Metal cleaning agent composition and metal cleaning solution

Abstract

Provided is a metal cleaning agent composition excellent in detergency, workability, and finish. 【Solution means】The metal cleaning agent composition according to one embodiment includes a nonionic surfactant (A) represented by the general formula (1) and a nonionic surfactant (B) represented by the general formula (2). In formula (1), R 1 represents an aliphatic hydrocarbon group, AO 1 represents an oxyalkylene group having 2 to 4 carbon atoms, m represents a number from 1 to 5, and n represents an average addition mole number and represents a number from 1 to 18. In formula (2), R 2 represents an aliphatic hydrocarbon group having 8 to 20 carbon atoms, AO 2 represents an oxyalkylene group having 3 to 4 carbon atoms, p and q are average addition mole numbers, p represents a number from 1 to 15, q represents a number from 0 to 5, and [(C2H4O) p / (AO 2 ) q represents a polymer chain with a molar ratio of p:q. TIFF0007881817000010.tif44148

Description

[Technical Field]

[0001] Embodiments of the present invention relate to a metal cleaning agent composition and a metal cleaning solution containing the same. [Background technology]

[0002] Iron-based metal materials, such as castings and steel plates, and non-ferrous metal materials, such as aluminum and copper, are processed and used in a variety of fields, including the automotive, machinery, metalworking, and electrical industries. In these processing steps, for example, iron-based metals undergo processes such as pressing, cutting, and annealing, while non-ferrous metals undergo processes such as pressing and cutting. After these processes, a cleaning treatment is performed to remove contaminants such as processing oil, chips, fingerprints, and dust adhering to the surface of the part, either as a final finish or preparation for the next process.

[0003] As a cleaning agent composition that has sufficient cleaning performance at low temperatures for cleaning such metals, Patent Document 1 discloses a metal cleaning agent composition comprising a nonionic surfactant consisting of a compound obtained by adding an alkylene oxide to a branched higher alcohol, and a nonionic surfactant having a specific polyoxyalkylene structure. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2009-084621 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0005] In cleaning metal parts as described above, excellent cleaning performance is required, as well as improved work efficiency by shortening the cleaning process by omitting or reducing the rinsing step performed after treatment with the metal cleaning solution, and a finish that leaves no drying marks on the metal surface after cleaning.

[0006] An embodiment of the present invention aims to provide a metal cleaning agent composition excellent in detergency, workability, and finish.

Means for Solving the Problems

[0007] The present invention includes the following embodiments. [1] A metal cleaning agent composition containing a nonionic surfactant (A) represented by the following general formula (1) and a nonionic surfactant (B) represented by the following general formula (2).

Chemical Formula

Chemical Formula

[0008] [2] The metal cleaning agent composition according to [1], wherein the mass ratio (A) / (B) of the content of the nonionic surfactant (A) to the content of the nonionic surfactant (B) is 0.2 to 5.0. [3] The metal cleaning agent composition according to [1] or [2], further containing a carboxylic acid amine salt. [4] The metal cleaning agent composition according to [3], wherein the mass ratio of the content of the carboxylic acid amine salt to the total amount of the nonionic surfactant (A) and the nonionic surfactant (B) is 0.01 to 0.5. [5] The metal cleaning agent composition according to [3] or [4], wherein the total amount of the nonionic surfactant (A) and the nonionic surfactant (B) in the metal cleaning agent composition is 5 to 35% by mass, and the content of the carboxylic acid amine salt is 0.5 to 10% by mass. A metal cleaning solution comprising the metal cleaning agent composition described in any one of items [6] [1] to [5], wherein the solid content concentration is 0.1 to 35% by mass and the pH at 25°C is 6.5 to 8.5. [Effects of the Invention]

[0009] According to this embodiment, a metal cleaning agent composition with excellent cleaning properties, workability, and finish can be provided. [Modes for carrying out the invention]

[0010] The metal cleaning agent composition according to this embodiment contains a nonionic surfactant (A) and a nonionic surfactant (B). By combining the nonionic surfactant (A) and the nonionic surfactant (B), excellent cleaning performance is achieved when cleaning metal parts, and the oil-water separation performance is improved, allowing for the omission or reduction of the rinsing step and improving work efficiency. Furthermore, drying marks on the metal surface after cleaning are reduced, improving the finish.

[0011] Nonionic surfactant (A) is a surfactant represented by the following general formula (1). [ka]

[0012] R in equation (1) 1 R represents an aliphatic hydrocarbon group, which may be linear or branched, saturated or unsaturated, and is a monovalent group. 1The number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. In one embodiment, R 1 The group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0013] In equation (1), m is C6H5-CH(R 1 The average number of substituent substitutions represented by )- is a number between 1 and 5. m is preferably between 1 and 3, and more preferably between 1 and 2. The substitution position of the substituent is not particularly limited, but is preferably the ortho position and / or the para position.

[0014] AO in equation (1) 1 represents an oxyalkylene group with 2 to 4 carbon atoms, which can be linear or branched. AO 1 If multiple entries are included, they may be identical or different. AO 1 Examples include oxyethylene groups, oxypropylene groups, and oxybutylene groups, and any one of these or two or more may be used in combination. (AO 1 ) n is an addition polymerization chain of alkylene oxide, and its addition form is not particularly limited, for example, AO 1 For example, single addition is also possible when there is only one type of oxyalkylene group. Alternatively, AO 1 If it contains two or more oxyalkylene groups, AO 1 The addition method may be random addition, block addition, or a combination of both. In the case of block addition, the order of each block is not limited. Here, random addition is used as a concept that includes chain sequences that follow statistical laws (the same applies to random addition in equation (2)).

[0015] AO 1 The oxyalkylene group is preferably an oxyethylene group, and if it contains two or more types of oxyalkylene groups, it is preferable that one of them be an oxyethylene group. For example, (AO1 ) n , AO 1 It is preferable that the oxyethylene group is contained in an amount of 50 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol% relative to the total number of moles.

[0016] In formula (1), n ​​represents the average number of moles of oxyalkylene groups added, and is a number from 1 to 18. When n is 1 or greater, the cleaning performance and finish can be improved, and when n is 18 or less, the cleaning performance can be improved. n is preferably 3 to 17, more preferably 5 to 16, and even more preferably 10 to 15.

[0017] Nonionic surfactant (B) is a polyoxyalkylene alkyl ether type surfactant represented by the following general formula (2). [ka]

[0018] R in equation (2) 2 This represents the hydrophobic portion of the nonionic surfactant (B), and is an aliphatic hydrocarbon group with 8 to 20 carbon atoms. 2 The aliphatic hydrocarbon group is a monovalent group that can be linear or branched, saturated or unsaturated. 2 R is preferably an alkyl group or alkenyl group having 8 to 20 carbon atoms, and more preferably a linear alkyl group. 2 The number of carbon atoms is preferably 10 to 18, and more preferably 12 to 15.

[0019] In equation (2) [(C2H4O) p / ( AO 2 ) q ] is the hydrophilic group portion of the nonionic surfactant (B). AO 2This represents an oxyalkylene group having 3 to 4 carbon atoms, that is, it may be an oxyalkylene group with 3 carbon atoms, or an oxyalkylene group with 4 carbon atoms, or both may be used in combination. The oxyalkylene group may be linear or branched. AO 2 Preferably, the group is an oxypropylene group and / or an oxybutylene group.

[0020] p is the average number of moles of oxyethylene groups (C2H4O) added, and represents a number from 1 to 15. When p is 15 or less, the oil-water separation performance is improved and workability can be enhanced. p is preferably 3 to 14, and more preferably 6 to 13. q is an oxyalkylene group (AO). 2 This is the average number of moles added, and represents a number from 0 to 5. When q is 5 or less, the finish quality can be improved. q is preferably between 0 and 4, and more preferably between 1 and 4.

[0021] [(C2H4O) p / ( AO 2 ) q ] represents a polymerization chain with a molar ratio p:q. The addition form of the polymerization chain may be the addition of an oxyethylene group alone when q=0. Alternatively, if the polymerization chain is a copolymer, its addition form may be random addition, block addition, or a combination of these random and block additions. That is, at least two oxyalkylene groups selected from oxyalkylene groups having 2 to 4 carbon atoms, provided that they contain an oxyethylene group, may be in a copolymer chain having random addition, block addition, or a combination thereof. In one embodiment, the addition form of the polymerization chain is preferably block addition, or a combination of random and block addition. In the case of block addition, the order of each block is not limited.

[0022] The metal cleaning agent composition according to the embodiment preferably contains a carboxylate amine salt along with nonionic surfactants (A) and (B). By incorporating a carboxylate amine salt, rust prevention for ferrous metals can be improved without impairing cleaning performance and finish. The carboxylate amine salt may be incorporated into the cleaning agent composition as a carboxylate amine salt, or the carboxylic acid and amine may be incorporated separately. When incorporated separately, it is preferable to adjust the mixing ratio of the two such that when the metal cleaning agent composition is diluted with water to a solid content concentration of 1 to 35% by mass, the pH of the aqueous solution at 40°C falls within the range of 6.5 to 8.5.

[0023] Examples of carboxylic acids that constitute a carboxylic acid amine salt include saturated fatty acids such as caproic acid, caprylic acid, octic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid; unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid; aromatic carboxylic acids such as pt-butylbenzoic acid; and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, brassic acid, pentadecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, and octadecanedicarboxylic acid. Any one of these carboxylic acids may be used, or two or more may be used in combination. Among these, fatty acids are preferred as carboxylic acids, and therefore, it is preferable to incorporate fatty acid amine salts into metal cleaning agent compositions. More preferably, the carboxylic acid is a fatty acid having 8 to 22 carbon atoms, and even more preferably a fatty acid having 12 to 20 carbon atoms.

[0024] Examples of amines that make up carboxylate amine salts include ammonia, hydroxylamine, hydrazine, guanidine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-n-propylamine, di-n-propylamine, tri-n-propylamine, mono-n-butylamine, di-n-butylamine, tri-n-butylamine, 2-ethylhexylamine, 3-ethoxypropylamine, t-butylamine, ethylenediamine, hexamethylenediamine, triethylenediamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, di Examples include isopropanolamine, triisopropanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-(2-aminoethyl)ethanolamine, N-methyl-N,N-diethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, cyclohexylamine, o-aminophenol, m-aminophenol, p-aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, piperazine, piperidine, morpholine, N-methylmorpholine, N-ethylmorpholine, etc. These amines may be used individually or in combination of two or more. Among these, it is preferable to use alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-(2-aminoethyl)ethanolamine, N-methyl-N,N-diethanolamine, N,N-dibutylethanolamine, and N-methylethanolamine as the amine.

[0025] In a metal cleaning agent composition, the mass ratio (A) / (B) of the content of nonionic surfactant (A) to the content of nonionic surfactant (B) is preferably 0.2 to 5.0. By setting the mass ratio (A) / (B) to this extent, the effect of improving cleaning performance, workability, and finish can be enhanced. The mass ratio (A) / (B) is more preferably 0.3 to 3.0, even more preferably 0.5 to 2.0, and even more preferably 0.7 to 1.5.

[0026] When a metal cleaning agent composition contains a carboxylate amine salt, the mass ratio (C) / {(A)+(B)} of the content of the carboxylate amine salt (C) to the total amount of nonionic surfactant (A) and nonionic surfactant (B) is preferably 0.01 to 0.5. A mass ratio (C) / {(A)+(B)} of 0.01 or higher enhances the rust prevention effect on ferrous metals, while a mass ratio of 0.5 or lower helps to suppress the rise in pH of the metal cleaning agent composition and reduce the impact on nonferrous metals. A more preferable mass ratio (C) / {(A)+(B)} is 0.02 to 0.1, and even more preferable is 0.03 to 0.07. Here, the content of the carboxylate amine salt (C) is the total amount of both when the carboxylic acid and amine are blended separately as described above.

[0027] The metal cleaning agent composition may be an aqueous solution containing water along with a nonionic surfactant (A), a nonionic surfactant (B), and an optional carboxylate amine salt. In this case, the total amount of nonionic surfactant (A) and nonionic surfactant (B) in the metal cleaning agent composition is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass. If a carboxylate amine salt is included, the content of the carboxylate amine salt in the metal cleaning agent composition is preferably 0.5 to 10% by mass, more preferably 0.7 to 5% by mass, and even more preferably 0.8 to 3% by mass. The solid content concentration of the metal cleaning agent composition is preferably, for example, 5.5 to 40% by mass, more preferably 8 to 35% by mass, and even more preferably 10 to 30% by mass. In this specification, solid content refers to all components excluding water, and is also called nonvolatile content.

[0028] The amounts of nonionic surfactant (A) and nonionic surfactant (B) in the solid content of the metal cleaning agent composition are not particularly limited, but the total amount of nonionic surfactant (A) and nonionic surfactant (B) is preferably 60 to 99% by mass, more preferably 80 to 98% by mass, and even more preferably 90 to 97% by mass.

[0029] The amount of carboxylate amine salt in the solid content of the metal cleaning agent composition is not particularly limited, but is preferably 0.5 to 35% by mass, more preferably 1 to 15% by mass, and even more preferably 2.5 to 10% by mass.

[0030] The metal cleaning agent composition of this embodiment may further contain known preservatives, antioxidants, etc., as needed. In addition, known anionic surfactants, amphoteric surfactants, fluorinated surfactants, etc., may be added as needed.

[0031] The metal cleaning agent composition according to this embodiment may be used as is as a metal cleaning solution for cleaning metal parts, or it may be diluted with water to adjust the solid content concentration before being used as a metal cleaning solution. The solid content concentration of the metal cleaning solution is preferably 0.01 to 25% by mass. Therefore, a metal cleaning solution according to a preferred embodiment contains the above metal cleaning agent composition and has a solid content concentration of 0.01 to 25% by mass. The solid content concentration of the metal cleaning solution is more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 2% by mass.

[0032] The metal cleaning solution preferably has a pH of 6.5 to 8.5 at 25°C, more preferably 6.7 to 8.0, even more preferably 6.9 to 7.7, and even more preferably 7.0 to 7.5. A pH of 6.5 or higher enhances the rust prevention and cleaning effects on ferrous metals, while a pH of 8.5 or lower reduces the effects on non-ferrous metals, such as discoloration.

[0033] In one embodiment, the metal cleaning agent composition preferably has a pH of 6.5 to 8.5 at 25°C when it is an aqueous solution with a solid content concentration of 1% by mass, more preferably 6.7 to 8.0, even more preferably 6.9 to 7.7, and even more preferably 7.0 to 7.5.

[0034] In the process of cleaning metal parts with a metal cleaning solution, the cleaning method is not particularly limited, but various cleaning methods such as immersion, ultrasonic cleaning, immersion agitation, spraying, and manual wiping can be used individually or in combination.

[0035] In a cleaning method according to one embodiment, after treating metal parts with a metal cleaning solution by immersion or ultrasonic cleaning, a rinsing step using water may be performed, but it is preferable to omit the rinsing step. After that, the metal parts may be dried by, for example, air blowing or hot air drying. The metal cleaning agent composition and metal cleaning solution according to this embodiment have excellent oil-water separation properties, and therefore have an excellent effect in preventing the re-adhesion of dirt such as oil, and thus the rinsing step can be omitted or reduced. This shortens the cleaning process and improves work efficiency. Furthermore, by omitting the rinsing step, nonionic surfactants and carboxylate amine salts can be left on the metal surface after cleaning, which can provide improved rust prevention and suppression of drying marks.

[0036] The metal cleaning agent composition and metal cleaning liquid according to this embodiment can be used to clean both ferrous and non-ferrous metals. Ferrous metal materials are represented by steel plates, bars, etc., made of castings, mild steel, hard steel, stainless steel, and other alloy steels. Non-ferrous metal materials are represented by aluminum, copper, zinc, and their alloys. These materials are subjected to processes such as pressing, cutting, and annealing in various fields such as the automotive industry, machinery industry, metal industry, and electrical industry, and then, as a final finishing or preparation for the next process, a cleaning treatment is performed to remove contaminants adhering to the surface of the parts. The metal cleaning agent composition and metal cleaning liquid according to this embodiment are suitably used to remove contaminants such as processing oil, chips, fingerprints, and dust adhering to the surface of the above-mentioned parts. [Examples]

[0037] The present invention will be described in more detail below based on examples and comparative examples, but it is not limited thereto.

[0038] [Synthesis Example 1] 230 g (1.0 mol) of styrene-modified phenol is transferred to an autoclave, and 572 g (13 mol) of ethylene oxide is added under alkaline catalyst conditions of 147 kPa pressure and 150°C, thereby producing the surfactant (a1)(R) represented by formula (1). 1 : Methyl group, (AO1 ) n : Ethylene oxide alone was added (n=13).

[0039] [Synthesis Example 2] 230 g (1.0 mol) of styrene-modified phenol is transferred to an autoclave, and 440 g (10 mol) of ethylene oxide and 174 g (3 mol) of propylene oxide are added under alkaline catalyst conditions of 147 kPa pressure and 150 °C, thereby producing the surfactant (a2)(R) represented by formula (1). 1 : Methyl group, (AO 1 ) n Random addition of 10 moles of ethylene oxide and 3 moles of propylene oxide (n=13) was obtained.

[0040] [Synthesis Example 3] 230 g (1.0 mol) of styrene-modified phenol is transferred to an autoclave, and 440 g (10 mol) of ethylene oxide and 216 g (3 mol) of butylene oxide are added under alkaline catalyst conditions of 147 kPa pressure and 150°C, thereby producing the surfactant (a3)(R) represented by formula (1). 1 : Methyl group, (AO 1 ) n Random addition of 10 moles of ethylene oxide and 3 moles of butylene oxide (n=13) was obtained.

[0041] [Synthesis Example 4] 230 g (1.0 mol) of styrene-modified phenol is transferred to an autoclave, and 352 g (8 mol) of ethylene oxide is added under alkaline catalyst conditions of 147 kPa pressure and 150°C, thereby producing the surfactant (a4)(R) represented by formula (1). 1 : Methyl group, (AO 1 ) n We obtained the result of ethylene oxide addition alone (n=8).

[0042] [Synthesis Example 5] 230 g (1.0 mol) of styrene-modified phenol is transferred to an autoclave, and 132 g (3 mol) of ethylene oxide is added under alkaline catalyst conditions of 147 kPa pressure and 130°C, thereby producing the surfactant (a5)(R) represented by formula (1). 1 : Methyl group, (AO 1 ) n We obtained the result of ethylene oxide addition alone (n=3).

[0043] [Synthesis Example 6] 230 g (1.0 mol) of styrene-modified phenol is transferred to an autoclave, and 704 g (16 mol) of ethylene oxide is added under alkaline catalyst conditions of 147 kPa pressure and 150°C, thereby producing the surfactant (a6)(R) represented by formula (1). 1 : Methyl group, (AO 1 ) n We obtained the result of ethylene oxide addition alone (n=16).

[0044] [Synthesis Example 7] In the presence of an alkaline catalyst, first, 186 g (1 mole) of lauryl alcohol was reacted with 232 g (4 moles) of propylene oxide at 80-150°C. Subsequently, 440 g (10 moles) of ethylene oxide was added and reacted at 80-150°C to obtain surfactant (b1) (polyoxyalkylene lauryl ether) represented by formula (2). In surfactant (b1), R in formula (2) is present. 2 is a lauryl group, AO 2 This is an oxypropylene group, p=10, q=4, [(C2H4O) p / ( AO 2 ) q ] is (PO)4-(EO) 10 (Block added)

[0045] [Synthesis Example 8] In the presence of an alkaline catalyst, first, 186 g (1 mole) of lauryl alcohol was reacted with 232 g (4 moles) of propylene oxide at 80-150°C. Subsequently, 176 g (4 moles) of ethylene oxide was added and reacted at 80-150°C to obtain the surfactant (b2) (polyoxyalkylene lauryl ether) represented by formula (2). In surfactant (b2), R in formula (2) 2 is a lauryl group, AO 2 This is an oxypropylene group, p=4, q=4, [(C2H4O) p / ( AO 2 ) q ] is (PO)4-(EO)4 (block addition).

[0046] [Synthesis Example 9] In the presence of an alkaline catalyst, first, 200 g (1 mole) of tridecyl alcohol was reacted with 132 g (3 moles) of ethylene oxide at 80-150°C. Subsequently, 396 g (9 moles) of ethylene oxide and 116 g (2 moles) of propylene oxide were added and reacted at 80-150°C to obtain the surfactant (b3) (polyoxyalkylene tridecyl ether) represented by formula (2). In surfactant (b3), R in formula (2) is present. 2 is a tridecyl group, AO 2 This is an oxypropylene group, p=12, q=2, [(C2H4O) p / ( AO 2 ) q ] is (EO)3-{(EO)9 / (PO)2} (block addition of a random copolymer chain of 3 moles of EO and 9 moles of EO / 2 moles of PO).

[0047] [Synthesis Example 10] In the presence of an alkaline catalyst, first, 200 g (1 mole) of tridecyl alcohol was reacted with 132 g (3 moles) of ethylene oxide at 80-150°C. Subsequently, 44 g (1 mole) of ethylene oxide and 116 g (2 moles) of propylene oxide were added and reacted at 80-150°C to obtain the surfactant (b4) (polyoxyalkylene tridecyl ether) represented by formula (2). In surfactant (b4), R in formula (2) is present. 2is a tridecyl group, AO 2 This is an oxypropylene group, p=4, q=2, [(C2H4O) p / ( AO 2 ) q ] is (EO)3-{(EO)1 / (PO)2} (block addition of 3 moles of EO and a random copolymer chain of 1 mole of EO / 2 moles of PO).

[0048] [Synthesis Example 11] In the presence of an alkaline catalyst, 200 g (1 mole) of tridecyl alcohol was reacted with 440 g (10 moles) of ethylene oxide at 80-150°C to obtain the surfactant (b5) (polyoxyethylene tridecyl ether) represented by formula (2). In surfactant (b5), R in formula (2) 2 This is a tridecyl group, p=10, q=0, [(C2H4O) p / ( AO 2 ) q ] is (EO) 10 That is the case.

[0049] [Synthesis Example 12] In the presence of an alkaline catalyst, 186 g (1 mole) of lauryl alcohol was reacted with 352 g (8 moles) of ethylene oxide and 72 g (1 mole) of butylene oxide at 80-150°C to obtain the surfactant (b6) (polyoxyalkylene lauryl ether) represented by formula (2). In surfactant (b6), R in formula (2) 2 is a lauryl group, AO 2 This is an oxybutylene group, p=8, q=1, [(C2H4O) p / ( AO 2 ) q ] is (EO)8 / (BO)1 (random addition).

[0050] [Synthesis Example 13] In the presence of an alkaline catalyst, 186 g (1 mole) of lauryl alcohol was reacted with 176 g (4 moles) of ethylene oxide at 80-150°C to obtain the surfactant (b7) (polyoxyethylene lauryl ether) represented by formula (2). In surfactant (b7), R in formula (2)2 is a lauryl group, p = 4, q = 0, [(C2H4O) p / (AO 2 ) q is (EO)4.

[0051] [Synthesis Example 14] In the presence of an alkali catalyst, 440 g (10 mol) of ethylene oxide and 174 g (3 mol) of propylene oxide were added to 186 g (1 mol) of lauryl alcohol, and the mixture was reacted at 80 to 150 °C to obtain a surfactant (b8) (polyoxyalkylene lauryl ether) represented by the formula (2). In the surfactant (b8), R in the formula (2) 2 is a lauryl group, AO 2 is an oxypropylene group, p = 10, q = 3, [(C2H4O) p / (AO 2 ) q is (EO) 10 / (PO)3 (random addition).

[0052] [Synthesis Example 15] In the presence of an alkali catalyst, 176 g (4 mol) of ethylene oxide and 116 g (2 mol) of propylene oxide were added to 186 g (1 mol) of lauryl alcohol, and the mixture was reacted at 80 to 150 °C to obtain a surfactant (b9) (polyoxyalkylene lauryl ether) represented by the formula (2). In the surfactant (b9), R in the formula (2) 2 is a lauryl group, AO 2 is an oxypropylene group, p = 4, q = 2, [(C2H4O) p / (AO 2 ) q is (EO)4 / (PO)2 (random addition).

[0053] [Synthesis Example 16] In the presence of an alkaline catalyst, 158 g (1 mole) of branched decyl alcohol was reacted with 116 g (2 moles) of propylene oxide at 80-150°C. Subsequently, 528 g (12 moles) of ethylene oxide was reacted at 80-150°C to obtain the surfactant (b10) (polyoxyalkylene branched decyl ether) represented by formula (2). In surfactant (b10), R in formula (2) 2 is a branched decyl group, AO 2 This is an oxypropylene group, p=12, q=2, [(CH2H4O) p / ( AO 2 ) q ] is (PO)2-(EO) 12 (Block added)

[0054] [Synthesis Example 17] In the presence of an alkaline catalyst, 268 g (1 mole) of oleyl alcohol was reacted with 528 g (12 moles) of ethylene oxide at 80-150°C to obtain the surfactant (b11) (polyoxyalkylene oleyl ether) represented by formula (2). In surfactant (b11), R in formula (2) 2 This is an oleyl group, p=12, q=0, [(C2H4) p / ( AO 2 ) q ] is (EO) 12 That is the case.

[0055] [Synthesis Example 18 (Comparative Example)] 230 g (1.0 mol) of styrene-modified phenol is transferred to an autoclave, and 880 g (20 mol) of ethylene oxide is added under alkaline catalyst conditions of 147 kPa pressure and 150°C, thereby producing a surfactant (a'1) (in formula (1), R 1 : Methyl group, (AO 1 ) n We obtained the result of ethylene oxide addition alone (n=20).

[0056] [Synthesis Example 19 (Comparative Example)] In the presence of an alkaline catalyst, 200 g (1 mole) of tridecyl alcohol is reacted with 792 g (18 moles) of ethylene oxide at 80-150°C to produce a surfactant (b'1) (in formula (2), R 2 A tridecyl group (p=18, q=0) was obtained.

[0057] [Synthesis Example 20 (Comparative Example)] In the presence of an alkaline catalyst, 200 g (1 mole) of tridecyl alcohol is reacted with 464 g (8 moles) of propylene oxide at 80-150°C to produce a surfactant (b'2) (in formula (2), R 2 A tridecyl group (p=0, q=8) was obtained.

[0058] [Preparation and evaluation of metal cleaning agent compositions] Metal cleaning agent compositions for Examples 1-24 and Comparative Examples 1-6 were prepared by dissolving a surfactant, fatty acid, and amine in water according to the formulations (parts by mass) shown in Tables 1-3 below. In Table 4, "Styrene-phenol" refers to "Styrene-phenol" manufactured by Kawaguchi Chemical Industry Co., Ltd., and the R in formula (1) 1 : A compound with a methyl group and n=0.

[0059] The obtained metal cleaning agent compositions were evaluated for their cleaning performance, effects on non-ferrous metals, rust prevention properties, oil-water separation properties, and finish quality. The evaluation method is as follows.

[0060] (cleanability) The cleaning performance on ferrous metals was evaluated using the following method. Stainless steel (SUS) parts were immersed in a water-soluble cutting fluid for 3 hours, heat-treated at 105°C for 10 minutes, and then tested after cooling. The metal cleaning agent composition was diluted 20 times with water (dilution to a concentration of 5% by mass) to obtain a metal cleaning solution. The obtained metal cleaning solution was heated to 40°C, and the SUS parts were cleaned using a 36kHz, 600W ultrasonic cleaner, followed by air blowing and hot air drying at 80°C for 5 minutes. Next, the oil and cleaning agent residue remaining on the SUS parts were extracted using a solvent and measured by spectrophotometric method. The ratio (mass%) of oil remaining after cleaning to the oil attached before cleaning was determined, and the cleaning performance was evaluated according to the following criteria. <Standards> A: Removal rate of 95% or more B: Removal rate 70% or more but less than 95% C: Removal rate 50% or more but less than 70% D: Removal rate less than 50%

[0061] (Effects on non-ferrous metals) The effects on non-ferrous metals were evaluated using the following method. The metal cleaning agent composition was diluted 20 times with water to obtain a metal cleaning solution. The obtained metal cleaning solution was heated to 40°C, and a 70mm × 25mm × 2mm aluminum plate (A6061P) was immersed in this solution for 1 hour. After removing the aluminum plate, its surface was air-blown, and the surface condition of the aluminum plate was evaluated according to the following criteria. The pH of the metal cleaning solution at 25°C is also indicated in the table. <Standards> A: No change in color tone B: There are one or more but less than three changes in color tone. C: Color changes in 3 or more but less than 5 locations D: More than 5 places with changes in color tone

[0062] (Rust-resistant) The rust prevention properties of ferrous metals were evaluated using the following method. A metal cleaning agent composition was diluted 100 times with water to obtain a metal cleaning solution. Cast iron powder (FC20) was spread to a thickness of about 1 mm at the bottom of a bottle with an inner diameter of approximately 30 mm. Ten drops of the metal cleaning solution were added to the cast iron powder, and the mixture was left at room temperature for 2 hours, after which it was dried at 80°C for 5 minutes. The mass of the cast iron powder was measured before and after treatment, and the increase in mass was evaluated as the amount of rust produced according to the following criteria. <Standards> A: Rust generation amount less than 0.15% B: Rust generation amount 0.15% or more and less than 0.5% C: Rust generation amount 0.5% or more and less than 0.85% D: Rust amount 0.85% or more

[0063] (Oil / water separability) The oil-water separation properties were evaluated by the following method. The metal cleaning agent composition was diluted 20 times with water as a stock solution to obtain a metal cleaning solution. 50 mL of the obtained metal cleaning solution was placed in a 100 mL graduated Nessler tube, and 5 mL of oily cutting fluid was added, and the mixture was heated to 40°C. Next, the Nessler tube was vigorously shaken 100 times over 30 seconds, then allowed to stand, and the separation of oil was checked after 5 minutes. The separation rate was defined as the ratio of the volume of oil after 5 minutes of standing to the volume of oil before shaking, and the oil-water separation properties were evaluated according to the following criteria. A higher separation rate indicates better oil-water separation properties and superior effectiveness in preventing re-adhesion of oil stains, resulting in better workability. <Standards> A: Separation rate 55% or more B: Separation rate 30% or more but less than 55% C: Separation rate 5% or more but less than 30% D: Separation rate less than 5%

[0064] (Finish quality) The finish quality was evaluated using the following method. The metal cleaning agent composition was diluted 100 times with water as the undiluted solution to obtain a metal cleaning solution. The obtained metal cleaning solution was heated to 40°C, and a metal plate (SUS304) was immersed in this solution for 1 minute. After removing the metal plate, it was dried with hot air at 80°C, and the surface finish was evaluated according to the following criteria. <Standards> A: Area of ​​dry marks is less than 5% B: Area of ​​drying marks is 5% or more but less than 10% C: Area of ​​drying marks is 10% or more but less than 20% D: Area of ​​drying marks is 20% or more

[0065] [Table 1]

[0066] [Table 2]

[0067] [Table 3]

[0068] As shown in Tables 1-3, the metal cleaning agent compositions of Examples 1-24 exhibited high removal rates in cleaning tests and excellent cleaning performance for metal parts. Furthermore, their excellent oil-water separation properties allowed for the omission or reduction of the rinsing step, resulting in improved workability. They also reduced drying marks on the metal surface after cleaning, resulting in excellent finish. Moreover, they produced minimal rust, offered excellent rust prevention for ferrous metals, and suppressed color changes during cleaning of non-ferrous metals.

[0069] Furthermore, the various numerical ranges described in the specification can be any combination of their upper and lower limits, and all such combinations are described herein as preferred numerical ranges. Also, the description of a numerical range as "X~Y" means X or greater and Y or less.

[0070] Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their omissions, substitutions, and modifications are included in the scope and spirit of the invention, as well as in the claims and their equivalents.

Claims

1. The product comprises a nonionic surfactant (A) represented by the following general formula (1), and a nonionic surfactant (B) represented by the following general formula (2). 【Chemistry 1】 In formula (1), R １ represents an aliphatic hydrocarbon group, AO １ represents an oxyalkylene group with 2 to 4 carbon atoms, m represents a number from 1 to 5, n is the average number of moles added and represents a number from 1 to 18, AO １ AO when it contains two or more oxyalkylene groups １ The addition method can be random addition, block addition, or a combination of these. 【Chemistry 2】 In formula (2), R ２ represents an aliphatic hydrocarbon group having 8 to 20 carbon atoms, AO ２ represents an oxyalkylene group having 3 to 4 carbon atoms, p and q are the average number of moles added, p represents a number from 1 to 15, q represents a number from 0 to 5, and [(C ２ H ４ O) ｐ / (AO ２ ) ｑ represents a polymerized chain with a molar ratio of p:q, and the addition form in the case where the polymerized chain is a copolymerized chain may be random addition, block addition, or a combination of these. Metal cleaning agent composition.

2. The metal cleaning agent composition according to claim 1, wherein the mass ratio (A) / (B) of the content of the nonionic surfactant (A) to the content of the nonionic surfactant (B) is 0.2 to 5.

0.

3. The metal cleaning agent composition according to claim 1, further comprising a carboxylic acid amine salt.

4. The metal cleaning agent composition according to claim 3, wherein the mass ratio of the content of the carboxylic acid amine salt to the total amount of the nonionic surfactant (A) and the nonionic surfactant (B) is 0.01 to 0.

5.

5. The metal cleaning agent composition according to claim 3, wherein the total amount of the nonionic surfactant (A) and the nonionic surfactant (B) in the metal cleaning agent composition is 5 to 35% by mass, and the content of the carboxylic acid amine salt is 0.5 to 10% by mass.

6. A metal cleaning solution comprising the metal cleaning agent composition according to any one of claims 1 to 5, wherein the solid content concentration is 0.1 to 35% by mass and the pH at 25°C is 6.5 to 8.5.

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