JP7597142B2 - Stock solution for cleaning agent composition, and cleaning agent composition containing said stock solution for cleaning agent composition - Google Patents

Description

The present invention relates to a concentrate for a cleaning composition and a cleaning composition containing the concentrate for a cleaning composition.

Traditionally, halogenated hydrocarbon solvents such as trichloroethylene, perchloroethylene, methylene chloride, and fluorocarbons have been used to clean various electronic components and individual alloy components. However, the use of these solvents is currently restricted due to their toxicity to the human body and environmental issues such as air and soil pollution, and as a result, alternative non-halogenated cleaners such as hydrocarbon cleaners, glycol cleaners, and benzyl alcohol cleaners have been proposed (see Patent Documents 1 and 2).

In recent years, in order to further reduce the environmental impact, water-diluted cleaning agents in which organic components such as glycol ether compounds are diluted with water have been proposed (see Patent Documents 1 and 2). Because water-diluted cleaning agents have a high mass ratio of water, it is possible to reduce costs, reduce the amount of organic components used, and suppress the emission of VOCs (volatile organic compounds), and it is expected that the environmental impact will be reduced. Another advantage is that the cleaning power can be adjusted by changing the ratio of organic components depending on the type of dirt.

Water-diluted cleaners can be classified into diluted products (see Patent Document 3) and undiluted products (see Patent Document 4) based on the timing of dilution. Diluted products are used by transporting and storing the cleaner composition after dilution with water, whereas undiluted products are used by transporting and storing the undiluted cleaner composition, and diluting it with water just before use.

Japanese Patent Application Publication No. 10-046198 JP 2009-190089 A JP 2013-181060 A JP 2015-218295 A

However, the inventors' investigations revealed that cleaning performance was sometimes insufficient when cleaning was performed using a water-diluted cleaning agent containing the above-mentioned glycol ether-based compound.

In addition, water-diluted cleaners classified as concentrates are superior to diluted cleaners in that the organic components can be transported and stored more efficiently. However, if the concentrates are non-uniform, the concentration of the organic components in the water-diluted cleaner obtained from them will not be constant, and the quality of the cleaner will not be stable, which can cause problems with handling when producing the cleaner.

In addition, when electronic components are soldered to the copper electrode surface of a circuit board, if an oxide film (copper oxide film) is formed on the copper surface due to heat, this can cause poor wire bonding and poor adhesion of the sealing resin in the subsequent soldering and cleaning processes, so it is necessary to remove the copper oxide film. However, it has been difficult to sufficiently remove this copper oxide film with known cleaning agents. Even if the copper oxide film can be removed once, if the copper surface is reoxidized, a new oxide film will be formed, so there has been a demand for cleaning agents that can remove the copper oxide film to also suppress the reoxidation of copper.

The objective of the present invention is to provide a stock solution for a cleaning composition that is easy to handle and that produces a water-dilutable cleaning agent that has excellent cleaning properties, can remove copper oxide films, and can suppress reoxidation of copper surfaces.

Another object of the present invention is to provide a cleaning composition that has excellent cleaning properties, can remove copper oxide films, and can suppress reoxidation of copper surfaces.

As a result of extensive research into achieving the above-mentioned objectives, the inventors have discovered that the above-mentioned objectives can be achieved by a stock solution for a cleaning composition that contains a specific non-halogenated organic solvent, 3-amino-4-octanol, and, if necessary, water in a specific mass ratio. That is, the present invention relates to the following stock solution for a cleaning composition, and a cleaning composition that contains the same.

1. A non-halogenated organic solvent (A) which is a glycol ether (A1) and/or benzyl alcohol (A2) having a solubility in water at 20° C. of 10% by mass or less;
3-amino-4-octanol (B), and optionally water (C),
The content of each component in the concentrate for a cleaning composition is 50 to 99.9 mass % of component (A), 0.1 to 45 mass % of component (B), and 0 to 20 mass % of component (C),
a cleaning composition obtained by mixing 100 parts by mass of the cleaning composition concentrate with 100 to 1,500 parts by mass of water becomes cloudy at 1 to 90° C.
Concentrate for cleaning composition.

2. The concentrate for a cleaning composition according to item 1 above, wherein component (A1) is at least one selected from the group consisting of dipropylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, ethylene glycol mono n-hexyl ether, diethylene glycol mono n-hexyl ether, ethylene glycol mono 2-ethylhexyl ether, diethylene glycol mono 2-ethylhexyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol butyl methyl ether, and diethylene glycol di-n-butyl ether.

3. A cleaning composition concentrate according to claim 1 or 2, comprising water,
3. A cleaning composition, comprising 100 to 1,500 parts by mass of water per 100 parts by mass of the concentrate for cleaning compositions according to item 1 or 2.

4. The cleaning composition described in item 3 above, for removing flux residue.

The concentrate for the cleaning composition of the present invention is a homogeneous solution in which the organic components are concentrated, allowing efficient transport and storage, and also providing a water-dilutable cleaning agent of stable quality, making it easy to handle.

The cleaning composition obtained by diluting the cleaning composition stock solution of the present invention with water has reduced costs and environmental impact because the main component is water, and excellent cleaning properties can be maintained even if the dilution ratio of water is increased. In addition, the above-mentioned cleaning composition can sufficiently remove copper oxide films formed on the copper electrode surfaces of circuit boards, and can suppress reoxidation of the copper surface.

[Stock solution for cleaning composition]
The concentrate for a cleaning composition of the present invention (hereinafter also referred to as the concentrate) is a composition containing a specific non-halogenated 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-based organic solvent (A)>
The component (A) is not particularly limited, and various known ones can be used, so long as it is a glycol ether (A1) (hereinafter referred to as component (A1)) and/or a benzyl alcohol (A2) (hereinafter referred to as component (A2)) having a solubility in water of 10 mass% or less at 20° C. The component (A) may be used alone or in combination of two or more kinds.

(Glycol Ether (A1))
The component (A1) is not particularly limited as long as it is a glycol ether having a solubility of 10% by mass or less in water at 20° C. The component (A1) may be used alone or in combination of two or more types.

When the solubility of component (A1) in water at 20°C (hereinafter also simply referred to as water solubility) exceeds 10% by mass, the hydrophilicity of the cleaning composition becomes high and sufficient cleaning properties cannot be obtained. The solubility in water at 20°C is preferably 5% by mass or less in order to impart appropriate hydrophobicity to the cleaning composition and thereby exhibit excellent cleaning properties. In addition, the solubility in water at 20°C is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.1 to 5% by mass, for the same reasons as above.

Examples of the (A1) component include aliphatic glycol ethers having a water solubility of 10% by mass or less, and aromatic glycol ethers having a water solubility of 10% by mass or less.

Examples of the aliphatic glycol ether 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, and tripropylene glycol dialkyl ether.

Examples of the ethylene glycol monoalkyl ether include ethylene glycol mono n-hexyl ether, ethylene glycol mono n-heptyl ether, ethylene glycol mono n-octyl ether, and ethylene glycol mono 2-ethylhexyl ether.

Examples of the diethylene glycol monoalkyl ether include diethylene glycol mono n-hexyl ether, diethylene glycol mono n-heptyl ether, diethylene glycol mono n-octyl ether, and diethylene glycol mono 2-ethylhexyl ether.

Examples of the triethylene glycol monoalkyl ether include triethylene glycol mono n-hexyl ether, triethylene glycol mono n-heptyl ether, triethylene glycol mono n-octyl ether, and triethylene glycol mono 2-ethylhexyl ether.

Examples of the propylene glycol monoalkyl ether include propylene glycol mono n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono n-pentyl ether, propylene glycol mono n-hexyl ether, propylene glycol mono n-heptyl ether, propylene glycol mono n-octyl ether, and propylene glycol mono 2-ethylhexyl ether.

Examples of the dipropylene glycol monoalkyl ether include dipropylene glycol mono n-propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono n-butyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol mono-t-butyl ether, dipropylene glycol mono n-pentyl ether, dipropylene glycol mono n-hexyl ether, dipropylene glycol mono n-heptyl ether, dipropylene glycol mono n-octyl ether, and dipropylene glycol mono 2-ethylhexyl ether.

Examples of the tripropylene glycol monoalkyl ether include tripropylene glycol mono n-propyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol mono n-butyl ether, tripropylene glycol monoisobutyl ether, tripropylene glycol mono-t-butyl ether, tripropylene glycol mono n-pentyl ether, tripropylene glycol mono n-hexyl ether, tripropylene glycol mono n-heptyl ether, tripropylene glycol mono n-octyl ether, and tripropylene glycol mono 2-ethylhexyl ether.

Examples of the ethylene glycol dialkyl ether include ethylene glycol di-n-butyl ether, ethylene glycol diisobutyl ether, ethylene glycol di-t-butyl ether, ethylene glycol butyl methyl ether, ethylene glycol isobutyl methyl ether, ethylene glycol methyl t-butyl ether, ethylene glycol methyl n-pentyl ether, and ethylene glycol methyl n-hexyl ether.

Examples of the diethylene glycol dialkyl ether include diethylene glycol di-n-butyl ether, diethylene glycol diisobutyl ether, diethylene glycol di-t-butyl ether, diethylene glycol butyl methyl ether, diethylene glycol isobutyl methyl ether, and diethylene glycol methyl t-butyl ether.

Examples of the triethylene glycol dialkyl ether include triethylene glycol di-n-butyl ether, triethylene glycol diisobutyl ether, and triethylene glycol di-t-butyl ether.

Examples of the propylene glycol dialkyl ether include 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 butyl methyl ether, propylene glycol isobutyl methyl ether, propylene glycol methyl t-butyl ether, propylene glycol ethyl butyl ether, propylene glycol ethyl isobutyl ether, and propylene glycol ethyl t-butyl ether.

Examples of the dipropylene glycol dialkyl ether include 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 butyl methyl ether, dipropylene glycol isobutyl methyl ether, dipropylene glycol methyl t-butyl ether, dipropylene glycol ethyl n-propyl ether, dipropylene glycol ethyl isopropyl ether, dipropylene glycol ethyl butyl ether, dipropylene glycol ethyl isobutyl ether, and dipropylene glycol ethyl t-butyl ether.

Examples of the tripropylene glycol dialkyl ether include 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 butyl methyl ether, tripropylene glycol isobutyl methyl ether, tripropylene glycol methyl t-butyl ether, tripropylene glycol ethyl butyl ether, tripropylene glycol ethyl isobutyl ether, and tripropylene glycol ethyl t-butyl ether.

Examples of the aromatic glycol ether include ethylene glycol monophenyl ether, propylene glycol monophenyl ether, ethylene glycol diphenyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, and ethylene glycol dibenzyl ether.

The (A1) component is preferably at least one selected from the group consisting of dipropylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, ethylene glycol mono n-hexyl ether, diethylene glycol mono n-hexyl ether, ethylene glycol mono 2-ethylhexyl ether, diethylene glycol mono 2-ethylhexyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol butyl methyl ether, and diethylene glycol di n-butyl ether, from the viewpoint of particularly good cleaning properties in the detergent composition, and from the similar viewpoint, more preferably at least one selected from the group consisting of dipropylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, propylene glycol monophenyl ether, and diethylene glycol di n-butyl ether.

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

The content of component (A) is 50 to 99.9% by mass relative to 100% by mass of the original solution. When the content of component (A) is 50 to 99.9% by mass, the cleaning composition exhibits excellent cleaning properties.

If the content of component (A) is less than 50% by mass relative to 100% by mass of the original solution, the detergent composition tends not to exhibit sufficient cleaning properties. In order to provide excellent cleaning properties in the detergent composition, the content of component (A) is preferably about 60 to 99% by mass relative to 100% by mass of the original solution, more preferably about 70 to 99% by mass, and particularly preferably about 80 to 99% by mass.

<3-Amino-4-octanol (B)>
As component (B), any of various known 3-amino-4-octanol can be used without any particular restrictions. It has been difficult to sufficiently remove copper oxide films formed on copper electrode surfaces of circuit boards using conventionally known cleaning agents, but the present inventors have found, as a result of extensive research, that by using 3-amino-4-octanol in a water-diluted cleaning agent, it is possible to sufficiently remove copper oxide films while exhibiting excellent cleaning properties and also to suppress reoxidation of the copper surface.

The content of component (B) is 0.1 to 45% by mass relative to 100% by mass of the original solution. When the content of component (B) is 0.1 to 45% by mass, the cleaning composition exhibits excellent cleaning properties, can remove copper oxide films, and inhibits reoxidation of the copper surface.

When the content of component (B) is less than 0.1% by mass relative to 100% by mass of the original solution, the cleaning composition tends not to exhibit sufficient cleaning properties, not to sufficiently remove the copper oxide film, and not to suppress reoxidation of the copper surface. On the other hand, when the content of component (B) is more than 45% by mass relative to 100% by mass of the original solution, the cleaning composition tends not to exhibit sufficient cleaning properties. The content of component (B) is preferably about 1 to 15% by mass, more preferably about 1 to 10% by mass, relative to 100% by mass of the original solution, in order to achieve excellent cleaning properties and excellent removability of the copper oxide film in the cleaning composition and to suppress reoxidation of the copper surface.

(Water (C))
The above-mentioned concentrate for the cleaning composition may contain water (C) (hereinafter, referred to as component (C)) as an optional component. By containing component (C), the concentrate for the cleaning composition for the cleaning composition has no flash point and is classified as a non-hazardous material under the Fire Service Act, making it easier to handle.

Component (C) is not particularly limited as long as it is water, and examples include ultrapure water, pure water, ion-exchanged water, purified water, etc.

The content of component (C) is not particularly limited, but from the viewpoint of excellent transport efficiency, storage properties, and handleability in the concentrate, it is preferably 0 to 20% by mass, and more preferably about 1 to 10% by mass, relative to 100% by mass of the concentrate. If the content of component (C) exceeds 20% by mass relative to 100% by mass of the concentrate, the concentrate tends to become non-uniform and difficult to handle, and the detergent composition tends not to exhibit sufficient cleaning properties.

(Glycol Ether (D))
The above-mentioned concentrate for the cleaning composition may further contain a glycol ether (D) (hereinafter referred to as component (D)) having a solubility in water at 20° C. of more than 10% by mass, as long as the effects of the present invention are obtained. The component (D) is not particularly limited as long as it is a glycol ether having a solubility in water at 20° C. of more than 10% by mass. The component (D) may be used alone or in combination of two or more kinds.

Examples of the (D) component include aliphatic glycol ethers having a water solubility of more than 10% by mass. Examples of the aliphatic glycol ethers include ethylene glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-t-butyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether.

The content of component (D) is not particularly limited, but from the viewpoint of excellent cleaning properties in the detergent composition, it is preferably 0 to 30% by mass relative to 100% by mass of the original solution, and from the same viewpoint, it is more preferably about 0 to 10% by mass relative to 100% by mass of the original solution.

(Ratio of each component)
In the concentrate solution for the cleaning composition, the mass ratio of the component (A) to the component (B) is not particularly limited, but from the viewpoints of providing excellent cleaning properties and excellent removability of a copper oxide film in the cleaning composition and suppressing reoxidation of the copper surface, it is preferably about 85 to 99:1 to 15.

In the above-mentioned concentrate for the cleaning composition, the mass ratio of the total of components (A) and (B) to component (C) is not particularly limited, but is preferably about 90-99:1-10, since the concentrate has no flash point and is classified as a non-hazardous material under the Fire Service Act, the cleaning composition exhibits excellent cleaning properties, can remove copper oxide films, and can inhibit reoxidation of the copper surface.

In the above-mentioned concentrate for the cleaning composition, the mass ratio of components (A), (B) and (C) is not particularly limited, but is preferably about 75-98:1-15:1-10, because the concentrate has no flash point and is classified as a non-hazardous material under the Fire Service Act, the cleaning composition exhibits excellent cleaning properties, can remove copper oxide films and inhibit reoxidation of the copper surface.

(Other ingredients)
The concentrate for the cleaning composition may contain components other than the components (A) to (D) (hereinafter, referred to as other components) as long as the effects of the present invention are obtained. Examples of other components include organic solvents other than the components (A), (B), and (D), additives, etc.

Specific examples of the organic solvent include hydrocarbon solvents such as hexane, heptane, and octane; alcohol solvents such as methanol, ethanol, propanol, and 3-methoxydimethyl-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; and nitrogen-containing 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 solvents may be used alone or in combination of two or more.

Specific examples of the additives include rust inhibitors, surfactants, antifoaming agents, antioxidants, chelating agents, organic acids, amine compounds, and organic phosphorus compounds. The additives may be used alone or in combination of two or more.

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 surfactants may be used alone or in combination of two or more.

Examples of the nonionic 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 from 0 to 20), ethylene oxide adducts of fatty acid amides, sorbitan fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, and the corresponding polyoxypropylene surfactants and polyoxyalkyleneamine surfactants.

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

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

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

The amount of the surfactant is not particularly limited, but is preferably 0 to 15% by mass relative to 100% by mass of the original solution, in order for the cleaning composition to exhibit excellent cleaning properties, remove copper oxide films, and inhibit reoxidation of the copper surface.

The chelating agent is not particularly limited as long as it is a metal chelating agent capable of coordinating to metal ions, and various known chelating agents can be used. Examples of the chelating agent include carboxylic acid chelating agents, amino acid chelating agents, phosphonic acid chelating agents, phosphoric acid chelating agents, aminocarboxylic acid chelating agents, and hydroxycarboxylic acid chelating agents. These chelating agents may be salts such as sodium salts, potassium salts, and ammonium salts, or may be hydrolyzable ester derivatives. The chelating agents may be used alone or in combination of two or more.

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 agents include glycine, alanine, lysine, arginine, asparagine, tyrosine, etc.

Examples of the phosphonic acid chelating agent include hydroxyethanediphosphonic acid, nitrilotrismethylenephosphonic acid, and N,N,N',N'-tetrakis(phosphonomethyl)ethylenediamine.

Examples of the phosphate chelating agents include orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, etc.

Examples of the aminocarboxylic acid chelating agents 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 agents include malic acid, citric acid, isocitric acid, glycolic acid, gluconic acid, salicylic acid, tartaric acid, and lactic acid.

The amine compound is not particularly limited, and various known compounds can be used. Examples of the amine compound include aliphatic amines and alkanolamines. These amine compounds may be salts. The amine compounds may be used alone or in combination of two or more. The amine compounds do not include component (B).

Examples of the aliphatic amines include 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; and bis(2-dimethylaminoethyl) ) ether, bis(2-diethylaminoethyl) ether, bis(2-diisopropylaminoethyl) ether, bis(2-di-n-propylaminoethyl) ether and other diaminoalkyl ethers; 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, 4-methyl-1,1,7,7-tetra-n-propyldiethylenetriamine and other triamines.

Examples of the alkanolamines include 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, and N,N-dimethylamine. Examples of such ethanolamine include 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-t-butyldiethanolamine, N-cyclohexyldiethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, and N,N-dibutylpropanolamine.

The above-mentioned organophosphorus compound is not particularly limited, and various known compounds can be used. Examples of the above-mentioned organophosphorus compounds include phosphate esters, phosphites, and phosphonic acids. These organophosphorus compounds may be salts. The above-mentioned organophosphorus compounds may be used alone or in combination of two or more.

Examples of the phosphate esters include 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, diundecyl phosphate, triundecyl phosphate, monododecyl phosphate, didodecyl phosphate, tridodecyl phosphate, monotridecyl phosphate, ditridecyl phosphate, tritridecyl phosphate, monostearyl phosphate, distearyl phosphate, tristearyl phosphate, monooleyl phosphate, dioleyl phosphate, trioleyl phosphate, monophenyl phosphate, diphenyl phosphate, and triphenyl phosphate.

The above-mentioned phosphite esters 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, Examples include tridecyl phosphite, monoundecyl phosphite, diundecyl phosphite, triundecyl phosphite, monododecyl phosphite, didodecyl phosphite, tridodecyl phosphite, monotridecyl phosphite, ditridecyl phosphite, tritridecyl phosphite, monostearyl phosphite, distearyl phosphite, tristearyl phosphite, monooleyl phosphite, dioleyl phosphite, trioleyl phosphite, monophenyl phosphite, diphenyl phosphite, and triphenyl phosphite.

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 above-mentioned concentrate for the cleaning composition, the method for mixing the components (A) to (D) and other components is not particularly limited, and a general liquid mixing method is used. A specific mixing method is a stirring method.

[Cleaning agent composition]
The cleaning composition of the present invention can be obtained by mixing about 100 to 1500 parts by mass of water with 100 parts by mass of a cleaning composition concentrate containing the components (A) and (B) and, if necessary, the component (C). If the amount of water is less than 100 parts by mass, the cost and environmental impact of the cleaning composition will be high, and the characteristics of a water-diluted cleaning agent will not be utilized, which is not preferable. If the amount of water is more than 1500 parts by mass, sufficient cleaning properties will not be obtained, which may cause poor cleaning.

The amount of water in the above cleaning composition is preferably about 200 to 1,200 parts by mass, and more preferably about 400 to 900 parts by mass, per 100 parts by mass of the cleaning composition concentrate, in order to reduce the cost and environmental impact of the cleaning composition and to obtain sufficient cleaning properties.

By mixing the concentrate for the cleaning composition and water in the above mass ratio, the appearance of the above cleaning composition becomes cloudy with oil droplets dispersed in water at 1 to 90°C (hereinafter, also referred to as a completely cloudy system).

Water-diluted cleaning agents are classified into three types based on the suspension state of the cleaning agent composition after dilution with water: homogeneous, heated cloudy, and the completely cloudy type of the present invention. The homogeneous type is a cleaning agent that is transparent at 1 to 90°C, and the heated cloudy type is a cleaning agent that is transparent at temperatures lower than the cloud point and becomes cloudy at temperatures equal to or higher than the cloud point. Among water-diluted cleaning agents, the completely cloudy type generally has a higher ability to remove oil-soluble and water-soluble dirt and has sufficient cleaning properties compared to the homogeneous and heated cloudy types. In other words, the cleaning agent composition of the present invention is a completely cloudy type, and therefore exhibits superior cleaning properties compared to the homogeneous and heated cloudy water-diluted cleaning agents.

In the above-mentioned cleaning composition, the method for mixing the above-mentioned cleaning composition concentrate and water is not particularly limited, and a general liquid mixing method is used. A specific mixing method includes a stirring method.

The above-mentioned cleaning compositions can be classified according to the object to be cleaned, for example, cleaning agents for flux residue, cleaning agents for soldering flux, cleaning agents for solder paste, cleaning agents for industrial oils, etc. Also, when classified according to the object to be cleaned, for example, cleaning agents for electronic materials, etc. can be mentioned.

Examples of the electronic materials include glass processed products such as photomasks, optical lenses, vacuum discharge tubes, touch panels, and glass for display devices; metal processed products such as metal masks, pallets, printed circuit boards, flexible wiring boards, ceramic wiring boards, semiconductor elements, semiconductor packages, magnetic media, power modules, camera modules, lead frames, magnetic disks, and heat sinks; resin processed products such as glass epoxy boards, polyimide boards, paper phenol boards, and plastic molded parts; wafers such as silicon (Si), sapphire (Al ₂ O ₃ ), silicon carbide (SiC), diamond (C), gallium nitride (GaN), gallium phosphide (GaP), gallium arsenide (GaAs), and indium phosphide (InP), and products cut (slicing, dicing, etc.), ground (back grinding, blasting, etc.), chamfered (beveling, barreling, etc.), and polished (lapping, polishing, buffing, etc.), and further jigs, carriers, magazines, etc. used when processing, mounting, welding, cleaning, and transporting these articles.

[Cleaning target]
The object to be cleaned with the cleaning composition of the present invention is not particularly limited, and examples thereof include soldering flux, solder paste, flux residue, industrial oil, cutting chips, etc. Among these, one selected from the group consisting of soldering flux, solder paste, and flux residue is suitable as the object to be cleaned with the cleaning composition.

In this specification, "soldering flux" refers to a composition used to remove oxide films from the surfaces of solder and base materials (metal electrodes, etc.) and facilitate bonding between the two. It generally contains a base resin, an activator, and an organic solvent, and may contain a thixotropic agent, an antioxidant, and other additives as necessary. Soldering flux is further classified according to its composition into flux for solder paste, flux for wire solder, post flux, pre flux, and other non-solder paste fluxes.

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, tall oil rosin, and wood rosin. Examples of the rosin derivative include hydrogenated and disproportionated products of natural rosin;
Examples of the polymerized rosin include polymerized rosin, unsaturated acid-modified rosin, rosin ester, and hydrogenated unsaturated acid-modified rosin. The polymerized rosin, unsaturated acid-modified rosin, and rosin ester can be produced using the natural rosin, or a hydrogenated or disproportionated product 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, and maleic acid. Examples of the non-rosin-based base resin include epoxy resin, acrylic resin, polyimide resin, nylon resin, polyacrylonitrile resin, vinyl chloride resin, vinyl acetate resin, polyolefin resin, fluorine-based resin, ABS resin, isoprene rubber, styrene butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber, nylon rubber, nylon-based elastomer, and polyester-based elastomer.

Examples of the activator include succinic acid, adipic acid, azelaic acid, glutaric acid, sebacic acid, dodecanoic diacid, 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, diethylamine bromate, diethylamine hydrochloride, and methylamine bromate.

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, and tetradecene.

Examples of the thixotropic agent include castor oil, hydrogenated castor oil, beeswax, carnauba wax, stearic acid amide, and 12-hydroxystearic acid ethylene bisamide.

Examples of the antioxidant include 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-t-butyl-4-hydroxy-hydrocinnamamide), 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, and tris(tridecyl)phosphite.

The other additives mentioned above include, for example, antifungal agents, matting agents, anti-thickening agents, surfactants, etc.

In this specification, the term "solder paste" refers to a mixture of soldering flux and solder powder. Examples of solder powder include lead-free solder powders such as Sn-Ag, Sn-Cu, Sn-Sb, and Sn-Zn solder powders, as well as lead-containing solder powders that contain lead as a component. These solder metals may be doped with one or more of the following elements: Ag, Al, Au, Bi, Co, Cu, Fe, Ga, Ge, In, Ni, P, Pt, Sb, and Zn. The solder paste is supplied onto the electrodes through a metal mask by screen printing, and after electronic components are placed on it, soldering is performed under heat.

Examples of articles to which the above-mentioned soldering flux or solder paste is attached include metal masks for screen printing, squeegees, nozzles for dispensing methods, syringes, and jigs for fixing substrates.

The above-mentioned flux residue is a residue that is generated after electronic components, etc. are joined to electrodes using solder paste, solder wire, soldering flux, pre-flux, post-flux, etc. Flux residue corrodes the solder metal and base material and reduces the insulation resistance of the board, so it must be removed by cleaning.

Examples of articles to which the flux residue is attached include printed circuit boards, ceramic wiring boards, semiconductor element mounting boards, wafers, TAB tapes, lead frames, power modules, and camera modules. In addition, the corresponding items may have electronic components such as ICs, capacitors, resistors, diodes, transistors, coils, and CSPs soldered to them, BGAs, PGAs, and LGAs may be formed, and pre-processing such as solder leveling may be performed.

Examples of the above industrial oils include processing oil, cutting oil, mineral oil, machine oil grease, lubricating oil, rust-preventive oil, wax, pitch, paraffin, oils and fats, and grease. These are used in fields such as machining and metal processing to reduce friction between materials and tools to prevent seizure, to reduce the force required for processing to make it easier to form, and to prevent rust and corrosion of products.

Examples of articles to which the above-mentioned industrial oils have adhered include molded parts such as bolts, nuts, ferrules, and washers, automobile parts such as engine pistons, industrial machinery parts such as gears, shafts, sprockets, and chains, HDD parts, and electronic parts such as lead frames.

Other objects to be cleaned include, for example, printed circuit boards, ceramic wiring boards, semiconductor element mounting boards, cover glass, and chips generated during dicing of wafers, etc.

[Cleaning method]
The method for cleaning the object to be cleaned with the cleaning composition is not particularly limited, and various known methods can be applied. Specifically, for example, there is a cleaning method including a cleaning step, a water rinsing step, and a drying step.

The cleaning process is a process in which the object to be cleaned is removed by contacting the cleaning composition with the cleaning agent. The water rinsing process is a process in which the object to be cleaned is contacted with rinsing water to remove the cleaning agent composition adhering to the object to be cleaned. The drying process is a process in which the rinsing water adhering to the object to be cleaned is removed.

The means for contacting the object to be cleaned with the cleaning composition and rinsing water is not particularly limited, and examples include the immersion stirring method, the submerged shower method, the air shower method, and the ultrasonic cleaning method.

The above-mentioned cleaning composition exhibits excellent cleaning properties when mixed to form a cloudy white state, so the air shower method is preferred as a cleaning method because it has a strong ability to mix the cleaning composition and is excellent in cleaning properties and productivity.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "%" and "parts" mean "% by mass" and "parts by mass" unless otherwise specified.

[Preparation of detergent composition stock solution and detergent composition]
Example 1
A stock solution for a cleaning agent composition was prepared by mixing 90 parts of dipropylene glycol mono-n-propyl ether (component (A)), 5 parts of 3-amino-4-octanol (component (B)), and 5 parts of water (component (C)). Then, 400 parts of water were added to 100 parts of the stock solution for a cleaning agent composition to prepare a cleaning agent composition X (concentration of the stock solution for a cleaning agent composition: 20% by mass). Also, 900 parts of water were added to 100 parts of the stock solution for a cleaning agent composition to prepare a cleaning agent composition Y (concentration of the stock solution for a cleaning agent composition: 10% by mass).

Examples 2 to 26 and Comparative Examples 1 to 18
The detergent composition concentrate solution of Example 1 was prepared in the same manner as in Example 1, except that the components of the concentrate solution were changed to those shown in Tables 1 and 2. The units of values in Tables 1 and 2 are parts by mass. When the detergent compositions X and Y of Examples 1 to 26 were heated to 1 to 90° C., they became cloudy in appearance at all temperatures.

The abbreviations of each component in Tables 1 and 2, and the solubility in water of components (A) and (D) are as shown in Table 3.

The appearance was evaluated using the cleaning composition concentrates obtained in Examples 1 to 26 and Comparative Examples 1 to 18. In addition, the cleaning properties, copper oxide film removal properties, and copper reoxidation prevention properties were evaluated using the cleaning composition X and Y obtained in Examples 1 to 26 and Comparative Examples 1 to 18. The results are shown in Tables 4 and 5.

The notes in Table 5 are as follows:
(1) Since the concentrate solution for the detergent composition was non-uniform, the detergent compositions X and Y were not evaluated.
(2) Since the copper oxide film remained in the evaluation of copper oxide film removal property, the copper reoxidation prevention property was not evaluated.

<Appearance evaluation>
The detergent composition stock solutions in Tables 1 and 2 were placed in a 50 mL glass container, and the uniformity at 25° C. was visually confirmed. In Tables 4 and 5, "uniform" means that the appearance is transparent and the detergent composition stock solution is in a completely compatible state, and "heterogeneous" means that the appearance is cloudy or the stock solution is separated into two layers, an aqueous layer and an oil layer, and the detergent composition stock solution is phase-separated.

<Evaluation of cleaning ability>
(Preparation of test pieces for cleaning test)
A commercially available lead-free, halogen-free solder paste (product name "Eco Solder Paste M705-S70G-HF Type 4", manufactured by Senju Metal Industry Co., Ltd.) was printed on the copper pattern of a glass epoxy copper-clad laminate (50 × 50 × thickness 1.0 mm) using a metal mask, and reflowed with the following profile to produce a test board with flux attached.

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

(Washability test)
Using the above test substrate, a cleaning property test was performed by an air shower method under the following cleaning and water rinsing conditions. The test substrate was brought into contact with the cleaning composition X or Y obtained in Examples 1 to 26 and Comparative Examples 1 to 18 at a liquid temperature of 60° C., and cleaning was performed for 30 seconds or 1 minute. Next, the test substrate was brought into contact with rinsing water at a liquid temperature of 25° C., and pre-rinsed for 1 minute. Furthermore, a finish rinse was performed with running ion-exchanged water for 1 minute. Thereafter, the test substrate was air-blowed for 1 minute to remove moisture and dried. The surface of the test substrate after drying was visually judged based on the following criteria to evaluate cleaning property.
⊚: The flux was successfully removed in both cases where the cleaning time was 30 seconds and 1 minute (the surface area of the flux residue was 0%).
◯: When the cleaning time was 30 seconds, flux remained, but when the cleaning time was 1 minute, the flux was successfully removed (the surface area of the flux residue was 0%).
Δ: When the cleaning time was 1 minute, a small amount of flux remained (the surface area of the flux residue was more than 0% and 10% or less).
×: When the cleaning time was 1 minute, a considerable amount of flux remained (the surface area of the flux residue exceeded 10%).

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

<Evaluation of copper oxide film removal ability>
(Preparation of test substrate for evaluating 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 on which a copper oxide film was formed.

(Copper oxide film removal test)
A copper oxide film removal test by immersion and stirring was carried out using the above test substrate. A test substrate for evaluating copper oxide film removability was brought into contact with the cleaning composition X or Y obtained in Examples 1 to 26 and Comparative Examples 1 to 18 at a liquid temperature of 60° C. for 10 minutes to perform cleaning. Next, the test substrate was brought into contact with ion-exchanged water at a liquid temperature of 25° C. for 10 minutes to perform pre-rinsing. Furthermore, a finish rinse was performed with running ion-exchanged water for 1 minute. Thereafter, the test substrate was air-blowed for 1 minute to remove moisture and dried. The surface of the test substrate after drying was visually judged based on the following criteria to evaluate the copper oxide film removability.
◯: The copper oxide film was removed.
×: Copper oxide film remained.

<Evaluation of copper reoxidation prevention ability>
After the copper oxide film removal test, the test substrate from which the copper oxide film had been removed was stored for 14 days in a thermostatic chamber at 23° C. After storage, the surface of the test substrate was visually observed and evaluated for copper reoxidation prevention property based on the following criteria.
◯: After the copper oxide film was removed, the sample was stored in a thermostatic chamber at 23° C. for 14 days, and no copper oxide film was formed.
×: After removing the copper oxide film, when the sample was stored in a thermostatic chamber at 23° C. for 14 days, a copper oxide film was generated.

Claims (3)

A concentrate solution for a cleaning composition comprising a non-halogenated organic solvent (A) which is a glycol ether (A1) and/or benzyl alcohol (A2) having a solubility in water at 20° C. of 10% by mass or less, 3-amino-4-octanol (B), and, as necessary, water (C), wherein the content ratios of the respective components are 50 to 99.9% by mass for component (A), 0.1 to 45% by mass for component (B), and 0 to 20% by mass for component (C), and the glycol ether (A1) is selected from the group consisting of dipropylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, and the like. and wherein the concentrate for a cleaning composition is at least one selected from the group consisting of ethylene glycol mono-n-hexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol butyl methyl ether and diethylene glycol di-n-butyl ether, and a cleaning composition obtained by mixing 100 parts by mass of the concentrate for a cleaning composition with 100 to 1,500 parts by mass of water becomes cloudy at 1 to 90°C. A cleaning composition comprising the stock solution for a cleaning composition according to claim 1 and water, the water being 100 to 1,500 parts by mass per 100 parts by mass of the stock solution for a cleaning composition according to claim 1 . The cleaning composition according to claim 2 , which is for removing flux residue.