JP7761028B2 - Detergent composition and water-dilutable detergent - Google Patents

Description

The present invention relates to a cleaning agent composition and a water-dilutable cleaning agent.

Traditionally, halogenated hydrocarbon solvents such as trichloroethylene, perchloroethylene, methylene chloride, and chlorofluorocarbons 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 concerns such as air and soil pollution. As a result, alternative non-halogen cleaners such as hydrocarbon-based cleaners, glycol-based cleaners, and benzyl alcohol-based cleaners have been proposed (see Patent Documents 1 and 2).

Glycol-based cleaners are cleaners whose main ingredients are various glycol compounds (glycol, glycol ether), and are said to be excellent at removing flux, ionic residue, oil adhering to metals, etc. Furthermore, they generally have no or very high flash points and are non-hazardous, meaning they are also advantageous in that they do not require explosion-proof cleaning equipment.

Japanese Patent Application Publication No. 10-046198 JP 2009-190089 A

However, the inventors' investigations have revealed that cleaning performance is sometimes insufficient even when using conventional cleaning agents such as those described above. Furthermore, when using conventional cleaning agents to clean items containing highly corrosive metals such as aluminum, the cleaning agent can corrode the item, resulting in corrosion of the aluminum or other metal parts.

Furthermore, when electronic components are soldered to the copper electrode surface of a circuit board, heat can form an oxide film (copper oxide film) on the copper surface. 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 using known cleaning agents.

The objective of the present invention is to provide a novel cleaning composition that has excellent cleaning properties, inhibits corrosion of articles containing metals such as aluminum, and is capable of removing copper oxide films.

As a result of extensive research to achieve the above-mentioned objectives, the inventors have discovered that the above-mentioned objectives can be achieved by a cleaning composition containing 3-amino-4-octanol, a specific organophosphorus compound, and, if necessary, water. The inventors have also discovered that the above-mentioned objectives can also be achieved by a cleaning agent obtained by diluting such a cleaning composition with water (a water-diluted cleaning agent). In other words, the present invention relates to the following cleaning composition and water-diluted cleaning agent.

1. 3-amino-4-octanol (A),
A cleaning agent composition comprising: at least one organic phosphorus compound (B) selected from the group consisting of an acidic phosphoric acid ester (B1), an organic phosphonic acid (B2) and a salt thereof; and optionally water (C).

2. The cleaning composition according to item 1, further comprising an organic solvent (D).

3. The cleaning composition according to item 1 or 2 above, which is used to remove flux residue.

4. A cleaning agent composition comprising the cleaning composition according to item 1 or 2 and water,
3. A water-dilutable cleaning agent comprising 100 to 1,500 parts by mass of water per 100 parts by mass of the cleaning composition according to item 1 or 2.

5. The water-dilutable cleaning agent described in paragraph 4 above, for removing flux residue.

The cleaning composition and water-diluted cleaning agent of the present invention have excellent cleaning properties, particularly for various industrial soils such as flux, ion residues, and oil adhering to metals. Furthermore, the cleaning liquid composition and water-diluted cleaning agent inhibit corrosion of highly corrosive metals such as aluminum, making them suitable for cleaning items containing such metals. Furthermore, the cleaning composition and water-diluted cleaning agent can sufficiently remove copper oxide films formed on copper electrode surfaces of circuit boards, etc.

Throughout this specification, the range of values for each physical property, content, etc. may be set as appropriate (for example, by selecting from the values described in each item below). Specifically, if the example of value α is A3, A2, or A1 (assuming A3 > A2 > A1), the range of value α may be, for example, A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and less than A2), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 ... and more than A1 and less than A3. Note that in this specification, the term "to" is used to mean that the values before and after it are included as both the lower and upper limits. The components and manufacturing methods of the present invention are described in detail below.

[Cleaning composition]
The cleaning composition of the present invention is a composition containing 3-amino-4-octanol (A) (hereinafter referred to as component (A)) and a predetermined organophosphorus compound (B) (hereinafter referred to as component (B)).

<3-Amino-4-octanol (A)>
Any known 3-amino-4-octanol can be used as component (A) without any particular restrictions, as long as it is 3-amino-4-octanol. Conventionally known cleaning agents have had difficulty in adequately removing copper oxide films formed on copper electrode surfaces of circuit boards, etc. However, after extensive research, the present inventors have found that by using 3-amino-4-octanol in a cleaning composition and a water-dilutable cleaning agent described below, it is possible to adequately remove copper oxide films while exhibiting excellent cleaning performance.

The content of component (A) in the cleaning composition is not particularly limited. Examples of the content of component (A) in the cleaning composition, relative to 100% by mass of the cleaning composition, include 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 19% by mass, 18% by mass, 17% by mass, 16% by mass, 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, and 1% by mass.

The content of component (A) in the cleaning composition is preferably 1% by mass or more, relative to 100% by mass of the cleaning composition, from the viewpoints of exhibiting excellent cleaning properties in the cleaning composition and sufficiently removing copper oxide films. The content of component (A) in the cleaning composition is preferably 55% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to 100% by mass of the cleaning composition, from the viewpoints of exhibiting excellent cleaning properties in the cleaning composition, suppressing corrosion of metals such as aluminum, and sufficiently removing copper oxide films. The content of component (A) in the cleaning composition is preferably approximately 1 to 55% by mass, more preferably approximately 1 to 35% by mass, and even more preferably approximately 1 to 30% by mass, relative to 100% by mass of the cleaning composition, from the viewpoints of exhibiting excellent cleaning properties in the cleaning composition, suppressing corrosion of metals such as aluminum, and sufficiently removing copper oxide films.

<Organophosphorus Compound (B)>
The component (B) is not particularly limited as long as it is at least one selected from the group consisting of an acidic phosphate ester (B1) (hereinafter referred to as component (B1)), an organic phosphonic acid (B2) (hereinafter referred to as component (B2)), and salts thereof, and various known components can be used. The component (B) may be used alone or in combination of two or more.

Although previously known cleaning agents have excellent cleaning properties, they can sometimes cause corrosion of metal parts such as aluminum. However, after extensive research, the inventors have discovered that by using component (B) in the above cleaning composition and the water-dilutable cleaning agent described below, corrosion of metals such as aluminum can be inhibited while maintaining excellent cleaning properties.

(Acidic phosphate ester (B1))
The component (B1) is not particularly limited as long as it is an acidic phosphate ester, and various known compounds can be used. The component (B1) may be used alone or in combination of two or more. The acidic phosphate ester refers to a phosphate ester having at least one hydroxyl group (—OH) bonded to the phosphorus atom in the phosphate group.

Examples of component (B1) include compounds represented by the following general formula (1):

(In formula (1), R ¹ represents a linear or branched alkyl group having 1 to 24 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms, and n represents an integer from 0 to 20. X represents a hydroxyl group or a group represented by general formula (2): R ² O—(CH ₂ CH ₂ O) _m — (In formula (2), R ² represents a linear or branched alkyl group having 1 to 24 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms, and m represents an integer from 0 to 20).

In the above general formulas (1) and (2), the number of carbon atoms in ^R1 and ^R2 is preferably 5 or more, more preferably 6 or more, even more preferably 8 or more, and still more preferably 10 or more, from the viewpoint of inhibiting corrosion of metals such as aluminum. In the above general formulas (1) and (2), the number of carbon atoms in ^R1 and ^R2 is preferably 21 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and still more preferably 13 or less, from the viewpoint of exhibiting excellent detergency. In the above general formulas (1) and (2), the number of carbon atoms in ^R1 and ^R2 is preferably 5 to 21, more preferably 6 to 18, even more preferably 8 to 18, and still more preferably 10 to 18, from the viewpoint of inhibiting corrosion of metals such as aluminum while exhibiting excellent detergency.

In the above general formulas (1) and (2), R ¹ and R ² are preferably a linear or branched alkyl group having 1 to 24 carbon atoms, more preferably a linear or branched alkyl group having 5 to 21 carbon atoms, even more preferably a linear or branched alkyl group having 6 to 18 carbon atoms, still more preferably a linear or branched alkyl group having 8 to 18 carbon atoms, and particularly preferably a linear or branched alkyl group having 10 to 18 carbon atoms, from the viewpoint of suppressing corrosion of metals such as aluminum while exhibiting excellent cleaning properties.

In the above general formulas (1) and (2), n and m are preferably 0 or greater, more preferably 3 or greater, and even more preferably 4 or greater, in order to exhibit excellent cleaning performance. In the above general formulas (1) and (2), n and m are preferably 16 or less, more preferably 14 or less, even more preferably 12 or less, and even more preferably 10 or less, in order to exhibit excellent cleaning performance. In the above general formulas (1) and (2), n and m are preferably 0 to 16, more preferably 0 to 14, even more preferably 3 to 14, even more preferably 4 to 12, and even more preferably 4 to 10, in order to exhibit excellent cleaning performance.

There are no particular limitations on the salt of component (B1), and various known salts can be used. Examples of salts of component (B1) include metal salts of component (B1), such as sodium salts and potassium salts of component (B1), ammonium salts of component (B1), and alkanolamine salts of component (B1).

(Organic phosphonic acid (B2))
The component (B2) is not particularly limited as long as it is an organic phosphonic acid, and various known organic phosphonic acids can be used. The component (B2) may be used alone or in combination of two or more.

Examples of component (B2) include compounds represented by the following general formula (3), alkylenediphosphonic acid, alkylaminophosphonic acid, hydroxyalkylphosphonic acid, 3-phosphonopropionic acid, L-O-phosphoserine, and 2-phosphonobutane-1,2,4-tricarboxylic acid.

(In formula (3), ^R3 represents a linear or branched alkyl group having 1 to 24 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms.)

In the above general formula (3), the number of carbon atoms in R ³ is preferably 5 or more, more preferably 6 or more, and even more preferably 8 or more, from the viewpoint of inhibiting corrosion of metals such as aluminum. In the above general formula (3), the number of carbon atoms in R ³ is preferably 21 or less, more preferably 18 or less, even more preferably 16 or less, and even more preferably 14 or less, from the viewpoint of exhibiting excellent detergency. In the above general formula (3), the number of carbon atoms in R ³ is preferably 5 to 21, more preferably 6 to 18, and even more preferably 8 to 14, from the viewpoint of inhibiting corrosion of metals such as aluminum while exhibiting excellent detergency.

In the above general formula (3), ^R3 is preferably a linear or branched alkyl group having 5 to 21 carbon atoms or a phenyl group, more preferably a linear or branched alkyl group having 6 to 18 carbon atoms or a phenyl group, and even more preferably a linear or branched alkyl group having 8 to 14 carbon atoms or a phenyl group, from the viewpoint of suppressing corrosion of metals such as aluminum while exhibiting excellent cleaning properties.

Examples of the alkylene diphosphonic acid include methylene diphosphonic acid, 1,2-ethylene diphosphonic acid, 1,3-propylene diphosphonic acid, 1,4-butylene diphosphonic acid, 1,5-pentylene diphosphonic acid, and 1,6-hexylene diphosphonic acid.

Examples of the alkylaminophosphonic acid include N,N,N',N'-tetrakis(phosphonomethyl)ethylenediamine, aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and alendronic acid.

Examples of the hydroxyalkylphosphonic acid include hydroxyethanediphosphonic acid.

Component (B2) is preferably a compound represented by general formula (3) above, as it exhibits excellent detergency in the detergent composition and inhibits corrosion of metals such as aluminum. For the same reasons, it is more preferably at least one selected from the group consisting of hexylphosphonic acid, octylphosphonic acid, and decylphosphonic acid.

The salt of component (B2) is not particularly limited, and various known salts can be used. Examples of salts of component (B2) include metal salts of component (B2), such as sodium salts and potassium salts of component (B2), ammonium salts of component (B2), and alkanolamine salts of component (B2).

However, if component (B) is replaced with an organic sulfonic acid compound such as a sulfonic acid surfactant (e.g., alkylbenzenesulfonic acid, its salts, or its esters) used in conventional cleaning agents, corrosion of metals such as aluminum cannot be suppressed, and the cleaning properties of the cleaning agent composition tend to be insufficient.

The content of component (B) in the cleaning composition is not particularly limited. Examples of the content of component (B) in the cleaning composition, relative to 100% by mass of the cleaning composition, include 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 19% by mass, 18% by mass, 17% by mass, 16% by mass, 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, and 3% by mass.

The content of component (B) in the above-mentioned cleaning composition is preferably 3% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 16% by mass or more, relative to 100% by mass of the cleaning composition, in order to ensure that the cleaning composition exhibits excellent cleaning properties and inhibits corrosion of metals such as aluminum. The content of component (B) in the above-mentioned cleaning composition is preferably 75% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to 100% by mass of the cleaning composition, in order to ensure that the cleaning composition exhibits excellent cleaning properties and inhibits corrosion of metals such as aluminum. The content of component (B) in the above-mentioned cleaning composition is preferably approximately 3 to 75% by mass, more preferably approximately 3 to 50% by mass, even more preferably approximately 10 to 50% by mass, and particularly preferably approximately 16 to 50% by mass, relative to 100% by mass of the cleaning composition, in order to ensure that the cleaning composition exhibits excellent cleaning properties and inhibits corrosion of metals such as aluminum.

In the cleaning composition, the molar ratio (H ⁺ /NH ₂ ) of the acid group (H ⁺ ) of the component (B) to the amino group (NH ₂ ) of the component (A) is not particularly limited. The molar ratio may be, for example, 0.99, 0.98, 0.97, 0.96, 0.95, 0.93, 0.92, 0.91, 0.90, 0.89, 0.88, 0.87, 0.86, 0.85, 0.84, 0.83, 0.82, 0.81, 0.80, 0.79, 0.78, 0.77, 0.76, 0.75, 0.74, 0.73, 0.72, 0.71, 0.70, 0.69, 0.68, 0.67, 0.66, 0.65, 0.64, 0.63, Examples of the molar ratio (H ⁺ /NH ₂ ) in the cleaning composition include 0.62, 0.61, 0.60, 0.59, 0.58, 0.57, 0.56, 0.55, 0.54, 0.53, 0.52, 0.51, 0.50, 0.49, 0.48, 0.47, 0.46, 0.45, 0.44, 0.43, 0.42, 0.41, 0.40, 0.35, 0.30, 0.25, 0.20, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.12, 0.11, and 0.10. In order to inhibit corrosion of metals such as aluminum, the molar ratio (H + /NH 2 ) in the cleaning composition is preferably 0.10 to 0.99, and more preferably 0.25 to 0.75.

In this specification, the molar ratio (H ⁺ /NH ₂ ) is a value calculated from the molar ratio (H ⁺ /NH ₂ ) = [content (mass%) of component (A) × first acid value (mg KOH/g) of component (A)] / [content (mass%) of component (B) × total amine value (mg KOH/g) of component (B)]. The first acid value of component (A) is measured according to the potentiometric titration method of JIS K0070:1992, and the acid value (mg KOH/g) is calculated from the first equivalent point in the obtained titration curve. The total amine value (mg KOH/g) of component (B) is a value measured in accordance with JIS K7237.

(Water (C))
The cleaning composition may contain water (C) (hereinafter referred to as "component (C)") as an optional component. By containing component (C), 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. Component (C) may be used alone or in combination of two or more types.

The content of component (C) in the cleaning composition is not particularly limited. Examples of the content of component (C) in the cleaning composition, relative to 100% by mass of the cleaning composition, include 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass.

The content of component (C) in the above-mentioned cleaning composition is preferably 0% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, relative to 100% by mass of the cleaning composition, in order to provide excellent handleability in the cleaning composition. The content of component (C) in the above-mentioned cleaning composition is preferably 15% by mass or less, more preferably 10% by mass or less, relative to 100% by mass of the cleaning composition, in order to provide excellent handleability in the cleaning composition and excellent cleaning performance in the cleaning composition. The content of component (C) in the above-mentioned cleaning composition is preferably approximately 0 to 15% by mass, more preferably approximately 0 to 10% by mass, and even more preferably approximately 5 to 10% by mass, relative to 100% by mass of the cleaning composition, in order to provide excellent handleability in the cleaning composition and excellent cleaning performance in the cleaning composition.

(Other ingredients)
The cleaning composition may optionally contain components other than components (A) to (C) (hereinafter referred to as "other components"), as long as the effects of the present invention are achieved. Examples of other components include an organic solvent (D) (hereinafter referred to as "component (D)") and additives.

(Organic solvent (D))
The component (D) is not particularly limited as long as it is an organic solvent, and various known organic solvents can be used. The component (D) may be used alone or in combination of two or more.

Component (D) is preferably a non-halogenated solvent because it has low toxicity to the human body and is environmentally friendly. Examples of such non-halogenated solvents include glycol ether (D1) (hereinafter referred to as component (D1)), hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, ester solvents, and nitrogen-containing compound solvents. The above organic solvents may be used alone or in combination of two or more.

(Glycol ether (D1))
The component (D1) is not particularly limited as long as it is a glycol ether, and various known glycol ethers can be used. The component (D1) may be used alone or in combination of two or more.

Examples of component (D1) include aliphatic glycol ethers and aromatic glycol ethers. There are no particular restrictions on the aliphatic glycol ethers and aromatic glycol ethers, and various known glycol ethers can be used.

Component (D1) is preferably a compound represented by the following general formula (4), as this provides excellent cleaning properties to the cleaning composition.

(In formula (4), ^R4 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group; ^R5 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 compounds represented by the above general formula (4) include ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, triethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ethers, tripropylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, tripropylene glycol dialkyl ethers, 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.

Examples of the ethylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-n-pentyl ether, and ethylene glycol mono-n-hexyl ether.

Examples of the diethylene glycol monoalkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-t-butyl ether, diethylene glycol mono-n-pentyl ether, and diethylene glycol mono-n-hexyl ether.

Examples of the triethylene glycol monoalkyl ether include triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol monoisopropyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol monoisobutyl ether, triethylene glycol mono-t-butyl ether, triethylene glycol mono-n-pentyl ether, and triethylene glycol mono-n-hexyl ether.

Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-pentyl ether, and propylene glycol mono-n-hexyl ether.

Examples of the dipropylene glycol monoalkyl ether include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 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, and dipropylene glycol mono-n-hexyl ether.

Examples of the tripropylene glycol monoalkyl ether include tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, 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, and tripropylene glycol mono-n-hexyl ether.

Examples of the ethylene glycol dialkyl ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, ethylene glycol diisobutyl 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, and ethylene glycol ethyl isopropyl ether.

Examples of the diethylene glycol dialkyl ether include 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, and diethylene glycol ethyl isopropyl ether.

Examples of the triethylene glycol dialkyl ether include 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, and triethylene glycol ethyl n-pentyl ether.

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

Examples of the dipropylene glycol dialkyl ether include 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, and dipropylene glycol ethyl t-butyl ether.

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

Component (D1) is particularly preferred because it has excellent detergency in the detergent composition, and is therefore particularly preferred for use in cleaning compositions containing ethylene glycol monoisopropyl ether, ethylene glycol mono t-butyl ether, ethylene glycol mono n-hexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono n-hexyl ether, diethylene glycol mono 2-ethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol mono n-butyl ether, propylene glycol mono n-propyl ether, propylene glycol At least one selected from the group consisting of glycol mono-n-butyl ether, propylene glycol monophenyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, and dipropylene glycol dimethyl ether is preferred, and from the same viewpoints, at least one selected from the group consisting of diethylene glycol mono-n-hexyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, and diethylene glycol di-n-butyl ether is more preferred.

(hydrocarbon solvents)
Examples of the hydrocarbon solvent include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, dodecylbenzene, diisopropylbenzene, tetraamylbenzene, dodecane, hexadecane, tetradecane, tetradecene, decalin, dimethyldecalin, diisopropylcyclohexane, butylcyclohexane, dodecylcyclohexane, dicyclohexylmethane, paramenthane, pinane, myrcene, menthane, 1-decene, limonene, isononane, isodecane, isoundecane, isododecane, 2,2,4,6,6-pentamethylheptane, and terpinene.

(alcohol-based solvent)
Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, 2-octanol, 2-methyl-1-butanol, 3-methyl-2-butanol, 4-methyl-2-pentanol, cyclohexanol, 2-ethylbutanol, 3,5-dimethyl-1-hexyn-3-ol, 3-heptanol, 2-heptanol, 2-ethylhexanol, tetrahydrofurfuryl alcohol, furfuryl alcohol, and benzyl alcohol.

(Ketone solvent)
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, di-n-propyl ketone, diisopropyl ketone, diisobutyl ketone, ethyl-n-butyl ketone, methyl hexyl ketone, methyl-n-amyl ketone, cyclohexanone, methylcyclohexanone, and methyl-n-hexyl ketone.

(Ether solvent)
The ether solvent is an ether solvent other than the above-mentioned component (D1), and examples thereof include diethyl ether, diisopropyl ether, ethyl t-butyl ether, dibutyl ether, ethyl isoamyl ether, diisoamyl ether, vinyl methyl ether, vinyl ethyl ether, amyl xylyl ether, hexyl ether, and tetrahydrofuran.

(ester solvent)
Examples of the ester solvent include ethyl acetate, methyl acetate, coconut fatty acid methyl ester, isopropyl myristate, 2-ethylhexyl stearate, methyl laurate, methyl oleate, isobutyl oleate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, propylene glycol diacetate, ethylene glycol monobutyl ether acetate, butyl lactate, methyl acetoacetate, ethyl acetoacetate, diethyl oxalate, and octanoate.

(Nitrogen-containing compound solvent)
Examples of the nitrogen-containing compound solvent include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylformamide.

Component (D) is preferably at least one selected from the group consisting of component (D1) and benzyl alcohol, as this provides particularly good cleaning properties in the detergent composition. For the same reasons, component (D) is preferably at least one selected from the group consisting of diethylene glycol mono-n-hexyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, and benzyl alcohol.

The content of component (D) in the cleaning composition is not particularly limited. Examples of the content of component (D) in the cleaning composition, relative to 100% by mass of the cleaning composition, include 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, and 0% by mass.

The content of component (D) in the cleaning composition is preferably 0% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, relative to 100% by mass of the cleaning composition, in order to ensure excellent cleaning performance in the cleaning composition. The content of component (D) in the cleaning composition is preferably 95% by mass or less, relative to 100% by mass of the cleaning composition, in order to ensure excellent cleaning performance in the cleaning composition, suppress corrosion of metals such as aluminum, and sufficiently remove copper oxide films. The content of component (D) in the cleaning composition is preferably approximately 0 to 95% by mass, more preferably approximately 30 to 95% by mass, and even more preferably approximately 50 to 95% by mass, relative to 100% by mass of the cleaning composition, in order to ensure excellent cleaning performance in the cleaning composition, suppress corrosion of metals such as aluminum, and sufficiently remove copper oxide films.

The content of component (D1) in the cleaning composition is not particularly limited. Examples of the content of component (D1) in the cleaning composition, relative to 100% by mass of the cleaning composition, include 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, and 0% by mass.

The content of component (D1) in the above cleaning composition is preferably 0% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, relative to 100% by mass of the cleaning composition, in order to ensure excellent cleaning performance in the cleaning composition. The content of component (D1) in the above cleaning composition is preferably 95% by mass or less, relative to 100% by mass of the cleaning composition, in order to ensure excellent cleaning performance in the cleaning composition, suppress corrosion of metals such as aluminum, and sufficiently remove copper oxide films. The content of component (D1) in the above cleaning composition is preferably approximately 0 to 95% by mass, more preferably approximately 30 to 95% by mass, and even more preferably approximately 50 to 95% by mass, relative to 100% by mass of the cleaning composition, in order to ensure excellent cleaning performance in the cleaning composition, suppress corrosion of metals such as aluminum, and sufficiently remove copper oxide films.

The content of benzyl alcohol in the cleaning composition is not particularly limited. Examples of the content of benzyl alcohol in the cleaning composition, relative to 100% by mass of the cleaning composition, include 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 19% by mass, 18% by mass, 17% by mass, 16% by mass, 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass.

The content of benzyl alcohol in the above cleaning composition is preferably 0% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, relative to 100% by mass of the cleaning composition, in order to ensure excellent cleaning performance in the cleaning composition. The content of benzyl alcohol in the above cleaning composition is preferably 95% by mass or less, relative to 100% by mass of the cleaning composition, in order to ensure excellent cleaning performance in the cleaning composition, suppress corrosion of metals such as aluminum, and sufficiently remove copper oxide films. The content of benzyl alcohol in the above cleaning composition is preferably approximately 0 to 95% by mass, more preferably approximately 30 to 95% by mass, and even more preferably approximately 50 to 95% by mass, relative to 100% by mass of the cleaning composition, in order to ensure excellent cleaning performance in the cleaning composition, suppress corrosion of metals such as aluminum, and sufficiently remove copper oxide films.

When component (D1) and benzyl alcohol are used in combination in component (D), the mass ratio of component (D1) to benzyl alcohol is not particularly limited, but from the standpoint of cleaning properties, a ratio of approximately 20-80:80-20 is preferred.

Specific examples of the additives include rust inhibitors, surfactants, antifoaming agents, antioxidants, chelating agents, organic acids, amine compounds, and organophosphorus compounds other than component (B). 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 general formula (5): R ⁶ -O-(CH2-CH2-O)e-H (wherein R ⁶ represents an alkyl group having 8 to 20 carbon atoms, and e represents an integer of 0 to 20), ethylene oxide adducts of fatty acid amides, sorbitan fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, and their corresponding polyoxypropylene surfactants and polyoxyalkyleneamine surfactants.

Examples of the anionic surfactant include sulfate ester-based anionic surfactants (such as sulfate ester salts of higher alcohols, alkyl sulfate ester salts, and polyoxyethylene alkyl sulfate ester salts), and sulfonate-based anionic surfactants (such as alkyl sulfonates and alkylbenzene sulfonates).

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

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

The content of the surfactant is not particularly limited, but is preferably 0 to 15% by mass, and more preferably 1 to 10% by mass, relative to 100% by mass of the cleaning composition, in order to ensure that the cleaning composition exhibits excellent cleaning properties and is able to sufficiently remove copper oxide films.

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 agents can be used. Examples of the chelating agent include carboxylic acid chelating agents, amino 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, and tyrosine.

Examples of the phosphate-based chelating agents include orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, and polyphosphoric acid.

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 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. Note that the amine compounds do not include component (B).

The above-mentioned 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; bis(2-dimethylaminoethyl) ) ether, bis(2-diethylaminoethyl) ether, bis(2-diisopropylaminoethyl) ether, bis(2-di-n-propylaminoethyl) ether, and other diaminoalkyl ethers; and 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.

Examples of the alkanolamine 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 include diethanolamine, 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 organophosphorus compound is not particularly limited as long as it is other than component (B), and various known compounds can be used. Examples of the organophosphorus compound include phosphate esters and phosphites other than component (B). These organophosphorus compounds may also be salts. The organophosphorus compounds may be used alone or in combination of two or more.

Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trihexyl phosphate, trioctyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tristearyl phosphate, trioleyl phosphate, and triphenyl phosphate.

Examples of the phosphite ester include 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 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.

It should be noted that it is not preferable to add an oxidizing agent to the above-mentioned cleaning composition, as this would accelerate metal corrosion. Examples of such oxidizing agents include hydrogen peroxide; other peroxy compounds such as salts and acids containing anions of peroxomonosulfuric acid, perborate, perchlorate, periodate, persulfate, permanganate, and peracetic acid; and amine-N-oxides.

Examples of additional oxidizing agents include _FeCl3 , _FeF3 , Fe( _NO3 ) ₃ , Sr( _NO3 ) ₂ , _CoF3 , _MnF3 , ozone ( _{2KHSO5 , KHSO4, K7SO4} ), iodic acid, vanadium(V) oxide, vanadium(IV, _V ) oxide, ammonium vanadate, polyatomic salts of ammonium ₍ e.g., ammonium peroxomonosulfate, ammonium chlorite ( _NH4ClO2 ), ammonium chlorate ( _NH4ClO3 ), ammonium iodate ( _{NH4IO3 )} , ammonium nitrate ( _{NH4NO3 )} , ammonium perborate (NH4BO3), ammonium _perchlorate ( _NH4ClO4 ), ammonium _periodate ( _{NH4IO4 ) ) .} ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), ammonium hypochlorite (NH ₄ ClO)), ammonium tungstate ((NH ₄ ) ₁₀ H ₂ (W ₂ O ₇ )), polyatotnic salts of sodium (e.g., sodium persulfate (Na ₂ S ₂ O ₈ ), sodium hypochlorite (NaClO), sodium perborate), polyatomic salts of potassium (e.g., potassium iodate (KIO ₃ ), potassium permanganate (KMnO ₄ ), potassium persulfate, nitric acid (HNO ₃ ), potassium persulfate (K ₂ S ₂ O ₈ ), potassium hypochlorite (KClO)), polyatomic salts of tetramethylammonium (e.g., tetramethylammonium chlorite ((N(CH ₃ ) ₄ )ClO ₂ ), tetramethylammonium chlorate ((N(CH ₃ ) ₄ ) _ClO3 ), tetramethylammonium iodate ((N( _CH3 ) ₄ ) _IO3 ), tetramethylammonium perborate ((N( _CH3 ) ₄ )BO3), tetramethylammonium perchlorate ((N( _CH3 ) ₄ ) _ClO4 ), tetramethylammonium periodate ((N( _CH3 ) ₄ ) _IO4 ), tetramethylammonium persulfate ((N( _CH3 ) _{4 )S2O8 )} ), polyatomic salts of tetrabutylammonium (e.g., tetrabutylammonium peroxomonosulfate), peroxotononosulfuric acid, ferric nitrate (Fe( _NO3 ) ₃ ), urea hydrogen peroxide (( _CO ( _NH2 ) ₂ ) _{H2O2 )} ), peracetic acid (CH ₃ (CO)OOH), 1,4-benzoquinone, toluquinone, dimethyl-1,4-benzoquinone, chloranil, alloxan, N-methylmorpholine N-oxide, trimethylamine N-oxide, and combinations thereof. Other examples of oxidizing agents include perbromic acid, telluric acid, trifluoroperacetic acid, m-chloroperbenzoic acid, t-butyl hydroperoxide, dibenzoyl peroxide, potassium peroxysulfate (e.g., Oxone® DuPont), methyl ethyl ketone peroxide, acetone peroxide, ethyl hydroperoxide, and cumene hydroperoxide.

In the above-mentioned cleaning composition, the method for blending components (A) to (C) and other components is not particularly limited, and any general liquid mixing method can be used. Specific blending methods include stirring.

[Water-diluted cleaning agent]
The water-diluted detergent of the present invention is a composition containing the above-mentioned detergent composition and water. In other words, the water-diluted detergent is a detergent obtained by diluting the above-mentioned detergent composition with water.

The water content in the water-dilutable detergent is not particularly limited. For example, the water content in the water-dilutable detergent is 1500 parts by weight, 1400 parts by weight, 1300 parts by weight, 1200 parts by weight, 1100 parts by weight, 1000 parts by weight, 900 parts by weight, 800 parts by weight, 700 parts by weight, 600 parts by weight, 500 parts by weight, 400 parts by weight, 300 parts by weight, 200 parts by weight, or 100 parts by weight, per 100 parts by weight of the detergent composition. The water content in the water-dilutable detergent is preferably about 200 to 1200 parts by weight, more preferably about 400 to 900 parts by weight, per 100 parts by weight of the detergent composition, in order to reduce the cost and environmental impact of the water-dilutable detergent and achieve sufficient cleaning performance.

The above water-dilutable cleaners are classified into three types based on the suspension state of the cleaner after dilution: homogeneous, heated milky white, and completely milky white. Homogeneous cleaners are transparent at temperatures between 1 and 90°C. Heat-induced milky white cleaners are transparent at temperatures below the cloud point and become milky white with oil droplets dispersed in water at temperatures above the cloud point. Completely milky white cleaners are milky white with oil droplets dispersed in water at temperatures between 1 and 90°C.

Among the above water-diluted cleaners, completely cloudy and heated cloudy types generally have a higher ability to remove oil-soluble and water-soluble stains and sufficient cleaning performance compared to homogeneous types due to their cloudiness during cleaning. Furthermore, completely cloudy water-diluted cleaners have better cleaning performance than heated cloudy types. On the other hand, homogeneous water-diluted cleaners have better rinsing properties in the water rinsing process compared to completely cloudy and heated cloudy types, and their uniform appearance makes it easier to control the concentration of the cleaner ingredients using optical instruments such as a refractometer. Furthermore, heated cloudy water-diluted cleaners have better rinsing properties and easier concentration control compared to completely cloudy types.

In the above-mentioned water-dilutable detergents, if the alkyl group in component (B1) has a high carbon number, or if the alkylene oxide chain in component (B1) is short or absent, the suspension tends to become completely cloudy or cloudy upon heating. On the other hand, if the alkyl group in component (B1) has a low carbon number, or if the alkylene oxide chain in component (B1) is long, the appearance of the water-dilutable detergent tends to be uniform.

In the above water-diluted detergents, if the solubility of component (D) in water at 20°C is 10% by mass or less, the suspension state of the water-diluted detergent tends to become completely cloudy or cloudy upon heating, and the cleaning performance of the water-diluted detergent tends to be high. On the other hand, if the solubility of component (D) in water at 20°C is more than 10% by mass, the appearance of the water-diluted detergent tends to be uniform.

In the above-mentioned water-diluted cleaning agent, the method for mixing the cleaning composition and water is not particularly limited, and any general liquid mixing method can be used. Specific mixing methods include stirring.

In order to inhibit corrosion of metals such as aluminum, the pH of the above water-diluted cleaning agent at 25°C is preferably approximately 5.0 to 11.0, and more preferably approximately 6.5 to 10.0.

The above-mentioned cleaning compositions and water-diluted cleaning agents can be classified by the object to be cleaned, and include, for example, cleaners for flux residue, cleaners for soldering flux, cleaners for solder paste, and cleaners for industrial oils. Examples of objects to be cleaned that have such cleaning objects include electronic materials.

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 substrates, polyimide substrates, paper phenolic substrates, 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 thereof that have been cut (slicing, dicing, etc.), ground (backgrinding, blasting, etc.), chamfered (beveling, barreling, etc.), or polished (lapping, polishing, buffing, etc.); and jigs, carriers, magazines, etc. used for processing, mounting, welding, cleaning, and transporting these articles.

[Cleaning target]
The cleaning target of the cleaning composition and the water-diluted cleaning agent is not particularly limited, but examples thereof include soldering flux, solder paste, flux residue, industrial oil, chips, etc. Among these, one selected from the group consisting of soldering flux, solder paste, and flux residue is suitable as the cleaning target of the cleaning composition and the water-diluted cleaning agent.

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

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 purified products thereof. Examples of natural rosin include gum rosin, tall oil rosin, and wood rosin. Examples of rosin derivatives include hydrogenated and disproportionated natural rosin;
Examples of suitable resins 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 polyhydric alcohols constituting the rosin ester include glycerin and pentaerythritol. Examples of unsaturated acids constituting the unsaturated acid-modified rosin include acrylic acid, fumaric acid, and maleic acid. Examples of non-rosin-based base resins include epoxy resins, acrylic resins, polyimide resins, nylon resins, polyacrylonitrile resins, vinyl chloride resins, vinyl acetate resins, polyolefin resins, fluorine-based resins, ABS resins, isoprene rubber, styrene-butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber, nylon rubber, nylon-based elastomers, and polyester-based elastomers.

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 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.

Examples of the other additives mentioned above include anti-mold agents, matting agents, anti-thickening agents, surfactants, etc.

In this specification, "solder paste" refers to a mixture of soldering flux and solder powder. Examples of solder powder include Sn-Ag, Sn-Cu, Sn-Sb, and Sn-Zn lead-free solder powders, as well as lead-containing solder powders. These solder metals may also 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 applied to electrodes via a metal mask by screen printing, and after electronic components are placed on top, 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 residue that is generated after joining electronic components 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 above-mentioned flux residue has adhered include printed circuit boards, ceramic wiring boards, semiconductor element mounting boards, wafers, TAB tape, lead frames, power modules, and camera modules. Furthermore, the corresponding items may have electronic components such as ICs, capacitors, resistors, diodes, transistors, coils, and CSPs soldered to them, or may have BGAs, PGAs, LGAs, etc. formed on them, or may have undergone pre-processing such as solder leveling.

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

Examples of items 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 components such as lead frames.

Other cleaning targets include, for example, printed circuit boards, ceramic wiring boards, semiconductor element mounting boards, cover glass, and chips generated during the dicing process of wafers, etc.

[Cleaning method]
The method for cleaning the object to be cleaned with the cleaning composition or the water-diluted cleaning agent is not particularly limited, and various known methods can be applied. Specific examples include cleaning methods including a cleaning step, a rinsing step with water, and a drying step.

The cleaning process is a process in which the object to be cleaned is brought into contact with the cleaning composition or the water-diluted cleaning agent to remove the object to be cleaned. The water rinsing process is a process in which the object to be cleaned is brought into contact with rinsing water to remove the cleaning composition or the water-diluted cleaning agent 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 or rinsing water is not particularly limited, and various known methods can be used. Examples include a method in which the cleaning composition or rinsing water is sprayed onto the object to be cleaned using a spray device (see JP 2007-096127 A), a method in which the object to be cleaned is immersed in the cleaning composition and ultrasonically cleaned, and a method using a direct-pass cleaning device (registered trademark "Direct Pass", manufactured by Arakawa Chemical Industries, Ltd., Patent No. 2621800, etc.).

The means for contacting the object to be cleaned with the water-diluted cleaning agent or rinsing water is not particularly limited, and various known methods can be used. Examples include immersion and agitation, submerged shower, air shower, and ultrasonic cleaning.

The water rinsing step may be repeated multiple times. For example, by performing a pre-rinsing process on the object to be cleaned and then a final rinsing process, the cleaning composition or water-diluted cleaning agent adhering to the surface of the object to be cleaned can be effectively removed.

The pre-rinsing process can be carried out using conventional pre-rinsing methods such as pure water. The final rinsing process can be carried out according to conventional methods, such as treating the pre-rinsed material with pure water.

The present invention will be explained in more detail below using 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 cleaning composition and water-dilutable cleaning agent]
Example 1
A cleaning composition was prepared by mixing 53 parts of 3-amino-4-octanol and 47 parts of a polyoxyethylene alkyl ether phosphate ester (in general formula (1), ^R1 is an alkyl group having 6 to 10 carbon atoms, n is 4, X is a hydroxyl group or a group represented by general formula (2), and in general formula (2), ^R2 is an alkyl group having 6 to 10 carbon atoms, and m is 4). 400 parts of water were added to 100 parts of the obtained cleaning composition to prepare a water-dilutable cleaning agent X (concentration of the cleaning agent composition: 20% by mass). 900 parts of water were added to 100 parts of the obtained cleaning agent composition to prepare a water-dilutable cleaning agent Y (concentration of the cleaning agent composition: 10% by mass).

Examples 2 to 24 and Comparative Examples 1 to 14
The detergent compositions of Example 1 were prepared in the same manner as in Example 1, except that the components of the detergent compositions were changed to those shown in Tables 1 and 2. The values in Tables 1 and 2 are in parts by mass.

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

In Table 3, R ¹ , n, and X mean R ¹ , n, and X in general formula (1). In Table 3, C6, C10, C12, C13, and C18 in R ¹ represent the number of carbon atoms in the alkyl group of R ¹ , for example, C6 means that the number of carbon atoms is 6.

Additionally, since B1 to B4 in Table 3 are all mixtures of monoesters and diesters, X in B1 to B4 represents a hydroxyl group or a group represented by general formula (2). ^R2 and m in Table 3 mean ^R2 and m in general formula (2). C6, C10, C12, C13, and C18 in R2 in Table ³ represent the number of carbon atoms in the alkyl group of ^R2 ; for example, C6 means that the number of carbon atoms is 6.

Using the cleaning compositions obtained in Examples 1 to 24 and Comparative Examples 1 to 14 and water-diluted cleaning agents X and Y, the cleaning performance, appearance, corrosion inhibition, and copper oxide film removal ability were evaluated, and the pH of water-diluted cleaning agents X and Y was measured. The results are shown in Tables 4 to 9.

<Appearance evaluation>
The cleaning compositions and water-diluted cleaning agents X and Y obtained in Examples 1 to 24 and Comparative Examples 1 to 14 were placed in 50 mL glass containers and left to stand in water baths at 20°C, 40°C, and 60°C for 1 hour, and the uniformity at 20°C, 40°C, and 60°C was visually confirmed. In Tables 4 to 9, "uniform" means that the appearance is transparent and the cleaning composition and the water-diluted cleaning agent are completely compatible, while "heterogeneous" means that the appearance is cloudy or separated into two layers, an aqueous layer and an oil layer, and the cleaning composition and the water-diluted cleaning agent are 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 × 1.0 mm thick) using a metal mask, and then reflowed according to the following profile to prepare a test substrate with flux adhered thereto.

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

(Detergency test of cleaning agent composition and water-diluted cleaning agent)
Using the above test substrates, cleaning tests were performed by an ultrasonic immersion method under the following cleaning and water rinsing conditions. Test substrates were brought into contact with the cleaning compositions and water-diluted detergents X and Y obtained in Examples 1 to 24 and Comparative Examples 1 to 14, and then cleaned by irradiating them with ultrasonic waves for 3, 5, 10, or 20 minutes. Next, the test substrates were immersed in ion-exchanged water at a liquid temperature of 25°C and irradiated with ultrasonic waves for 5 minutes to perform a pre-rinse. Furthermore, the test substrates were immersed in ion-exchanged water at a liquid temperature of 25°C and irradiated with ultrasonic waves for 5 minutes to perform a final rinse. The test substrates were then air-blown for 1 minute to remove moisture and then dried. The surfaces of the dried test substrates were visually evaluated for cleaning performance based on the following criteria.
⊚: When the cleaning time was 3 minutes, the flux was successfully removed.
◯+: When the cleaning time was 3 minutes, flux remained, but when the cleaning time was 5 minutes, the flux was successfully removed.
◯: When the cleaning time was 5 minutes, flux remained, but when the cleaning time was 10 minutes, the flux was successfully removed.
Δ: When the cleaning time was 10 minutes, some flux remained, but when the cleaning time was 20 minutes, the flux was successfully removed.
x: When the cleaning time was 20 minutes, flux remained.

(Conditions for cleaning using the immersion ultrasonic method and rinsing with water)
Ultrasonic frequency: 40 kHz
Ultrasonic output: 100W
Ultrasonic tank internal dimensions: 240mm x 140mm
Watt density: 0.30 W/ ^cm2

<Evaluation of corrosion inhibition>
An aluminum test panel (Nippon Test Panel, A1050P) was brought into contact with the cleaning liquid compositions obtained in Examples 1 to 24 and Comparative Examples 1 to 14 and the water-diluted cleaners X and Y at a liquid temperature of 60°C for 10 minutes under immersion and agitation conditions. Next, the test substrate was pre-rinsed by contacting it with ion-exchanged water at a liquid temperature of 25°C for 10 minutes. Furthermore, a final rinse was performed with running ion-exchanged water for 1 minute. After drying, the aluminum test panel was visually inspected for corrosion based on the following criteria.
○: No discoloration or change in appearance of the aluminum test panel.
×: Discoloration or change in appearance of aluminum test panel.

<Evaluation of copper oxide film removal ability>
(Preparation of test substrate for evaluation of copper oxide film removability)
A phosphorus-deoxidized copper plate (C1220P, 50 mm x 50 mm x 0.3 mm thick) 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)
Using the above test substrates, a copper oxide film removal test by immersion and agitation was conducted. Test substrates for evaluating copper oxide film removability were cleaned by contacting them with the cleaning compositions obtained in Examples 1 to 24 and Comparative Examples 1 to 14 and the water-diluted detergents X and Y for 10 minutes at a liquid temperature of 60°C. Next, the test substrates were pre-rinsed by contacting them with ion-exchanged water at a liquid temperature of 25°C for 10 minutes. Furthermore, a final rinse was performed with running ion-exchanged water for 1 minute. Thereafter, the test substrates were air-blown for 1 minute to remove moisture and then dried. After drying, the surfaces of the test substrates were visually observed according to the following criteria to evaluate copper oxide film removability.
◯: The copper oxide film was removed.
×: A copper oxide film remained.

<pH measurement>
Using a pH meter (trade name "D-54" manufactured by HORIBA, Ltd.), electrodes were immersed in the water-dilutable cleaning agents X and Y obtained in Examples 1 to 24 and Comparative Examples 1 to 14 at a liquid temperature of 25°C, and the water-dilutable cleaning agents X and Y were measured after stirring with a magnetic stirrer for 1 minute.

Claims (5)

3-amino-4-octanol (A),
At least one organic phosphorus compound (B) selected from the group consisting of acidic phosphate esters (B1), organic phosphonic acids (B2) and salts thereof, and
Contain water (C) as needed.fruit,
The acidic phosphate ester (B1) is a compound represented by general formula (1):
The organic phosphonic acid (B2) is a compound represented by general formula (3):
Cleaning composition.
(In formula (1), R ¹ represents a linear or branched alkyl group having 1 to 24 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms, and n represents an integer of 0 to 20. X represents a hydroxyl group or a group represented by the general formula (2): R ² O-(CH ₂ CH ₂ O) _m -(In formula (2), R ² represents a linear or branched alkyl group having 1 to 24 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms, and m represents an integer of 0 to 20.

(In formula (3), R ³ represents a linear or branched alkyl group having 1 to 24 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms) The cleaning composition according to claim 1, further comprising an organic solvent (D). The cleaning composition according to claim 1 or 2, which is used to remove flux residue. A cleaning agent composition comprising the cleaning composition according to claim 1 or 2 and water,
A water-dilutable cleaning agent comprising 100 to 1,500 parts by mass of water per 100 parts by mass of the cleaning composition according to claim 1 or 2. The water-diluted cleaning agent according to claim 4, which is used to remove flux residue.