen bond formed between the glycol ether and water is cut and the water solubility rapidly decreases.

  In one embodiment, the azeotropic cleaning agent according to this embodiment does not have a flash point. As a result, the azeotropic cleaning agent according to this embodiment can be used as a non-hazardous material.

  In one embodiment, the azeotropic cleaning agent according to this embodiment does not include a surfactant. The azeotropic cleaning agent according to this embodiment has sufficient cleaning and rinsing properties even when it does not contain a surfactant. In a further embodiment, the azeotropic cleaning agent according to this embodiment includes only the azeotropic mixture. The azeotropic cleaning agent according to the present embodiment has sufficient cleaning properties and rinsing properties even when it contains only an azeotropic mixture.

In the present disclosure, the “surfactant” is a substance that forms an association like a micelle at a critical micelle concentration or higher in a solution. Specific examples include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. For example, examples of the nonionic surfactant include acetylene alcohol, acetylene glycol, polyhydric alcohol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyhydric alcohol fatty acid ester, and the like. In addition, the glycol ether represented by the general formula: R—O—CH ₂ —CHX—O—H (wherein R represents an alkyl group having 1 to 4 carbon atoms and X represents hydrogen or a methyl group) is It is not a surfactant.

  In one embodiment, the azeotropic cleaning agent according to this embodiment includes a surface tension reducing agent (such as ethylene glycol monohexyl ether), a scale inhibitor, a chelating agent (such as sodium gluconate), and a rust inhibitor (such as ammonium carbonate). ), Acid neutralizers (tetraalkylammonium hydride, ammonia, etc.), alkali neutralizers (acetic acid, formic acid, hydrochloric acid, etc.), redox agents (hydrogen peroxide, etc.), antioxidants (butylhydrotoluene, etc.) obtain.

  In one embodiment, the azeotropic cleaning agent according to this embodiment is a rinse agent. The azeotropic cleaning agent according to this embodiment is excellent in drying properties. Therefore, even when water adheres to the object to be cleaned, it can be used as a rinse agent. As a result of further studies, the present inventors have found that not only water but also a cleaning agent is excellent in rinsing properties even when the cleaning agent adheres to an object to be cleaned. Preferably, the rinse agent is for a flux cleaning solution.

  In the present disclosure, the “rinsing agent” is an agent that removes water, a cleaning agent, or both water and a cleaning agent attached to an object to be cleaned after cleaning with the cleaning agent.

(2. Regeneration method of azeotropic detergent)
In one aspect, the present disclosure provides a method for regenerating an azeotropic cleaning agent, which includes a step of distilling a liquid containing the azeotropic cleaning agent to obtain the azeotropic mixture. The azeotropic cleaning agent according to this embodiment can be regenerated by distillation operation even if the waste liquid after cleaning contains a flux or a cleaning agent other than the azeotropic cleaning agent according to this embodiment. The composition ratio and the cleaning power of the azeotropic cleaning agent after regeneration hardly change even when compared with the azeotropic cleaning agent before use. As a result, since the azeotropic cleaning agent can be recycled, it is possible to reduce the cleaning agent waste liquid generated during cleaning.

  In one embodiment, the regeneration method comprises a step of vaporizing waste liquid, a step of concentrating, and a distillate obtained by a distiller equipped with a heat source such as a heater and a heat medium, and a condenser mechanism such as a condenser and a heat exchanger. Including a step of returning the liquid to the tank of the receiver or the washing machine, a step of removing contaminants concentrated as a kettle residue, and the like. In this distiller, a Raschig ring, a Dixon packing, a bubble cap tray, a demister, or the like may be installed as necessary for the purpose of increasing the purity of the distillate. The number of theoretical plates is arbitrary and may be increased as necessary. In addition, when the azeotropic cleaning agent contains a substance other than the azeotrope, it may include a step of adding a substance other than the azeotrope to the obtained azeotrope after the step of obtaining the azeotrope by distillation. .

  Examples of distillation performed during the regeneration method include simple distillation and azeotropic distillation, but are not limited thereto. Preferably, the azeotropic distillation is performed at 90 to 110 ° C. under normal pressure.

  In the above regeneration method, examples of the amount of the azeotrope obtained are 50% by mass, 60% by mass, 70% by mass, and 80% by mass of the amount of the azeotrope contained in the azeotropic detergent before regeneration. As mentioned above, it is 90 mass% or more, 95 mass% or more, and 100 mass%, Preferably it is 95 mass% or more, Most preferably, it is 100 mass%.

  Examples of the “liquid containing an azeotropic cleaning agent” include a waste liquid containing an azeotropic cleaning agent (hereinafter, also referred to as an azeotropic cleaning agent waste liquid) generated after washing with an azeotropic cleaning agent. The azeotropic cleaning agent waste liquid may include a contaminant attached to the object to be cleaned, a cleaning liquid other than the azeotropic cleaning agent according to the present embodiment, and the like.

  When regenerating the azeotropic cleaning agent, an agent other than the azeotropic cleaning agent according to this embodiment (for example, a contaminant or a cleaning agent other than the azeotropic cleaning agent according to this embodiment) from the azeotropic cleaning agent waste liquid. Is removed.

  In the above regeneration method, examples of the amount of contaminants to be removed include 50% by mass, 60% by mass, 70% by mass, 80% by mass, and 90% by mass of the amount of contaminants contained in the azeotropic detergent waste liquid. It is 95 mass% or more, 95 mass% or more, and 100 mass%, Preferably it is 95 mass% or more, Most preferably, it is 100 mass%.

  In the above regeneration method, an example of the amount of the cleaning agent other than the azeotropic cleaning agent according to this embodiment to be removed is the amount of the cleaning liquid other than the azeotropic cleaning agent according to this embodiment included in the azeotropic cleaning agent waste liquid. 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 100% by mass, preferably 95% by mass or more, and most preferably 100% by mass. %.

(3. Cleaning (rinsing) method using an azeotropic cleaning agent)
In one aspect, the present disclosure includes the step of contacting the azeotropic cleaning agent with a contaminant or cleaning agent attached to the article, wherein the cleaning agent attached to the article is not the azeotropic cleaning agent. Not provide a cleaning method. The azeotropic cleaning agent according to this embodiment is easily dried. As a result, since it does not remain on the surface of the object to be cleaned, it is possible to reduce the amount of the rinse agent and the rinse agent waste liquid generated after using the rinse agent. Furthermore, since the azeotropic cleaning agent according to this embodiment has good rinsing properties and good drying properties, it can also be used as a rinsing agent.

  In the above cleaning method, examples of the amount of contaminants to be removed are 60% by mass, 70% by mass, 80% by mass, 90% by mass or more of the amount of contaminants contained in the azeotropic cleaning agent before cleaning. 95 mass% or more and 100 mass%. The amount of contaminants removed is preferably 95% by weight or more, and most preferably 100% by weight.

  In the above cleaning method, the amount of the cleaning agent adhering to the article to be removed is 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more of the amount of contaminants, It is 100% by mass, preferably 100% by mass. The amount of the cleaning agent adhering to the article to be removed is preferably 95% by mass or more, and most preferably 100% by mass.

  Means for cleaning the article by bringing the azeotropic cleaning agent according to the present embodiment into contact with the article to which contaminants or the like are attached are not limited, and examples of the cleaning means include immersion cleaning, shower cleaning, spray cleaning, ultrasonic cleaning, Examples include submerged jet cleaning and direct-through cleaning (Direct Pass (registered trademark)). Moreover, as a well-known washing | cleaning apparatus, Unexamined-Japanese-Patent No. 7-328565, Unexamined-Japanese-Patent No. 2000-189912, Unexamined-Japanese-Patent No. 2001-932, Unexamined-Japanese-Patent No. 2005-144441 etc. are mentioned, for example. Note that the azeotropic cleaning agent according to the present embodiment does not burn because it is a non-hazardous material unlike the hydrocarbon solvent-based cleaning agent. Therefore, explosion-proof equipment is not necessary, and it is suitable for shower cleaning and spray cleaning.

(Washing soap)
In the present disclosure, the “cleaning agent” is an agent used for washing and removing dirt. Examples of cleaning agents include glycol ether cleaning agents, hydrocarbon cleaning agents, alcohol cleaning agents, chlorine cleaning agents, fluorine cleaning agents, and bromine cleaning agents.

(Pollutant)
In one embodiment, the contaminant comprises at least one of the group consisting of soldering flux, solder paste, and industrial oil. However, it is not limited to these.

(Soldering flux)
In the present disclosure, the “soldering flux” is a composition used to remove the oxide film on the surfaces of the solder and the base material (metal electrode or the like) and facilitate the joining of both. Generally, it contains a base resin, an activator and an organic solvent, and may contain a thixotropic agent, an antioxidant and other additives as necessary. The soldering flux is classified according to its composition into solder paste flux and non-solder paste flux such as yarn solder flux, post flux and preflux.

Examples of the base resin include rosin base resins and non-rosin base resins. Examples of the rosin base resin include natural rosin, rosin derivatives, and purified products thereof. Examples of natural rosins include gum rosin, tall oil rosin and wood rosin. Examples of rosin derivatives are hydrides and disproportionates of the above natural rosins;
Examples thereof include polymerized rosin, unsaturated acid-modified rosin, rosin ester, hydrides and disproportionates thereof. The polymerized rosin, the unsaturated acid-modified rosin, and the rosin ester can be produced using the natural rosin or a hydride or disproportionate of the natural rosin. Examples of the polyhydric alcohol constituting the rosin ester include glycerin and pentaerythritol. Examples of the unsaturated acid constituting the unsaturated acid-modified rosin include acrylic acid, fumaric acid, maleic acid and the like. Examples of non-rosin base resins are epoxy resin, acrylic resin, polyimide resin, nylon resin, polyacrylonitrile resin, vinyl chloride resin, vinyl acetate resin, polyolefin resin, fluorine resin, ABS resin, isoprene rubber, styrene butadiene rubber ( SBR), butadiene rubber (BR), chloroprene rubber, nylon rubber, nylon elastomer, polyester elastomer and the like.

  Examples of the activators are succinic acid, adipic acid, azelaic acid, glutaric acid, sebacic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, itaconic acid, trans-2,3-dibromo-1,4- Butenediol, cis-2,3-dibromo-1,4-butenediol, 3-bromopropionic acid, 2-bromovaleric acid, 5-bromo-n-valeric acid, 2-bromoisovaleric acid, ethylamine bromate, Examples include diethylamine bromate, diethylamine hydrochloride, methylamine bromate and the like.

  Examples of the organic solvents are ethanol, n-propanol, isopropanol, isobutanol, butyl carbitol, hexyl diglycol, hexyl carbitol, isopropyl acetate, ethyl propionate, butyl benzoate, diethyl adipate, n-hexane, dodecane , Tetradecene and the like.

  Examples of the thixotropic agent include castor oil, hydrogenated castor oil, beeswax, carnauba wax, stearamide, 12-hydroxystearic acid ethylenebisamide, and the like.

  Examples of the antioxidant are pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-p-cresol, triphenyl phosphite, triethyl phosphite, trilauryl trithiophosphite, tris (tridecyl) ) Phosphite and the like.

  Examples of the other additives include an antifungal agent, a matting agent, an anti-thickening agent, and a surfactant.

(Solder paste)
In the present disclosure, “solder paste” is a composition formed by mixing a soldering flux and solder powder. Examples of the solder powder include Sn-Ag-based, Sn-Cu-based, Sn-Sb-based and Sn-Zn-based lead-free solder powders, and lead-containing solder powders containing lead as a constituent component. These solder metals are doped with one or more elements of Ag, Al, Au, Bi, Co, Cu, Fe, Ga, Ge, In, Ni, P, Pt, Sb, and Zn. It may be. The solder paste is supplied onto the electrode through a metal mask by screen printing, and after the electronic component is placed thereon, soldering is performed under heating.

  Examples of the article to which the soldering flux or solder paste is attached include a metal mask for screen printing, a squeegee, a nozzle for dispensing system, a syringe, a jig for fixing a substrate, and the like.

  The flux residue is a residue that is generated after an electronic component or the like is bonded to an electrode using solder paste, yarn solder, preflux, postflux, or the like. The flux residue needs to be removed by cleaning in order to corrode the solder metal and the base material or to reduce the insulation resistance of the substrate.

  Examples of the article to which the flux residue is attached include a printed circuit board, a ceramic wiring board, a semiconductor element mounting board, a wafer, a TAB tape, a lead frame, a power module, and a camera module. In addition, as for the corresponding ones, electronic parts such as ICs, capacitors, resistors, diodes, transistors, coils, and CSPs are soldered, BGA, PGA, LGA, etc. are formed, solder leveling, etc. The pretreatment may be performed.

(Industrial oil)
Examples of industrial oils include processing oils, cutting oils, mineral oils, machine oil greases, lubricating oils, rust preventive oils, waxes, pitches, paraffins, oils and fats, greases and the like. These reduce the friction between materials and tools to prevent seizure in the fields of machining, metal processing, etc., reduce the force required for processing to make it easier to form, and prevent rust and corrosion of products. Used to In addition, if industrial oil remains in a part that is scheduled to be plated, defective plating may occur. Therefore, the cleaning agent according to this embodiment is particularly suitable for cleaning such parts.

  Examples of articles to which industrial oil adheres include molded parts such as bolts, nuts, ferrules and washers, automobile parts such as engine pistons, industrial machine parts such as gears, shafts, sprockets, and chains, HDD parts, And electronic components such as lead frames.

  Examples of other contaminants include chips produced when dicing a printed circuit board, a ceramic wiring board, a semiconductor element mounting board, a cover glass, and a wafer.

(3.1. Washing-rinsing method)
In one embodiment, the cleaning method comprises:
Formula (A): R ^A1 —O— (CH ₂ —CHR ^A2 —O) _a —R ^A3
(In the formula, R ^A1 represents an alkyl group having 1 to 6 carbon atoms or a benzyl group, R ^A2 represents a methyl group or a hydrogen atom, R ^A3 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, and a Represents an integer of 2 to 4.)
An organic solvent (A) represented by
Formula (B):
(In the formula, R ^B represents an alkyl group having 1 to 7 carbon atoms, B represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, b1 represents an integer of 1 to 15 and b2 represents 0 to 15) Represents an integer.)
An amine (B) represented by
And a non-azeotropic cleaning agent containing an amino group-free chelating agent (C) and a contaminant attached to the article, and the non-azeotropic cleaning agent attached to the article. And / or contacting with contaminants.

  Examples of the alkyl group having 5 carbon atoms are pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, Examples include 2,2-dimethylpropyl group.

  Examples of the alkyl group having 6 carbon atoms are hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 5-methylpentyl group, 1,1-dimethylbutyl group. 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group and the like.

  Examples of the alkyl group having 7 carbon atoms include heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group and the like.

(Organic solvent (A) (also referred to as component (A)))
Two or more organic solvents (A) can be used in combination. Examples of the component (A) include diethylene glycol ether, polyethylene glycol ether, propylene glycol ether (glycol ether having R ^A2 in the general formula (A) as a methyl group) and the like.
Examples of diethylene glycol ether include diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, diethylene glycol monobenzyl ether and the like.
Examples of the diethylene glycol monoalkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether and the like.
Examples of diethylene glycol dialkyl ether are diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl butyl ether, diethylene glycol ethyl butyl ether, diethylene glycol propyl butyl ether, Diethylene glycol dipentyl ether, diethylene glycol methyl pentyl ether, diethylene glycol ethyl pentyl ether, diethylene glycol propyl pentyl ether, diethylene glycol butyl pentyl ether Ether and the like.
Examples of the polyethylene glycol ether include triethylene glycol ether and tetraethylene glycol ether corresponding to the diethylene glycol ether.
Among these, triethylene glycol monobutyl ether and diethylene glycol monobenzyl ether are preferable from the viewpoint of not destroying the azeotropic composition of the azeotropic detergent.

  The non-azeotropic cleaning agent contains a non-halogen organic solvent other than the component (A) as necessary. Examples of non-halogen organic solvents are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono- iso-butyl ether, ethylene glycol mono-sec-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, propylene Glycol mono-n-butyl ether, propylene glycol mono-iso-butyl ether, Glycol ether solvents such as propylene glycol mono-sec-butyl ether and propylene glycol mono-tert-butyl ether; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl Nitrogen-containing compound solvents such as -2-imidazolidinone and N-methyl-2-pyrrolidone; hydrocarbon solvents such as hexane, heptane and octane; alcohol solvents such as methanol, ethanol and benzyl alcohol; ketone solvents such as acetone and methyl ethyl ketone A dialkyl ether solvent such as diethyl ether; a cyclic ether solvent such as tetrahydrofuran; and an ester solvent such as ethyl acetate and methyl acetate. Two or more of these can be used in combination.

(Amine (B) (also referred to as (B) component))
Two or more amines (B) can be used in combination. Examples of the component (B) include N-alkyl dialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-propyldiethanolamine;
Examples include primary aliphatic amines such as octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, 2-ethylhexylamine and the like, in which R ^B in general formula (B) is an alkyl group. Among these, the N-alkyl dialkanolamine is preferable from the viewpoints of safety and the like, in particular, antifouling property and low foaming property, and particularly N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine and N-propyl. At least one selected from the group consisting of diethanolamine is more preferable.

(Amino group-free chelating agent (C) (also referred to as component (C)))
Two or more amino group-free chelating agents (C) can be used in combination. As the component (C), various known compounds can be used without particular limitation as long as they are chelating agents having no amino group in the molecule. In particular, aliphatic hydroxycarboxylic acid chelating agents and / or (poly) phosphoric acid chelating agents are preferred from the viewpoints of gap cleaning properties and particularly antifouling properties.

  Examples of the aliphatic hydroxycarboxylic acid chelating agent include hydroxy having about 2 to 3 carboxyl groups and about 1 to 3 hydroxyl groups bonded to a straight chain alkyl group having about 2 to 5 carbon atoms as a basic skeleton. A carboxylic acid etc. are mentioned.

  Examples of the hydroxycarboxylic acid include citric acid, isocitric acid, malic acid, tartaric acid, and salts thereof (including sodium salt, potassium salt, ammonium salt, alkanolamine salt, etc. The same shall apply hereinafter). . Among these, at least one selected from the group consisting of citric acid, isocitric acid and malic acid is preferable, and citric acid is more preferable from the viewpoints of gap cleaning properties and particularly antifouling properties.

  The example of the (poly) phosphate chelating agent is preferably at least one selected from the group consisting of orthophosphoric acid, pyrophosphoric acid and triphosphoric acid, and more preferably pyrophosphoric acid, from the viewpoint of clearance cleaning properties and particularly antifouling properties.

(Additives in non-azeotropic detergents)
Note that various known additives may be included in the non-azeotropic cleaning agent. Two or more additives can be used in combination. Examples of the additive include various surfactants such as nonionic surfactants (excluding those corresponding to the components (A) and (B)), anionic surfactants, and cationic surfactants. Examples include foaming agents, rust inhibitors, and antioxidants.

Examples of the nonionic surfactant are those represented by the general formula (D): R ^d —O— (CH ₂ —CH ₂ —O) _d —H (wherein R ^d represents an alkyl group having 8 to 20 carbon atoms, d Represents an integer of 0 to 20)), ethylene oxide adducts of fatty acid amides, sorbitan fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, their corresponding polyoxypropylene surfactants, etc. Is mentioned.

  Examples of anionic surfactants include sulfate ester anionic surfactants (sulfate esters of higher alcohols, alkyl sulfate esters, polyoxyethylene alkyl sulfate salts, etc.), sulfonate anionic surfactants ( Alkyl sulfonates, alkyl benzene sulfonates, etc.).

  Examples of the cationic surfactant include alkylated ammonium salts and quaternary ammonium salts.

  Examples of amphoteric surfactants include amino acid type, betaine type amphoteric surfactants and the like.

  In the non-azeotropic detergent, the content of each component is not particularly limited. The content of the component (B) is preferably about 0.01 to 30 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A). As for content of (C) component, about 0.01-10 mass parts of (C) component is preferable with respect to 100 mass parts of (A) component, and 0.02-1 mass part is more preferable. About 0-10 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of water, 1-8 mass parts is more preferable. Further, the content of the additive is preferably less than about 5 parts by mass.

(4. Detergent kit)
In one aspect, the disclosure provides
Formula (A): R ^A1 —O— (CH ₂ —CHR ^A2 —O) _a —R ^A3
(In the formula, R ^A1 represents an alkyl group having 1 to 6 carbon atoms or a benzyl group, R ^A2 represents a methyl group or a hydrogen atom, R ^A3 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, and a Represents an integer of 2 to 4.)
An organic solvent (A) represented by
Formula (B):
(In the formula, R ^B represents an alkyl group having 1 to 7 carbon atoms, B represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, b1 represents an integer of 1 to 15 and b2 represents 0 to 15) Represents an integer.)
An amine (B) represented by
And a non-azeotropic detergent containing the amino group-free chelating agent (C) and a detergent kit comprising the azeotropic detergent. Examples of the organic solvent (A), amine (B), and amino group-free chelating agent (C) are the same as those described above.

  The present invention will be described more specifically according to the following production examples, preparation examples, preparation examples, examples and comparative examples, but the present invention is not construed as being limited thereto, and the technical disclosure disclosed in each example. Examples obtained by appropriately combining means are also included in the scope of the present invention.

Production Example: Preparation of Azeotropic Cleaning Agent An azeotropic cleaning agent was prepared by the following procedure.

Production Example 1: Preparation of an azeotropic detergent containing an azeotropic mixture of ethylene glycol monomethyl ether and water In a 200 ml eggplant-shaped flask, (1) component: 20 g of ethylene glycol monomethyl ether (EM) as glycol ether and water As a solution, 80 g of ion exchange water (hereinafter simply referred to as water) was added and mixed well.

  Next, a distillation column, a T-tube, a thermometer, and a Liebig condenser corresponding to the theoretical plate number N = 10 were connected to the eggplant-shaped flask. Next, the eggplant-shaped flask was heated in an oil bath under normal pressure to boil the azeotropic mixture, whereby an azeotropic cleaning agent was prepared by collecting only a fraction having a boiling point of 100 ° C. or lower.

  Subsequently, the composition ratio of the fraction was measured using a digital densitometer PR-201α (manufactured by ATAGO). The results are shown in Table 1.

Production Examples 2 to 11 and Comparative Production Example 1
In Production Example 1, azeotropic detergents were prepared in the same manner except that those shown in Table 1 were used as the component (1), and a distillation test was conducted in the same manner as described above. The composition ratio of the fraction was determined.
* The values in parentheses () are the values measured by the tag sealing method.

Production example: Production of test substrate (article to be cleaned) Substrate A and substrate B were produced as test substrates (articles to be cleaned) by the following procedure.

Production Example 1: Production of Substrate A A commercially available lead-free solder paste (Pine Solder TAS LF-219-1, manufactured by Arakawa Chemical Industries, Ltd.) was placed on a SUS304 test piece (75 × 25 × 0.3 mm). A test piece obtained by uniformly coating 0.0 g was used as a base material A.

Production Example 2: Production of Substrate B A commercially available lead-free solder paste (Pine Solder TAS LF-219-1, manufactured by Arakawa Chemical Industry Co., Ltd.) was used for a phosphorus deoxidized copper plate test piece (40 × 40 × 0.3 mm). A test piece obtained by uniformly coating 0.3 g on top was used as a base material B.

Preparation Example: Preparation of detergent used in rinsing test Detergent A and detergent B were prepared as detergents used in the rinsing test by the following procedure.

Preparation Example 1: Preparation of Detergent A A product obtained by adding 9 mol of ethylene oxide to benzyl alcohol (manufactured by Tokyo Ohka Kogyo Co., Ltd.) and 1 mol of a secondary alcohol having 12 to 14 carbon atoms (trade name Softanol 90 , Manufactured by Nippon Shokubai Co., Ltd.) was prepared at 99/1 wt% to prepare detergent A.

Preparation Example 2: Preparation of Detergent B By preparing dipropylene glycol mono-n-butyl ether (manufactured by Nippon Emulsifier Co., Ltd.) and Softanol 90 (manufactured by Nippon Shokubai Co., Ltd.) at 99/1 wt%, detergent B was prepared. Prepared.

Example 1-1: Cleaning test After 200 g of the azeotropic cleaning agent of each production example / comparative production example was placed in a 200 mL beaker and heated to 70 ° C, the test substrate was immersed, and 28 kHz ultrasonic waves were applied for 10 minutes. After irradiation, the substrate was taken out and dried for 10 minutes in an air circulation dryer at 80 ° C.

Evaluation Method and Evaluation Criteria for Substrates A and B The detergency of the lead-free solder paste was determined by determining the removal rate from the difference in mass of the test substrate before and after cleaning. In addition, the criteria for determining the cleaning property are as follows.
Removal rate (%) = {(test substrate mass before cleaning−test substrate mass after cleaning) / coating amount} × 100
◎: Removal rate of 95% or more ○: Removal rate of 80% or more and less than 95% Δ: Removal rate of 60% or more and less than 80% ×: Removal rate of less than 60%

The results of Example 1-1 are shown in Table 2.

Example 1-2: Cleaning test A test and an evaluation were performed in the same manner as in Example 1-1 except that the following test substrates A and B were used instead of the substrates A and B. The results are shown in Table 3.

(Test substrate A)
Lead-free solder paste (trade name “Pine Solder TAS LF219-1”, manufactured by Arakawa Chemical Industries, Ltd.) is placed on a copper pattern of a glass epoxy copper clad laminate (30 × 30 × T1.5 mm) through a metal mask. The substrate (test base material A) to which the flux residue was adhered was produced by reflowing the obtained laminated plate with the following profile.
(Test substrate reflow profile)
Atmosphere: Air heating rate: 2 ° C / second Preheating: 150 ° C, 60 seconds Peak temperature: 250 ° C, 60 seconds

(Test substrate B)
Using a soft bristle brush with 50 mg of rosin-based postflux (trade name “Pineflux WHS-002”, manufactured by Arakawa Chemical Industries, Ltd.) on a copper pattern of a JIS2 type comb-shaped substrate (50 × 50 × T1.5 mm) And then uniformly applied, dried in a dryer at 100 ° C. for 5 minutes, and then immersed in a eutectic solder bath (tin-lead alloy) at 235 ± 5 ° C. for 5 seconds. A substrate (test substrate B) was prepared.

Example 2: Rinse test Phosphorus deoxidized copper plate test piece (40 x 40 x 0.3 mm) was immersed in the cleaning agent A or B prepared in the preparation example for 1 minute, and then 200 g was prepared in a 200 ml beaker and set at 32 ° C. A test piece was placed in the azeotropic cleaning agent of each production example / comparative production example, irradiated with 28 kHz ultrasonic waves for 3 minutes, then taken out and dried for 10 minutes in an air circulation dryer at 80 ° C. I let you.

Evaluation Method and Evaluation Criteria The rinsing properties of the detergents A and B were determined by visual inspection of the presence or absence of an oil film remaining on the test piece. The criteria for rinsing properties are as follows.
○: No oil film ×: With oil film

The results of Example 2 are shown in Table 4.

Example 3: Drying test 1 g of the azeotropic cleaning agent of each production example / comparative production example was placed in an ointment can, and the time until drying was measured in an air circulation dryer heated to 80 ° C.

Evaluation method Dryness was evaluated by mass comparison before and after the test. Specifically, first, the mass of the ointment can before the test and the mass of the cleaning agent of each example charged into the ointment can were measured. Each sample was taken out from the dryer every predetermined time and weighed, and the drying property was evaluated by the time required until the mass of the dried sample became the same as the mass of the ointment can before the test.

The results of Example 3 are shown in Table 5.

Example 4-1: Distillation regeneration test (waste liquid with detergent)
A 200 ml eggplant-shaped flask was charged with 95 g of the azeotropic cleaning agent of Production Example 7 and 5 g of a commercially available lead-free cleaning agent (Pine Alpha ST-180K, manufactured by Arakawa Chemical Co., Ltd.), and mixed by stirring. Was prepared.

  Next, a toroid, a thermometer, and a Liebig condenser were attached to the eggplant-shaped flask, and this was immersed in an oil bath, and the waste liquid was heated to boiling under 1 atm. Then, 20 g of the first fraction, 3 times 20 g of the middle fraction, and less than about 20 g of the latter fraction were collected.

Table 6 shows the ratio of glycol ether to water (measured by gas chromatography) in each distillation section. As described in the table, it was found that the composition ratio of the waste liquid and the distillate did not change greatly in each distillation section, and was not significantly different from the composition ratio of the cleaning liquid before distillation. This confirmed that the azeotropic cleaning agent was regenerated from the waste liquid.

Example 4-2: Distillation regeneration test (fluxed detergent waste liquid)
In a 200 ml eggplant-shaped flask, 99 g of the azeotropic cleaning agent of Production Example 7 and 1 g of a flux component of a commercially available lead-free solder paste (Pine Solder TAS LF-219-1, manufactured by Arakawa Chemical Industries, Ltd.) are added and stirred. A waste liquid was prepared by mixing.

  Next, a toroid, a thermometer, and a Liebig condenser were attached to the eggplant-shaped flask, and this was immersed in an oil bath, and the waste liquid was heated to boiling under 1 atm. Then, 15 g of the first distillation section, 3 times of 15 g of the middle distillation section, and about 15 g of the rear distillation section were collected.

Table 7 shows the ratio of glycol ether to water in each distillation section (measurement with a digital densitometer PR-201α). As described in the table, it was found that the composition ratio of the waste liquid and the distillate did not change greatly in each distillation section, and was not significantly different from the composition ratio of the cleaning liquid before distillation. This confirmed that the azeotropic cleaning agent was regenerated from the waste liquid.

Example 4-3: Distillation regeneration test (confirmation of each composition concentration in each fraction)
The azeotropic detergent solution of Production Example 7 was distilled and regenerated by simple distillation, and the amount of liquid was reduced, so that a non-azeotropic detergent (containing triethylene glycol mono n-butyl ether, Nn-butyldiethanolamine and citric acid was included. The azeotropic detergent solution of Production Example 7 containing non-azeotropic detergent at a concentration of 10% was replenished. The above distillation-replenishment operation was repeated, and the composition of each fraction obtained by distillation was confirmed. The results (measurement with a digital densitometer PR-201α) are shown in Table 8 and FIG. From Table 8 and FIG. 1, since the density | concentration of each composition of each fraction was settled within 3% from the median, it has confirmed that the azeotropic cleaning agent solution was able to be reproduced | regenerated stably.

Claims (13)

Formula (1): R—O—CH ₂ —CHX—O—H
(In the formula, when X represents a hydrogen atom, R is selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Represents the selected group,
When X represents a methyl group, R is a group consisting of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Represents a group selected from: )
An azeotropic cleaning agent comprising an azeotropic mixture comprising glycol ether represented by The azeotropic cleaning agent according to claim 1, comprising an azeotropic mixture of the glycol ether and water. The glycol ether and the general formula (2): R ¹ R ² N— (CH ₂ ) _n —NR ³ R ⁴
(Wherein R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6)
The azeotropic cleaning agent according to claim 1, comprising an azeotropic mixture comprising diamine represented by The azeotropic cleaning agent according to any one of claims 1 to 3, wherein the azeotropic cleaning agent does not contain a surfactant. The azeotropic cleaning agent according to any one of claims 1 to 4, wherein the azeotropic cleaning agent contains only the azeotropic mixture. The azeotropic cleaning agent according to any one of claims 1 to 5, wherein the azeotropic cleaning agent does not have a cloud point. The azeotropic cleaning agent according to claim 1, wherein the azeotropic cleaning agent is a rinse agent. The azeotropic cleaning agent according to claim 7, wherein the rinse agent is for a flux cleaning solution. A method for regenerating an azeotropic cleaning agent, comprising a step of distilling a liquid containing the azeotropic cleaning agent according to any one of claims 1 to 8 to obtain the azeotropic mixture. A step of bringing the azeotropic cleaning agent according to any one of claims 1 to 8 into contact with a cleaning agent and / or a contaminant attached to an article, wherein the cleaning agent attached to the article includes: A cleaning method that is not the azeotropic cleaning agent according to any one of claims 1 to 8. Formula (A): R ^A1 —O— (CH ₂ —CHR ^A2 —O) _a —R ^A3
(In the formula, R ^A1 represents an alkyl group having 1 to 6 carbon atoms or a benzyl group, R ^A2 represents a methyl group or a hydrogen atom, R ^A3 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, and a Represents an integer of 2 to 4.)
An organic solvent (A) represented by
Formula (B):
(In the formula, R ^B represents an alkyl group having 1 to 7 carbon atoms, B represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, b1 represents an integer of 1 to 15 and b2 represents 0 to 15) Represents an integer.)
An amine (B) represented by
And a step of contacting a non-azeotropic cleaning agent containing an amino group-free chelating agent (C) with a contaminant adhering to the article, and the azeotropic cleaning agent according to any one of claims 1 to 8. The cleaning method according to claim 10, comprising a step of contacting the non-azeotropic cleaning agent and / or the contaminant attached to the article. The cleaning method according to claim 10 or 11, wherein the contaminant includes at least one of the group consisting of soldering flux, solder paste, and industrial oil. Formula (A): R ^A1 —O— (CH ₂ —CHR ^A2 —O) _a —R ^A3
(In the formula, R ^A1 represents an alkyl group having 1 to 6 carbon atoms or a benzyl group, R ^A2 represents a methyl group or a hydrogen atom, R ^A3 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, and a Represents an integer of 2 to 4.)
An organic solvent (A) represented by
Formula (B):
(In the formula, R ^B represents an alkyl group having 1 to 7 carbon atoms, B represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, b1 represents an integer of 1 to 15 and b2 represents 0 to 15) Represents an integer.)
An amine (B) represented by
And a non-azeotropic cleaning agent comprising the amino group-free chelating agent (C) and the azeotropic cleaning agent according to any one of claims 1 to 8.