TWI876328B - Cleaning composition and cleaning method - Google Patents

Abstract

The subject of the present invention is to provide a novel cleaning agent composition having excellent cleaning performance and capable of removing copper oxide films. A cleaning agent composition comprises at least one non-halogen organic solvent (A) selected from the group consisting of glycol ethers (A1) and benzyl alcohol (A2), 3-amino-4-octanol (B), and water (C) as required, wherein the content ratio of each component is 70% to 99.9% by mass for component (A), 0.1% to 25% by mass for component (B), and 0% to 15% by mass for component (C).

Description

Cleaning agent composition and cleaning method

The present invention relates to a cleaning agent composition and a cleaning method.

Previously, halogenated hydrocarbon solvents such as trichloroethylene, perchloroethylene, methylene chloride, and chlorofluorocarbons have been used to clean various electronic parts or alloy parts. However, the use of these solvents is currently restricted due to environmental issues such as toxicity to the human body, air pollution, and soil pollution, so hydrocarbon cleaning agents, glycol cleaning agents, and benzyl alcohol cleaning agents have been proposed as non-halogen cleaning agents instead (see Patent Documents 1 and 2).

Glycol cleaning agents are cleaning agents that use various glycol compounds (glycols, glycol ethers) as the main component, and are excellent in removing flux, ionic residues, oil attached to metals, etc. In addition, these generally have no flash point or a very high flash point, and since they are non-hazardous, they are also excellent in that they do not require explosion-proof cleaning equipment. [Prior art literature] [Patent literature]

[Patent document 1] Japanese Patent Publication No. 10-046198 [Patent document 2] Japanese Patent Publication No. 2009-190089

[Problem to be solved by the invention] However, the inventors of the present invention and others conducted research and found that the cleaning performance was not sufficient when a glycol-based cleaning agent was used for cleaning.

In addition, when electronic components are soldered to the copper electrode surface of the circuit board, if an oxide film (copper oxide film) is formed on the copper surface due to heat, it will lead to poor wire bonding and poor adhesion of the sealing resin in the subsequent steps of soldering and cleaning. Therefore, the copper oxide film needs to be removed, but it is difficult to fully remove the copper oxide film using known cleaning agents.

The subject of the present invention is to provide a novel cleaning agent composition that has excellent cleaning properties and can remove copper oxide films. [Means for solving the problem]

The inventors of the present invention have made repeated efforts to achieve the above-mentioned problem, and have found that the above-mentioned problem can be solved by a cleaning agent composition containing a specified non-halogen organic solvent, 3-amino-4-octanol, and water as needed in a specific mass ratio. That is, the present invention relates to the following cleaning agent composition and cleaning method.

1. A cleaning agent composition comprising: At least one non-halogen organic solvent (A) selected from the group consisting of glycol ethers (A1) and benzyl alcohol (A2), 3-amino-4-octanol (B), and Water (C) as required, wherein the content ratio of each component is 70% to 99.9% by mass for component (A), 0.1% to 25% by mass for component (B), and 0% to 15% by mass for component (C).

2. The cleaning agent composition according to item 1, wherein the component (A1) is a compound represented by the following general formula (1). (In formula (1), ^R1 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group, ^R2 represents a methyl group or a hydrogen atom, ^X1 represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and a represents an integer of 1 to 4)

3. The cleaning agent composition as described in item 1 or 2, further comprising a surfactant.

4. The cleaning agent composition as described in item 3, wherein the content of the surfactant is 0 mass % to 15 mass % relative to 100 mass % of the cleaning agent composition.

5. The cleaning agent composition as described in item 1 or 2, further comprising an amine compound (but excluding component (B)).

6. A cleaning agent composition as described in any one of items 1 to 5, used for removing flux residue.

7. A cleaning method, comprising the step of bringing an object to be cleaned, to which a cleaning object is attached, into contact with a cleaning agent composition as described in any one of items 1 to 5 to remove the cleaning object. [Effect of the invention]

The cleaning agent composition of the present invention has excellent cleaning performance, especially excellent cleaning performance for various industrial dirts such as flux, ion residues, oil attached to metal, etc. In addition, the cleaning agent composition can fully remove the copper oxide film formed on the copper electrode surface of the circuit substrate.

[Cleaning agent composition] The cleaning agent composition of the present invention is a composition containing a predetermined non-halogen organic solvent (A) (hereinafter referred to as component (A)) and 3-amino-4-octanol (B) (hereinafter referred to as component (B)) in a specific mass ratio.

<Non-halogen organic solvent (A)> Component (A) is not particularly limited as long as it is at least one selected from the group consisting of glycol ether (A1) (hereinafter referred to as component (A1)) and benzyl alcohol (A2) (hereinafter referred to as component (A2)), and various known ones can be used. Component (A) can be used alone or in combination of two or more.

(Diol ether (A1)) The component (A1) is not particularly limited as long as it is a glycol ether, and various known ones can be used. The component (A1) can be used alone or in combination of two or more.

Examples of the component (A1) include aliphatic glycol ethers and aromatic glycol ethers. The aliphatic glycol ethers and aromatic glycol ethers are not particularly limited, and various known ones can be used.

From the viewpoint of excellent cleaning properties of the cleaning agent composition, the component (A1) is preferably a compound represented by the following general formula (1).

[Chemistry 3]

(In formula (1), ^R1 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group, ^R2 represents a methyl group or a hydrogen atom, ^X1 represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and a represents an integer of 1 to 4)

Examples of the compound represented by the general formula (1) include ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, propylene glycol dialkyl ether, dipropylene glycol dialkyl ether, tripropylene glycol dialkyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, ethylene glycol diphenyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol dibenzyl ether, and diethylene glycol monobenzyl ether.

The ethylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-n-pentyl ether, ethylene glycol mono-n-hexyl ether, and the like.

The diethylene glycol monoalkyl ethers include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, diethylene glycol mono-t-butyl ether, diethylene glycol mono-n-pentyl ether, diethylene glycol mono-n-hexyl ether, and the like.

The triethylene glycol monoalkyl ethers include, for example, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol mono-isopropyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol mono-isobutyl ether, triethylene glycol mono-t-butyl ether, triethylene glycol mono-n-pentyl ether, triethylene glycol mono-n-hexyl ether, and the like.

The propylene glycol monoalkyl ethers include, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-pentyl ether, propylene glycol mono-n-hexyl ether, and the like.

The dipropylene glycol monoalkyl ethers include, for example, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-isopropyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-isobutyl ether, dipropylene glycol mono-t-butyl ether, dipropylene glycol mono-n-pentyl ether, dipropylene glycol mono-n-hexyl ether, and the like.

The tripropylene glycol monoalkyl ethers include, for example, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-isopropyl ether, tripropylene glycol mono-n-butyl ether, tripropylene glycol mono-isobutyl ether, tripropylene glycol mono-t-butyl ether, tripropylene glycol mono-n-pentyl ether, tripropylene glycol mono-n-hexyl ether, and the like.

The ethylene glycol dialkyl ethers include, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, ethylene glycol di-isobutyl ether, ethylene glycol di-t-butyl ether, ethylene glycol ethyl methyl ether, ethylene glycol methyl propyl ether, ethylene glycol methyl n-propyl ether, ethylene glycol methyl isopropyl ether, ethylene glycol methyl butyl ether, ethylene glycol methyl isobutyl ether, ethylene glycol methyl t-butyl ether, ethylene glycol methyl n-pentyl ether, ethylene glycol methyl n-hexyl ether, ethylene glycol ethyl propyl ether, ethylene glycol ethyl n-propyl ether, ethylene glycol ethyl isopropyl ether, and the like.

The diethylene glycol dialkyl ethers include, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, diethylene glycol diisobutyl ether, diethylene glycol di-t-butyl ether, diethylene glycol ethyl methyl ether, diethylene glycol methyl propyl ether, diethylene glycol methyl n-propyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol methyl butyl ether, diethylene glycol methyl isobutyl ether, diethylene glycol methyl t-butyl ether, diethylene glycol ethyl propyl ether, diethylene glycol ethyl n-propyl ether, diethylene glycol ethyl isopropyl ether, and the like.

The triethylene glycol dialkyl ethers include, for example, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol di-n-butyl ether, triethylene glycol diisobutyl ether, triethylene glycol di-t-butyl ether, triethylene glycol ethyl methyl ether, triethylene glycol methyl propyl ether, triethylene glycol methyl n-propyl ether, triethylene glycol methyl isopropyl ether, triethylene glycol methyl butyl ether, triethylene glycol methyl isobutyl ether, triethylene glycol methyl t-butyl ether, triethylene glycol methyl n-pentyl ether, triethylene glycol ethyl propyl ether, triethylene glycol ethyl n-propyl ether, triethylene glycol ethyl isopropyl ether, triethylene glycol ethyl butyl ether, triethylene glycol ethyl isobutyl ether, triethylene glycol ethyl t-butyl ether, triethylene glycol ethyl n-pentyl ether, and the like.

The propylene glycol dialkyl ethers include, for example, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol diisopropyl ether, propylene glycol di-n-butyl ether, propylene glycol diisobutyl ether, propylene glycol di-t-butyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl-n-propyl ether, propylene glycol methyl isopropyl ether, propylene glycol methyl butyl ether, propylene glycol methyl isobutyl ether, propylene glycol methyl t-butyl ether, propylene glycol ethyl propyl ether, propylene glycol ethyl-n-propyl ether, propylene glycol ethyl isopropyl ether, propylene glycol ethyl butyl ether, propylene glycol ethyl isobutyl ether, propylene glycol ethyl t-butyl ether and the like.

The dipropylene glycol dialkyl ethers include, for example, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol diisopropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol diisobutyl ether, dipropylene glycol di-t-butyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl isopropyl ether, dipropylene glycol methyl butyl ether, dipropylene glycol methyl isobutyl ether, dipropylene glycol methyl t-butyl ether, dipropylene glycol ethyl propyl ether, dipropylene glycol ethyl-n-propyl ether, dipropylene glycol ethyl isopropyl ether, dipropylene glycol ethyl butyl ether, dipropylene glycol ethyl isobutyl ether, dipropylene glycol ethyl t-butyl ether and the like.

The tripropylene glycol dialkyl ethers include, for example, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol di-n-propyl ether, tripropylene glycol diisopropyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol diisobutyl ether, tripropylene glycol di-t-butyl ether, tripropylene glycol ethyl methyl ether, tripropylene glycol methyl propyl ether, tripropylene glycol methyl-n-propyl ether, tripropylene glycol methyl isopropyl ether, tripropylene glycol methyl butyl ether, tripropylene glycol methyl isobutyl ether, tripropylene glycol methyl t-butyl ether, tripropylene glycol ethyl propyl ether, tripropylene glycol ethyl-n-propyl ether, tripropylene glycol ethyl isopropyl ether, tripropylene glycol ethyl butyl ether, tripropylene glycol ethyl isobutyl ether, tripropylene glycol ethyl t-butyl ether, and the like.

In terms of particularly good cleaning properties of the cleaning agent composition, the component (A1) is preferably at least one selected from the group consisting of ethylene glycol monoisopropyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-n-hexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol mono-n-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether and dipropylene glycol dimethyl ether.

(Benzyl alcohol (A2)) The component (A2) is not particularly limited as long as it is benzyl alcohol, and various known ones can be used.

The content of the component (A) is 70% by mass to 99.9% by mass relative to 100% by mass of the cleaning agent composition. When the content of the component (A) is 70% by mass to 99.9% by mass, the cleaning agent composition exhibits excellent cleaning performance.

If the content of component (A) is less than 70% by mass relative to 100% by mass of the cleaning agent composition, the cleaning agent composition tends to fail to exhibit sufficient cleaning performance. In terms of excellent cleaning performance of the cleaning agent composition, the content of component (A) is preferably about 75% by mass to 99.9% by mass, and more preferably about 80% by mass to 99.9% by mass relative to 100% by mass of the cleaning agent composition.

When the component (A) is used in combination with the component (A1) and the component (A2), the mass ratio of the component (A1) to the component (A2) is not particularly limited, but is preferably about 20 to 80:80 to 20 in terms of cleaning properties.

<3-amino-4-octanol (B)> As long as the component (B) is 3-amino-4-octanol, various known ones can be used without particular limitation. Previously known cleaning agents were difficult to fully remove the copper oxide film formed on the copper electrode surface of the circuit board, etc., but the inventors and others conducted diligent research and found that by using 3-amino-4-octanol in the cleaning agent composition, the copper oxide film can be fully removed while showing excellent cleaning properties.

The content of the component (B) is 0.1 mass % to 25 mass % relative to 100 mass % of the cleaning agent composition. When the content of the component (B) is 0.1 mass % to 25 mass %, the cleaning agent composition exhibits excellent cleaning properties and can sufficiently remove the copper oxide film.

If the content of component (B) is less than 0.1% by mass relative to 100% by mass of the cleaning agent composition, the cleaning agent composition may not be able to fully exert cleaning properties and may not be able to fully remove the copper oxide film. In addition, if the content of component (B) exceeds 25% by mass relative to 100% by mass of the cleaning agent composition, the cleaning agent composition may not be able to fully exert cleaning properties. In terms of excellent cleaning properties and copper oxide film removal properties of the cleaning agent composition, the content of component (B) is preferably about 0.1% by mass to 20% by mass relative to 100% by mass of the cleaning agent composition, and more preferably about 0.1% by mass to 10% by mass.

(Water (C)) The cleaning agent composition may also contain water (C) (hereinafter referred to as component (C)) as an optional component. Since the cleaning agent composition contains component (C), it has no flash point and is classified as a non-hazardous substance under the Fire Services Act, and is therefore easier to handle.

The component (C) is not particularly limited as long as it is water, and examples thereof include ultrapure water, pure water, ion-exchanged water, purified water, and the like.

The content of the component (C) is not particularly limited, but is preferably 0% to 15% by mass relative to 100% by mass of the cleaning agent composition in terms of excellent handling properties of the cleaning agent composition. In the same regard, it is more preferably about 0% to 10% by mass relative to 100% by mass of the cleaning agent composition. If the content of the component (C) exceeds 15% by mass relative to 100% by mass of the cleaning agent composition, the cleaning agent composition tends to fail to exhibit sufficient cleaning properties.

(Other components) The cleaning agent composition may contain components other than components (A) to (C) (hereinafter referred to as other components) as long as the effect of the present invention can be obtained. Examples of other components include organic solvents and additives other than components (A) and (B).

Specific examples of the organic solvent include hydrocarbon solvents such as hexane, heptane, and octane; alcohol solvents such as methanol, ethanol, propanol, and 3-methoxy-3-methyl-1-butanol; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate and methyl acetate; nitrogen compound solvents such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, and N-methyl-2-pyrrolidone. The organic solvent may be a single type or a combination of two or more types.

Specific examples of the additive include: anti-rust agent, surfactant, defoaming agent, antioxidant, chelating agent, organic acid, amine compound, organic phosphorus compound, etc. The additive may be a single type or a combination of two or more types.

The surfactant is not particularly limited, and various known surfactants can be used. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. The surfactant can be used alone or in combination of two or more.

Examples of the non-ionic surfactant include compounds represented by the general formula (3): R4-O-( _CH2 - _CH2 -O) _e -H (wherein R4 represents an alkyl group having 8 to 20 carbon atoms and e represents an integer of 0 to 20), or ethylene oxide adducts of fatty acid amides, sorbitan fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, and the corresponding polyoxypropylene-based surfactants and polyoxyalkyleneamine-based surfactants.

Examples of the anionic surfactant include sulfate-based anionic surfactants (sulfate salts of higher alcohols, alkyl sulfate salts, polyoxyethylene alkyl sulfate salts, etc.), sulfonate-based anionic surfactants (alkyl sulfonate salts, alkylbenzene sulfonate salts, etc.), polyoxyalkyl phosphate-based surfactants, etc.

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

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

The content of the surfactant is not particularly limited. In terms of the excellent cleaning performance of the cleaning agent composition and the ability to fully remove the copper oxide film, the content of the surfactant is preferably 0 mass % to 15 mass %, and more preferably 1 mass % to 10 mass %, relative to 100 mass % of the cleaning agent composition.

As the chelating agent, there is no particular limitation as long as it is a metal chelating agent having the ability to coordinate with metal ions, and various known ones can be used. The chelating agent can be, for example, carboxylic acid chelating agents, amino acid chelating agents, phosphonic acid chelating agents, phosphoric acid chelating agents, aminocarboxylic acid chelating agents, hydroxycarboxylic acid chelating agents, etc. These chelating agents can be salts such as sodium salts, potassium salts, and ammonium salts, and can also be ester derivatives that can be hydrolyzed. The chelating agent can be a single type or a combination of two or more types.

Examples of the carboxylic acid chelating agent include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, itaconic acid, acetylsalicylic acid, phthalic acid, trimellitic acid, and cyclopentanetetracarboxylic acid.

Examples of the amino acid chelating agent include glycine, alanine, lysine, arginine, aspartic acid, tyrosine, and the like.

Examples of the phosphonic acid chelating agent include hydroxyethanediphosphonic acid, nitrogen trimethylenephosphonic acid, N,N,N',N'-tetrakis(phosphonylmethyl)ethylenediamine, and the like.

Examples of the phosphoric acid-based chelating agent include orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, and the like.

Examples of the aminocarboxylic acid chelating agent include ethylenediaminetetraacetic acid (EDTA), cyclohexanediaminetetraacetic acid (CDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), iminodiacetic acid (IDA), N-(2-hydroxyethyl)iminodiacetic acid (HIMDA), and hydroxyethylethylenediaminetriacetic acid (HEDTA).

Examples of the hydroxycarboxylic acid chelating agent include: apple acid, citric acid, isocitric acid, glycolic acid, gluconic acid, salicylic acid, tartaric acid, lactic acid, and the like.

The amine compound is not particularly limited, and various known compounds can be used. Examples of the amine compound include aliphatic amines, alkanolamines, etc. These amine compounds may be salts. The amine compound may be a single type or a combination of two or more types. Furthermore, the amine compound does not include component (B).

The aliphatic amines include, for example, primary aliphatic amines such as octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, and 2-ethylhexylamine; tertiary diamines such as N,N,N',N'-tetramethylpentamethylenediamine, N,N,N',N'-tetraethylpentamethylenediamine, N,N,N',N'-tetraisopropylpentamethylenediamine, N,N,N',N'-tetra-n-propylpentamethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetraethylhexamethylenediamine, N,N,N',N'-tetraisopropylhexamethylenediamine, and N,N,N',N'-tetra-n-propylhexamethylenediamine; Diaminoalkyl ethers such as bis(2-dimethylaminoethyl) ether, bis(2-diethylaminoethyl) ether, bis(2-diisopropylaminoethyl) ether, and bis(2-di-n-propylaminoethyl) ether; triamines such as 1,1,7,7-tetramethyldiethylenetriamine, 1,1,7,7-tetraethyldiethylenetriamine, 1,1,7,7-tetraisopropyldiethylenetriamine, 1,1,7,7-tetra-n-propyldiethylenetriamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, 4-methyl-1,1,7,7-tetraethyldiethylenetriamine, 4-methyl-1,1,7,7-tetraisopropyldiethylenetriamine, and 4-methyl-1,1,7,7-tetra-n-propyldiethylenetriamine.

The alkanolamines include, for example, N-methylmethanolamine, N-ethylmethanolamine, N-n-propylmethanolamine, N-n-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-n-propylethanolamine, N-isopropylethanolamine, N-n-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-n-propylpropanolamine, N-isopropylpropanolamine, N-n-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-n-propylbutanolamine, N-isopropylbutanolamine, N-n-butylbutanolamine, N,N-dimethylethanolamine, N ...propylpropanolamine, N-isopropylpropanolamine, N-n-butylbutanolamine, N,N-dimethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N-n-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-isopropylpropanolamine, N-n-butylbutanolamine, N,N-dimethylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N-n-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-isopropylpropanolamine, N-n-butylbutanol Amine, N,N-diethylethanolamine, N,N-di-n-propylethanolamine, N,N-di-n-butylethanolamine, N,N-dimethylpropanolamine, N,N-dimethylisopropanolamine, N,N-dimethylbutanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-tert-butyldiethanolamine, N-cyclohexyldiethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N,N-dibutylpropanolamine, etc.

The organic phosphorus compound is not particularly limited, and various known compounds can be used. Examples of the organic phosphorus compound include phosphates, phosphites, phosphonic acids, etc. These organic phosphorus compounds may be salts. The organic phosphorus compound may be a single compound or a combination of two or more compounds.

The phosphoric acid esters include, for example, monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, monoethyl phosphate, diethyl phosphate, triethyl phosphate, monopropyl phosphate, dipropyl phosphate, tripropyl phosphate, monobutyl phosphate, dibutyl phosphate, tributyl phosphate, monohexyl phosphate, dihexyl phosphate, trihexyl phosphate, monooctyl phosphate, dioctyl phosphate, trioctyl phosphate, monodecyl phosphate, didecyl phosphate, tridecyl phosphate, monoundecyl phosphate, di-undecyl phosphate, tri-undecyl phosphate, monododecyl phosphate, didecyl phosphate, tri-dodecyl phosphate, monotridecyl phosphate, di-tridecyl phosphate, tri-tridecyl phosphate, monostearyl phosphate, distearyl phosphate, tristearyl phosphate, monooleyl phosphate, dioleyl phosphate, trioleyl phosphate, monophenyl phosphate, diphenyl phosphate, triphenyl phosphate, and the like.

The phosphites include, for example, monomethyl phosphite, dimethyl phosphite, trimethyl phosphite, monoethyl phosphite, diethyl phosphite, triethyl phosphite, monopropyl phosphite, dipropyl phosphite, tripropyl phosphite, monobutyl phosphite, dibutyl phosphite, tributyl phosphite, monohexyl phosphite, dihexyl phosphite, trihexyl phosphite, monooctyl phosphite, dioctyl phosphite, trioctyl phosphite, monodecyl phosphite, didecyl phosphite, tridecyl phosphite, Monoundecyl ester, di-undecyl phosphite, tri-undecyl phosphite, monododecyl phosphite, di-dodecyl phosphite, tri-dodecyl phosphite, monotridecyl phosphite, di-tridecyl phosphite, tri-tridecyl phosphite, monostearyl phosphite, distearyl phosphite, tristearyl phosphite, monooleyl phosphite, dioleyl phosphite, trioleyl phosphite, monophenyl phosphite, diphenyl phosphite, triphenyl phosphite, etc.

Examples of the phosphonic acid include methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, octylphosphonic acid, decylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid, tridecylphosphonic acid, stearylphosphonic acid, oleylphosphonic acid, and phenylphosphonic acid.

In the cleaning agent composition, the method for preparing the components (A) to (C) and other components is not particularly limited, and a common liquid mixing method can be used. As a specific preparation method, a stirring method can be cited.

If the cleaning agent composition is classified by the cleaning object, for example, cleaning agents for flux residue, cleaning agents for soldering flux, cleaning agents for solder paste, cleaning agents for industrial oil, etc. In addition, if it is classified by the object to be cleaned, for example, cleaning agents for electronic materials, etc. can be listed.

Examples of the electronic materials include: processed glass products such as photomasks, optical lenses, vacuum discharge tubes, touch panels, and glass for display devices; processed metal products such as metal masks, pallets, printed circuit boards, flexible wiring boards, ceramic wiring boards, semiconductor components, semiconductor packages, magnetic media, power modules, camera modules, lead frames, disks, and heat sinks; processed resin products such as glass epoxy substrates, polyimide substrates, phenolic paper substrates, and plastic molded parts; silicon (Si), sapphire (Al ₂ O ₃ ), silicon carbide (SiC), diamond (C), gallium nitride (GaN), gallium phosphide (GaP), gallium arsenide (GaAs), indium phosphide (InP) and other wafers and their processed products after cutting (slicing, dicing, etc.), grinding (back grinding, sandblasting, etc.), chamfering (beveling, barrel, etc.), and grinding (lapping, polishing, buffing, etc.); as well as fixtures, carriers, cassettes, etc. used for processing, mounting, welding, cleaning, and transporting these items.

[Cleaning Target] The cleaning target of the cleaning agent composition of the present invention is not particularly limited, and examples thereof include: solder flux, solder paste, flux residue, industrial oil, and cuttings. Among these, the cleaning target of the cleaning agent composition is preferably one selected from the group consisting of solder flux, solder paste, and flux residue.

In this manual, "soldering flux" is a composition used to remove the oxide film on the surface of solder and base material (metal electrode, etc.) to facilitate the bonding of the two. Generally speaking, it can contain a base resin, an activator and an organic solvent, and may also contain a thiocyanate, an antioxidant, and other additives as needed. In addition, soldering flux is classified into solder paste flux and non-solder paste flux such as solder wire flux, post-flux and pre-flux according to its composition.

Examples of the base resin include rosin-based base resins and non-rosin-based base resins. Examples of the rosin-based base resin include natural rosin, rosin derivatives, and refined products thereof. Examples of natural rosin include gum rosin, pine oil rosin, and wood rosin. Examples of rosin derivatives include hydrogenated and disproportionated natural rosin, polymerized rosin, unsaturated acid-modified rosin, rosin ester, and hydrogenated unsaturated acid-modified rosin. The polymerized rosin, the unsaturated acid-modified rosin, and the rosin ester can be produced using the natural rosin or the hydrogenated or disproportionated natural rosin. Examples of the polyol constituting the rosin ester include glycerol, pentaerythritol, and the like. Examples of the unsaturated acid constituting the unsaturated acid-modified rosin include acrylic acid, fumaric acid, maleic acid, etc. Examples of the non-rosin-based base resin include epoxy resins, acrylic resins, polyimide resins, nylon resins, polyacrylonitrile resins, vinyl chloride resins, vinyl acetate resins, polyolefin resins, fluorine-based resins, acrylonitrile butadiene styrene (ABS) resins, isoprene rubber, styrene butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber, nylon rubber, nylon elastomers, polyester elastomers, etc.

Examples of the active agent include 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 bromide, diethylamine bromide, diethylamine hydrochloride, methylamine bromide, and the like.

Examples of the organic solvent include 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 activator include castor oil, hardened castor oil, beeswax, carnauba wax, stearic acid amide, 12-hydroxy stearic acid ethylene diamide, and the like.

Examples of the antioxidant include pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-p-cresol, triphenylphosphite, triethylphosphite, trilauryl trithiophosphite, tri(tridecyl)phosphite, and the like.

The other additives include, for example, mold inhibitors, matting agents, thickening inhibitors, surfactants, etc.

In this specification, "solder paste" is a mixture of soldering flux and solder powder. Examples of solder powder include: lead-free solder powders of Sn-Ag, Sn-Cu, Sn-Sb, and Sn-Zn series; and lead-containing solder powders with lead as a structural component. In addition, these solder metals may be doped with one or more elements of Ag, Al, Au, Bi, Co, Cu, Fe, Ga, Ge, In, Ni, P, Pt, Sb, and Zn. Solder paste is supplied to an electrode by screen printing through a metal mask, and after electronic components are placed thereon, soldering is performed under heating.

Examples of articles to which the solder flux or solder paste is applied include a metal mask for screen printing, a squeegee, a nozzle for dispensing, a syringe, and a jig for fixing a substrate.

The flux residue is the residue generated after electronic components and electrodes are joined using solder paste, solder wire, solder flux, pre-flux, post-flux, etc. The flux residue corrodes the solder metal and the base material, or reduces the insulation resistance of the substrate, and therefore needs to be removed by cleaning.

Articles to which the flux residue is attached include, for example, printed circuit boards, ceramic wiring boards, semiconductor component mounting boards, wafers, tape automated bonding (TAB) tapes, lead frames, power modules, and camera modules. In addition, electronic parts such as integrated circuits (ICs), capacitors, resistors, diodes, transistors, coils, and chip size packages (CSPs) can be soldered, or ball grid arrays (BGAs), pin grid arrays (PGAs), and land grid arrays (LGAs) can be formed, or pre-treatments such as solder leveling can be performed.

The industrial oils include, for example, processing oil, cutting oil, mineral oil, machine oil, grease, lubricating oil, anti-rust oil, wax, asphalt, wax, grease, grease, etc. These are used in the fields of mechanical processing, metal processing, etc. to reduce the friction between materials and tools to prevent marks, or to reduce the force required for processing to facilitate formation, or to prevent rust or corrosion of products.

Examples of items to which the industrial oil is attached include: molded parts such as bolts, nuts, hoops and washers; automotive parts such as engine pistons; industrial mechanical parts such as gears, shafts, sprockets and chains; electronic parts such as components for hard disk drives (HDDs) and lead frames, etc.

Other cleaning targets include, for example, chips generated during dicing of printed circuit boards, ceramic wiring boards, semiconductor component mounting boards, cover glasses, and wafers.

[Cleaning method] The method of using the cleaning agent composition to clean the object to be cleaned to which the cleaning object is attached is not particularly limited, and various known methods can be applied. Specifically, for example, a cleaning method including a cleaning step, a water rinsing step, and a drying step can be listed.

The washing step is a step of making the object to be cleaned contact with the cleaning agent composition to remove the cleaning object. The water rinsing step is a step of making the object to be cleaned contact with rinsing water to remove the cleaning agent composition attached to the object to be cleaned. The drying step is a step of removing the rinsing water attached to the object to be cleaned.

The means for bringing the cleaning agent composition and the rinsing water into contact with the object to be cleaned is not particularly limited, and various known methods may be used. For example, there may be cited: a method of using a spray device to spray the cleaning agent composition or the rinsing water onto the object to be cleaned in the form of a spray (refer to Japanese Patent Publication No. 2007-096127), a method of immersing the object to be cleaned in the cleaning agent composition and performing ultrasonic cleaning, a method of using a straight-through cleaning device (registered trademark "Direct Pass", manufactured by Arakawa Chemical Industries, Ltd., Japanese Patent No. 2621800, etc.), etc.

The rinsing step may also be repeated multiple times. For example, after the object to be cleaned is pre-rinsed, a final rinsing step is performed to effectively remove the cleaning agent components attached to the surface of the object to be cleaned.

The pre-rinsing treatment can be performed using a previous pre-rinsing treatment method using pure water or the like. The final rinsing treatment can be performed according to a previously known method, such as a method of treating the pre-rinsing treatment product using pure water or the like. [Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, in the examples, "%" and "parts" refer to "mass %" and "mass parts" unless otherwise specified.

[Preparation of cleaning agent composition] Example 1 92 parts of dipropylene glycol monobutyl ether (component (A)), 3 parts of 3-amino-4-octanol (component (B)) and 5 parts of water (component (C)) were mixed to prepare a cleaning agent composition.

Examples 2 to 35 and Comparative Examples 1 to 12 In Example 1, the cleaning agent composition was prepared in the same manner as in Example 1 except that the components were changed to those shown in Tables 1 to 3. The values in Tables 1 to 3 are expressed in parts by mass.

[Table 1] Cleaning agent composition Cleanability Copper oxide film removal (A) (B) (C) Quality Quality Quality Embodiment 1 BDG 92 3A4O 3 water 5 ○ ○ Embodiment 2 iBDG 92 3A4O 3 water 5 ○ ○ Embodiment 3 HkDJ 92 3A4O 3 water 5 ○ ○ Embodiment 4 PhDG 92 3A4O 3 water 5 ○ ○ Embodiment 5 BZD 92 3A4O 3 water 5 ○ ○ Embodiment 6 iG 92 3A4O 3 water 5 ○ ○ Embodiment 7 iPG 92 3A4O 3 water 5 ○ ○ Embodiment 8 tB 92 3A4O 3 water 5 ○ ○ Embodiment 9 H 92 3A4O 3 water 5 ○ ○ Embodiment 10 BTG 92 3A4O 3 water 5 ○ ○ Embodiment 11 PFG 92 3A4O 3 water 5 ○ ○ Embodiment 12 BFG 92 3A4O 3 water 5 ○ ○ Embodiment 13 PFDG 92 3A4O 3 water 5 ○ ○ Embodiment 14 BFDG 92 3A4O 3 water 5 ○ ○ Embodiment 15 BZ 92 3A4O 3 water 5 ○ ○ Embodiment 16 DMDG 92 3A4O 3 water 5 ○ ○ Embodiment 17 MEDG 92 3A4O 3 water 5 ○ ○ Embodiment 18 DEDG 92 3A4O 3 water 5 ○ ○ Embodiment 19 DMFDG 92 3A4O 3 water 5 ○ ○

[Table 2] Cleaning agent composition Cleanability Copper oxide film removal (A) (B) (C) (D) Quality Quality Quality Quality Embodiment 20 BDG HeG 46 46 3A4O 3 water 5 ○ ○ Embodiment 21 BDG iPDG 46 46 3A4O 3 water 5 ○ ○ Embodiment 22 BDG PFG 46 46 3A4O 3 water 5 ○ ○ Embodiment 23 BDG BFDG 46 46 3A4O 3 water 5 ○ ○ Embodiment 24 BDG MEDG 46 46 3A4O 3 water 5 ○ ○ Embodiment 25 BZD 46 46 3A4O 3 water 5 ○ ○ Embodiment 26 BDG 94.9 3A4O 0.1 water 5 ○ ○ Embodiment 27 BDG 75 3A4O 20 water 5 ○ ○ Embodiment 28 BDG 97 3A4O 3 - - ○ ○ Embodiment 29 BDG 87 3A4O 3 water 10 ○ ○ Embodiment 30 BDG 91 3A4O 3 water 5 SD-60 1 ○ ○ Embodiment 31 BDG 82 3A4O 3 water 5 SD-60 10 ○ ○ Embodiment 32 BDG 91 3A4O 3 water 5 TDX-80 1 ○ ○ Embodiment 33 BDG 82 3A4O 3 water 5 TDX-80 10 ○ ○ Embodiment 34 BDG 91 3A4O 3 water 5 A212C 1 ○ ○ Embodiment 35 BDG 87 3A4O 3 water 5 A212C 5 ○ ○

[Table 3] Cleaning agent composition Cleanability Copper oxide film removal (A) (B), (B)' (C) Quality Quality Quality Comparison Example 1 BDG 95 - - water 5 × × Comparison Example 2 - - 3A4O 95 water 5 × ○ Comparison Example 3 BDG 60 3A4O 25 water 15 △ ○ Comparison Example 4 BDG 70 3A4O 3 water 27 △ ○ Comparison Example 5 BDG 45 3A4O 50 water 5 × ○ Comparative Example 6 BDG 92 MDA 3 water 5 △ × Comparison Example 7 BDG 92 MBD 3 water 5 △ × Comparative Example 8 BDG 92 MBM 3 water 5 × × Comparative Example 9 BDG 92 2B 3 water 5 × × Comparative Example 10 BDG 92 TMDAP 3 water 5 × × Comparative Example 11 BDG 92 MEA 3 water 5 △ × Comparative Example 12 BDG 92 AEE 3 water 5 △ ×

The abbreviations of the components in Tables 1 to 3 are shown in Table 4.

[Table 4] Abbreviation Compound Name (A) BDG Diethylene glycol mono-n-butyl ether iBDG Diethylene glycol monoisobutyl ether HkDJ Diethylene glycol mono-n-hexyl ether PhDG Diethylene glycol monophenyl ether BZD Diethylene glycol monobenzyl ether iG Diethylene glycol monoisopropyl ether iPG Ethylene glycol monoisopropyl ether tB Ethylene glycol mono-tert-butyl ether H Ethylene glycol mono-n-hexyl ether BTG Triethylene glycol mono-n-butyl ether PFG Propylene glycol mono-n-propyl ether BFG Propylene glycol mono-n-butyl ether PFDG Dipropylene glycol mono-n-propyl ether BFDG Dipropylene glycol mono-n-butyl ether BZ Benzyl alcohol DMDG Diethylene glycol dimethyl ether MEDG Diethylene glycol ethyl methyl ether DEDG Diethylene glycol diethyl ether DMFDG Dipropylene glycol dimethyl ether (B) 3A4O 3-Amino-4-octanol (C) water water (B)' MDA N-Methyldiethanolamine MBD N-Butyldiethanolamine MBM N-butylethanolamine 2B N,N-Dibutylethanolamine TMDAP N,N,N',N'-Tetramethyl-1,3-propanediamine MEA Monoethanolamine AEE Diethylene glycol amine SD-70 NOIGEN SD-70 (manufactured by Daiichi Industry Pharmaceutical Co., Ltd., non-ionic surfactant) (D) TDX-80 NOIGEN TDX-80 (manufactured by Daiichi Industry Pharmaceutical Co., Ltd., non-ionic surfactant) A212C PLYSURF A212C (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., anionic surfactant)

The cleaning properties and copper oxide film removal properties were evaluated using the cleaning agent compositions obtained in Examples 1 to 35 and Comparative Examples 1 to 12. The results are shown in Tables 1 to 3.

<Evaluation of cleaning performance> (Preparation of test pieces for cleaning performance test) A commercially available lead-free and halogen-free solder paste (trade name "ECO SOLDER PASTE" M705-S70G-HF Type 4, manufactured by Senju Metal Industries, Ltd.) was printed on the copper pattern of a glass epoxy copper-clad laminate (50 mm × 50 mm × thickness 1.0 mm) using a metal mask, and reflow was performed according to the following profile to prepare a test substrate with flux attached.

(Reflow profile of test substrate) Environment: Air Heating rate: 1°C/sec Peak temperature: 240°C, 10 sec

(Cleaning Test) Using the test substrate, a cleaning test was conducted using an air spray method under the following cleaning and water rinsing conditions. The test substrate was brought into contact with the cleaning agent composition obtained in Examples 1 to 35 and Comparative Examples 1 to 12 at a liquid temperature of 60°C for 1 minute of cleaning. Next, the test substrate was brought into contact with rinsing water at a liquid temperature of 25°C for 1 minute of pre-rinsing. Furthermore, a final rinse was performed using running ion exchange water for 1 minute. Thereafter, air was blown onto the test substrate for 1 minute to remove the water and dry it. The surface of the dried test substrate was visually judged based on the following criteria, and the cleaning properties were evaluated. ○: Flux can be removed well (the surface area of flux residue is 0%). △: Some flux remains (the surface area of flux residue exceeds 0% and is 10% or less). ×: Flux remains considerably (the surface area of flux residue exceeds 10%).

(Conditions for cleaning using air spray and water rinsing) Flow rate: 2.3 L/min Pressure: 0.1 MPa Distance between spray nozzle and test substrate: 50 mm

<Evaluation of copper oxide film removability> (Preparation of test substrate for evaluation of copper oxide film removability) A phosphorus-deoxidized copper plate (C1220P, 50 mm × 50 mm × thickness 0.3 mm) was heated in a circulating air dryer at 170°C for 10 minutes to prepare a test substrate with a copper oxide film formed thereon.

(Copper oxide film removal test) Using the test substrate, the copper oxide film removal test was performed by immersion stirring. The test substrate for copper oxide film removal evaluation was contacted with the cleaning agent composition obtained in Example 1 to Example 35 and Comparative Example 1 to Comparative Example 12 at a liquid temperature of 60°C for 10 minutes for cleaning. Then, the test substrate was contacted with ion exchange water at a liquid temperature of 25°C for 10 minutes for pre-rinsing. Furthermore, the final rinse was performed for 1 minute using running ion exchange water. Thereafter, the test substrate was blown for 1 minute to remove the water and dried. The surface of the dried test substrate was visually judged based on the following judgment criteria, and the copper oxide film removability was evaluated. ○: The copper oxide film can be removed. ×: The copper oxide film remains.

without

without

Claims (7)

A cleaning agent composition comprises the following components: at least one non-halogen organic solvent (A) selected from the group consisting of glycol ether (A1) and benzyl alcohol (A2); 3-amino-4-octanol (B); and water (C) as required, wherein the content ratio of each component is 70% to 99.9% by mass for component (A), 0.1% to 25% by mass for component (B), and 0% to 15% by mass for component (C). The cleaning agent composition as claimed in claim 1, wherein the component (A1) is a compound represented by the following general formula (1);

(In formula (1), ^R1 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group, ^R2 represents a methyl group or a hydrogen atom, ^X1 represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and a represents an integer of 1 to 4). The cleaning agent composition as described in claim 1 further comprises a surfactant. The cleaning agent composition as described in claim 3, wherein the content of the surfactant is 1 mass % to 15 mass % relative to 100 mass % of the cleaning agent composition. The cleaning agent composition as described in claim 1 further comprises an amine compound (but not component (B)). A cleaning agent composition as described in any one of claim 1 to claim 5, used for removing flux residue. A cleaning method includes the step of bringing an object to be cleaned, to which a cleaning object is attached, into contact with the cleaning agent composition as described in any one of claims 1 to 5 to remove the cleaning object.