Stock solution for cleaning agent composition, and cleaning agent composition containing said stock solution for cleaning agent composition

Abstract

To provide an easy-to-handle stock solution for detergent compositions that can yield a water-dilutable detergent, which has superior detergency, can remove a copper oxide film, and can suppress re-oxidation of the copper surface.SOLUTION: A stock solution for detergent compositions includes a halogen-free organic solvent (A), which is a glycol ether (A1) and / or benzyl alcohol (A2) with a water solubility of 10 mass% or less at 20°C, 3-amino-4-octanol (B), and optionally water (C). The proportion of each component is: 50-99.9 mass% of the component (A), 0.1-45 mass% of the component (B), and 0-20 mass% of the component (C). When 100-1500 pts.mass of water is mixed with 100 pts.mass of the stock solution for detergent compositions, the resulting detergent composition turns whitely turbid at 1-90°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a concentrate for a cleaning composition, and a cleaning composition containing the concentrate for a cleaning composition. [Background technology]

[0002] Conventionally, halogenated hydrocarbon solvents such as trichloroethylene, perchloroethylene, methylene chloride, fluorocarbons, etc. 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 problems such as air pollution and soil pollution, and as a result, alternative non-halogen cleaners such as hydrocarbon cleaners, glycol cleaners, and benzyl alcohol cleaners have been proposed (see Patent Documents 1 and 2).

[0003] In recent years, in order to further reduce the environmental burden, 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). Since the mass ratio of water in water-diluted cleaning agents is high, 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 to reduce the environmental burden. In addition, it has an advantage in that the cleaning power can be adjusted by changing the ratio of the organic components depending on the type of dirt.

[0004] Water-diluted cleaners can be classified into diluted products (see Patent Document 3) and undiluted products (see Patent Document 4) from the viewpoint of the timing of dilution with water. 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. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 10-046198 [Patent Document 2] JP 2009-190089 A [Patent Document 3] JP 2013-181060 A [Patent Document 4] JP 2015-218295 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, the inventors have found through their investigations that when cleaning is performed using a water-diluted cleaning agent containing the above-mentioned glycol ether-based compound, the cleaning ability is sometimes insufficient.

[0007] Furthermore, water-diluted cleaning agents classified as undiluted products are superior to diluted products in that the organic components can be transported and stored more efficiently. However, if the undiluted products are non-uniform, the concentrations of the organic components in the water-diluted cleaning agents obtained from them will not be constant, and the quality of the cleaning agents will not be stable, which poses a problem in terms of handling in the production of the cleaning agents.

[0008] In addition, when an electronic component is soldered to the copper electrode surface of a circuit board, if an oxide film (copper oxide film) is formed on the copper surface by heat, this can cause poor wire bonding and poor adhesion of the sealing resin in the post-soldering and cleaning processes, so it is necessary to remove the copper oxide film, but 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 a cleaning agent that can remove the copper oxide film to also suppress the reoxidation of copper.

[0009] An object of the present invention is to provide a stock solution for a cleaning composition which is easy to handle and which gives a water-dilutable cleaning agent which has excellent cleaning properties, is capable of removing a copper oxide film, and is capable of suppressing reoxidation of a copper surface.

[0010] Another object of the present invention is to provide a cleaning composition which has excellent detergency, is capable of removing a copper oxide film, and is capable of suppressing reoxidation of the copper surface. [Means for solving the problem]

[0011] As a result of intensive research aimed at achieving the above object, the present inventors have found that the above object can be achieved by a stock solution for a cleaning composition containing 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 containing the same.

[0012] 1. A non-halogenated organic solvent (A) which is a glycol ether (A1) and / or benzyl alcohol (A2) having a solubility in water of 10 mass% or less at 20°C; 3-amino-4-octanol (B), and Water (C) may be included as necessary. The content of each component in the concentrate for a cleaning composition is 50 to 99.9 mass% for component (A), 0.1 to 45 mass% for component (B), and 0 to 20 mass% for 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 is in a cloudy state at 1 to 90°C; Concentrate for cleaning composition.

[0013] 2. The concentrate for a cleaning composition according to item 1, wherein the 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.

[0014] 3. A cleaning composition concentrate according to claim 1 or 2, comprising water, A cleaning composition, comprising 100 to 1,500 parts by mass of water based on 100 parts by mass of the concentrate for cleaning compositions according to item 1 or 2.

[0015] 4. The cleaning composition according to item 3, which is for removing flux residue. Effect of the Invention

[0016] The concentrate for the cleaning composition of the present invention is a homogeneous solution in which the organic components are concentrated, and therefore can be efficiently transported and stored. In addition, a water-dilutable cleaning agent of stable quality can be obtained, and therefore the concentrate for the cleaning composition of the present invention is easy to handle.

[0017] 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 can maintain excellent cleaning properties even when the dilution ratio of water is increased. In addition, the cleaning composition can sufficiently remove copper oxide films formed on copper electrode surfaces of circuit boards and the like, and can suppress reoxidation of the copper surface. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] [Detergent composition stock solution] 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.

[0019] <Non-halogenated 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% by mass or less at 20° C. The component (A) may be used alone or in combination of two or more kinds.

[0020] (Glycol Ether (A1)) There are no particular limitations on the component (A1), so long as it is a glycol ether that has 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 different types.

[0021] If the solubility of the (A1) component in water at 20°C (hereinafter also simply referred to as water solubility) exceeds 10% by mass, the hydrophilicity of the detergent 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 detergent 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.

[0022] Examples of the component (A1) 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.

[0023] Examples of the aliphatic glycol ether 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, and tripropylene glycol dialkyl ethers.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] From the viewpoint that the cleaning properties in the detergent composition are particularly good, the component (A1) 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, and from the same viewpoint, 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 is more preferable.

[0038] (Benzyl alcohol (A2)) The component (A2) is not particularly limited so long as it is benzyl alcohol, and various known compounds can be used.

[0039] The content of the component (A) is 50 to 99.9% by mass relative to 100% by mass of the concentrate. When the content of the component (A) is 50 to 99.9% by mass, the detergent composition exhibits excellent cleaning properties.

[0040] If the content of component (A) is less than 50% by mass relative to 100% by mass of the concentrate, 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, more preferably about 70 to 99% by mass, and particularly preferably about 80 to 99% by mass relative to 100% by mass of the concentrate.

[0041] <3-amino-4-octanol (B)> As component (B), any known 3-amino-4-octanol can be used without any particular restrictions. Conventionally known cleaning agents have difficulty in adequately removing copper oxide films formed on copper electrode surfaces of circuit boards, etc. However, the present inventors have conducted extensive research and found that the use of 3-amino-4-octanol in a water-diluted cleaning agent can adequately remove copper oxide films while exhibiting excellent cleaning properties, and can also suppress reoxidation of the copper surface.

[0042] The content of component (B) is 0.1 to 45 mass% relative to 100 mass% of the original solution. When the content of component (B) is 0.1 to 45 mass%, the cleaning composition exhibits excellent cleaning properties, can remove copper oxide film, and inhibits reoxidation of the copper surface.

[0043] If the content of the (B) component is less than 0.1% by mass relative to 100% by mass of the original solution, the cleaning composition will tend not to exhibit sufficient cleaning properties, will not be able to sufficiently remove the copper oxide film, and will not suppress reoxidation of the copper surface. If the content of the (B) component is more than 45% by mass relative to 100% by mass of the original solution, the cleaning composition will tend not to exhibit sufficient cleaning properties. The content of the (B) component 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 provide excellent cleaning properties and copper oxide film removability in the cleaning composition and to suppress reoxidation of the copper surface.

[0044] (Water(C)) The 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.

[0045] The component (C) is not particularly limited as long as it is water, and examples thereof include ultrapure water, pure water, ion-exchanged water, purified water, and the like.

[0046] The content of component (C) is not particularly limited, but from the viewpoint of excellent transport efficiency, storage property and handling property in the concentrate, it is preferably 0 to 20 mass% relative to 100 mass% of the concentrate, and more preferably about 1 to 10 mass%. If the content of component (C) exceeds 20 mass% relative to 100 mass% of the concentrate, the concentrate tends to become non-uniform and poor in handling property, and the detergent composition tends not to exhibit sufficient cleaning properties.

[0047] (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, so long as the effects of the present invention can be 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.

[0048] Examples of the (D) component include aliphatic glycol ethers having a water solubility of more than 10% by mass, such as 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.

[0049] 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 mass % relative to 100 mass % of the original solution, and from the same viewpoint, it is more preferably about 0 to 10 mass % relative to 100 mass % of the original solution.

[0050] (Ratio of each ingredient) In the concentrate 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 85-99:1-15.

[0051] In the above-mentioned cleaner composition concentrate, the mass ratio of the total of the components (A) and (B) to the component (C) is not particularly limited, but is preferably about 90-99:1-10, because the concentrate has no flash point and is classified as a non-hazardous material under the Fire Service Act, the cleaner composition exhibits excellent cleaning properties, can remove copper oxide film, and can inhibit re-oxidation of the copper surface.

[0052] In the above-mentioned cleaner composition concentrate, the mass ratio of the (A), (B) and (C) components 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 cleaner composition exhibits excellent cleaning properties, can remove copper oxide film, and can inhibit re-oxidation of the copper surface.

[0053] (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.

[0054] 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.

[0055] Specific examples of the additives include rust inhibitors, surfactants, antifoaming agents, antioxidants, chelating agents, organic acids, amine compounds, organic phosphorus compounds, etc. The additives may be used alone or in combination of two or more.

[0056] 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.

[0057] Examples of the nonionic surfactant include a compound represented by the general formula (3): R4-O-(CH2-CH2-O)eH (wherein R4 represents an alkyl group having 8 to 20 carbon atoms, and e represents an integer of 0 to 20), an ethylene oxide adduct of a fatty acid amide, a sorbitan fatty acid ester, a sucrose fatty acid ester, a fatty acid alkanolamide, and their corresponding polyoxypropylene surfactants and polyoxyalkyleneamine surfactants.

[0058] Examples of the anionic surfactant include sulfate ester-based anionic surfactants (sulfate salts of higher alcohols, alkyl sulfate ester salts, polyoxyethylene alkyl sulfate ester salts, etc.), sulfonate-based anionic surfactants (alkyl sulfonates, alkylbenzene sulfonates, etc.), polyoxyalkylene phosphate-based surfactants, and the like.

[0059] Examples of the cationic surfactant include alkylated ammonium salts and quaternary ammonium salts.

[0060] Examples of the amphoteric surfactant include amino acid type and betaine type amphoteric surfactants.

[0061] The content of the surfactant is not particularly limited, but from the viewpoints of enabling the cleaning composition to exhibit excellent cleaning properties, remove a copper oxide film, and inhibit reoxidation of the copper surface, it is preferably 0 to 15 mass% relative to 100 mass% of the stock solution.

[0062] The chelating agent is not particularly limited as long as it is a metal chelating agent capable of coordinating to a metal ion, and various known ones 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.

[0063] 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.

[0064] Examples of the amino acid chelating agent include glycine, alanine, lysine, arginine, asparagine, and tyrosine.

[0065] Examples of the phosphonic acid chelating agent include hydroxyethanediphosphonic acid, nitrilotrismethylenephosphonic acid, and N,N,N',N'-tetrakis(phosphonomethyl)ethylenediamine.

[0066] Examples of the phosphoric acid-based chelating agent include orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, and polyphosphoric acid.

[0067] 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).

[0068] Examples of the hydroxycarboxylic acid chelating agent include malic acid, citric acid, isocitric acid, glycolic acid, gluconic acid, salicylic acid, tartaric acid, and lactic acid.

[0069] 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 the component (B).

[0070] Examples of the aliphatic amine 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; 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, 4-methyl-1,1,7,7-tetra-n-propyldiethylenetriamine and other triamines.

[0071] Examples of the alkanolamine include N-methylmethanolamine, N-ethylmethanolamine, Nn-propylmethanolamine, Nn-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-propylethanolamine, N-isopropylethanolamine, Nn-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, Nn-propylpropanolamine, N-isopropylpropanolamine, Nn-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, Nn-propylbutanolamine, N-isopropylbutanolamine, Nn-butylbutanolamine, and N,N-dimethylethanolamine. Examples of the 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, Nn-butyldiethanolamine, Nt-butyldiethanolamine, N-cyclohexyldiethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, and N,N-dibutylpropanolamine.

[0072] The above-mentioned organic phosphorus compound is not particularly limited, and various known compounds can be used. The above-mentioned organic phosphorus compound can be, for example, a phosphoric acid ester, a phosphorous acid ester, a phosphonic acid, etc. These organic phosphorus compounds can be salts. The above-mentioned organic phosphorus compounds can be used alone or in combination of two or more kinds.

[0073] Examples of the phosphate ester 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.

[0074] 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.

[0075] 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.

[0076] 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 can be used. A specific mixing method includes a stirring method.

[0077] [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 (A) to (B) components and, if necessary, the (C) component. 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 features 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.

[0078] The amount of water in the 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, from the viewpoints of reducing the cost and environmental impact of the cleaning composition and obtaining sufficient cleaning properties.

[0079] The above-mentioned cleaning composition is prepared by mixing the concentrate for the cleaning composition and water in the above-mentioned mass ratio, and has an appearance of milky white with oil droplets dispersed in water at 1 to 90°C (hereinafter, also referred to as a completely milky white system).

[0080] From the viewpoint of the suspension state of the cleaning composition after dilution with water, water-diluted cleaning agents are classified into three types: homogeneous, heated cloudy, and the completely cloudy type of the present invention. The homogeneous type is a cleaning agent that has a transparent appearance at 1 to 90°C, and the heated cloudy type is a cleaning agent that has a transparent appearance at a temperature lower than the cloud point and becomes cloudy at a temperature equal to or higher than the cloud point. Among water-diluted cleaning agents, the completely cloudy type water-diluted cleaning agent generally has a higher ability to remove oil-soluble and water-soluble stains and has sufficient cleaning properties compared to the homogeneous and heated cloudy types. That is, the cleaning 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.

[0081] In the cleaning composition, the method for mixing the cleaning composition concentrate and water is not particularly limited, and a general liquid mixing method can be used. Specific examples of the mixing method include a stirring method.

[0082] The cleaning composition can be classified according to the object to be cleaned, for example, into cleaning agents for flux residue, cleaning agents for soldering flux, cleaning agents for solder paste, cleaning agents for industrial oil, etc. Also, when classified according to the object to be cleaned, for example, into cleaning agents for electronic materials, etc.

[0083] 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 (Al2O3), 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.), as well as jigs, carriers, magazines, etc. used when processing, mounting, welding, cleaning, and transporting these articles.

[0084] [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.

[0085] In this specification, "soldering flux" refers to a composition used to remove oxide films on the surfaces of solder and base materials (metal electrodes, etc.) and facilitate bonding between the two. In general, it contains a base resin, an activator, and an organic solvent, and may contain a thixotropic agent, an antioxidant, and other additives as necessary. Soldering fluxes are classified into solder paste fluxes and non-solder paste fluxes such as wire solder fluxes, post fluxes, and pre fluxes, depending on their composition.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] Examples of the thixotropic agent include castor oil, hydrogenated castor oil, beeswax, carnauba wax, stearic acid amide, and 12-hydroxystearic acid ethylenebisamide.

[0090] 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.

[0091] Examples of the other additives include antifungal agents, matting agents, thickening inhibitors, surfactants, and the like.

[0092] In this specification, the term "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 containing lead as a constituent. These solder metals may be doped with one or more of Ag, Al, Au, Bi, Co, Cu, Fe, Ga, Ge, In, Ni, P, Pt, Sb, and Zn. The solder paste is supplied onto an electrode through a metal mask by screen printing, and after an electronic component is placed thereon, soldering is performed under heating.

[0093] Examples of the article to which the soldering flux or solder paste is attached include a metal mask for screen printing, a squeegee, a nozzle for a dispensing method, a syringe, and a jig for fixing a substrate.

[0094] The flux residue is a residue that is generated after electronic components, etc. are bonded to electrodes using solder paste, wire solder, 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 is necessary to remove it by cleaning.

[0095] Examples of the 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, camera modules, etc. In addition, the corresponding items may have electronic components such as ICs, capacitors, resistors, diodes, transistors, coils, and CSPs soldered thereto, BGAs, PGAs, LGAs, etc. formed thereon, or may have been subjected to pretreatment such as solder leveling.

[0096] Examples of the industrial oil include processing oil, cutting oil, mineral oil, machine oil grease, lubricating oil, rust-preventive oil, wax, pitch, paraffin, oils and fats, grease, etc. 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 facilitate forming, and to prevent rust and corrosion of products.

[0097] Examples of articles to which the above-mentioned industrial oil has 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.

[0098] Other objects to be cleaned include, for example, printed circuit boards, ceramic wiring boards, semiconductor element mounting boards, cover glasses, and chips generated during dicing of wafers and the like.

[0099] [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.

[0100] The cleaning step is a step of contacting the object to be cleaned with the cleaning composition to remove the object to be cleaned. The water rinsing step is a step of contacting the object to be cleaned with rinsing water to remove the cleaning composition adhering to the object to be cleaned. The drying step is a step of removing the rinsing water adhering to the object to be cleaned.

[0101] The means for contacting the object to be cleaned with the cleaning composition and the rinse water is not particularly limited, and examples thereof include an immersion stirring method, a submerged shower method, an air shower method, and an ultrasonic cleaning method.

[0102] The above-mentioned cleaning composition exhibits excellent cleaning properties when mixed to form a cloudy white state. Therefore, as a cleaning method, the air shower method is preferred because it has a strong mixing force for the cleaning composition and is excellent in cleaning properties and productivity. EXAMPLES

[0103] 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.

[0104] [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).

[0105] 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.

[0106] [Table 1]

[0107] [Table 2]

[0108] The abbreviations of the components in Tables 1 and 2, and the water solubilities of components (A) and (D) are as shown in Table 3.

[0109] [Table 3]

[0110] Appearance was evaluated using the cleaning composition concentrates obtained in Examples 1 to 26 and Comparative Examples 1 to 18. In addition, cleaning performance, copper oxide film removal performance, and copper reoxidation prevention performance 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.

[0111] [Table 4]

[0112] [Table 5] The notes in Table 5 are as follows: (1) Since the concentrate for the cleaning composition was inhomogeneous, the cleaning compositions X and Y were not evaluated. (2) Since the copper oxide film remained in the evaluation of copper oxide film removal, the copper reoxidation prevention property was not evaluated.

[0113] <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.

[0114] <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 then reflowed with the following profile to produce a test board with flux attached.

[0115] (Reflow profile of test board) Atmosphere: Air Heating rate: 1℃ / sec Peak temperature: 240℃, 10 seconds

[0116] (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 rinse 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. ◎: Flux was removed well in both cleaning times of 30 seconds and 1 minute. The flux residue was removed (surface area was 0%). ◯: When the cleaning time was 30 seconds, flux remained, but when the cleaning time was 1 minute, the flux was successfully removed (surface area of ​​flux residue was 0%). △: When the cleaning time was 1 minute, a small amount of flux remained (the surface area of ​​the flux residue was more than 0% but not more than 10%). ×: When the cleaning time was 1 minute, a considerable amount of flux remained (the surface area of ​​the flux residue exceeded 10%).

[0117] (Conditions for cleaning using the air shower method and rinsing with water) Flow rate: 2.3L / min Pressure: 0.1MPa Distance between the injection nozzle and the test substrate: 50 mm

[0118] <Evaluation of copper oxide film removal ability> (Preparation of test substrates for evaluating copper oxide film removal properties) 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.

[0119] (Copper oxide film removal test) A copper oxide film removal test by immersion and stirring was performed using the above test substrate. A test substrate for evaluating copper oxide film removability was brought into contact with cleaning compositions X and 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. A: The copper oxide film was removed. ×: The copper oxide film remained.

[0120] <Evaluation of copper reoxidation prevention properties> 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 properties based on the following criteria. ◯: After removing the copper oxide film, when the sample was stored in a thermostatic chamber at 23° C. for 14 days, 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

1. 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.

2. 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.

3. The cleaning composition according to claim 2, which is for removing flux residue.

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