Washing composition containing N-substituted piperazine

Abstract

A composition comprising at least the following components a) and b): a) at least one N-substituted piperazine selected from Structure 1 as described herein, and b) water.

Description

[Technical Field]

[0001] Metal cleaning is an essential task in modern industrial production, performed before and / or after metalworking processes, as well as during the lifespan of metal equipment. Industrial contaminants typically include cutting fluids, grinding residues, drawing oils, rust, corrosion inhibitors, stamping oils, fingerprints, and dust. Room temperature (or low temperature) cleaning is a recent trend, helping to reduce energy consumption and improve environmental protection. Lowering the operating (cleaning) temperature can also result in significant cost savings. [Background technology]

[0002] In room temperature (or low temperature) cleaning operations, foaming from surfactants is a significant issue to address, in addition to the cleaning performance of the cleaning composition. One approach to "reducing foaming" is to use low-foaming nonionic surfactants, which the industry employs in metal cleaning agents. Foaming of nonionic surfactants is suppressed when the temperature is higher than the surfactant's cloud point. However, low-foaming surfactants are typically designed to have a low cloud point (e.g., below 40°C). To achieve extremely low foaming at room temperature, the cloud point is usually below 20°C. This approach has several problems, including the following: a) Compatibility: Low-foaming surfactants are generally hydrophobic and do not solubilize sufficiently in alkaline formulations, resulting in a cloudy appearance or phase separation of the cleaning composition, which further affects the cleaning effect. b) Foaming: Low-foaming surfactants may still produce foam under conditions involving strong mechanical force, such as when using sprayers, shakers, or mixers. Furthermore, surfactants may lose their low-foaming properties when solubilized by hydrotropes. c) Emulsification: Strong oil binding is undesirable in metal cleaning because it can shorten the bath's usage time. Surfactants typically have good emulsifying power with oil and can bind closely to it, thereby being removed from the cleaning bath along with the oil.

[0003] There is a need for a metal cleaning composition that possesses excellent oil removal performance and low foaming properties without sacrificing solubility in alkaline formulations, and that can be used at low / ambient temperatures.

[0004] U.S. Patent Application Publication No. 2022 / 0254624 discloses a method for cleaning a semiconductor substrate. The cleaning solution is alkaline and contains: a) Component A, which is at least one selected from the group consisting of primary amines, secondary amines, and tertiary amines (excluding the compound represented by the specific formula (a) described in the above specification); and b) Component B, which is a compound represented by the specific formula (a). The mass ratio of Component B to Component A is 0.01 or less. The temperature of the cleaning solution supplied to the semiconductor substrate is 30°C or higher. See abstract. Component A may be monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), 2-(methylamino)-2-methyl-1-propanol (N-MAMP), diethanolamine (DEA), diethylene glycolamine (DEGA), tris(hydroxymethyl)aminomethane, ethylenediamine (EDA), 1,3-propanediamine (PDA), diethylenetriamine (DETA), triethylenetetramine (TETA), N-(2-amino-ethyl)piperazine (AEP), 1,4-bis(2-hydroxyethyl)piperazine (BHEP), 1,4-bis(3-aminopropyl)-piperazine (BAPP), or bis(aminopropyl)ethylenediamine (BAPEDA). See paragraph

[0059] .

[0005] U.S. Patent No. 9,045,717 discloses a composition comprising a cyclic polyamine, a polyphenol-based reducing agent having 2 to 5 hydroxyl groups, a quaternary ammonium hydroxide, ascorbic acid, and water, which is useful for removing material from the surface of microelectronic devices. See Claim 1. The cyclic polyamines are N-ethylpiperazine, N-isobutylpiperazine, N-aminomethylpiperazine, N-aminopropylpiperazine, N-hydroxypropylpiperazine, 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,4-diisopropylpiperazine, 1,4-dibutylpiperazine, 1-aminomethyl-4-methylpiperazine, 1-hydroxymethyl-4-methylpiperazine, 1-aminoethyl-4-ethylpiperazine, 1-H Selected from the group consisting of droxyethyl-4-ethylpiperazine, 1,4-(bis-aminoethyl)piperazine, 1,4-(bis-hydroxyethyl)-piperazine, 1,4-(bis-aminopropyl)piperazine, 1,4-(bis-hydroxypropyl)piperazine, 1-amino-ethyl-4-hydroxyethylpiperazine, 1-aminopropyl-4-hydroxypropylpiperazine, N-aminoisobutyl-morpholine, and combinations thereof. See Claim 1. See also Column 7, Line 64 to Column 9, Line 5.

[0006] International Publication No. 2013 / 138278 discloses a cleaning composition and process for cleaning residues and contaminants after chemical mechanical polishing (CMP) from microelectronic devices having said residues and contaminants. See abstract. The cleaning composition comprises at least one solvent, at least one corrosion inhibitor, at least one polyamine species, and at least one quaternary base, wherein the at least one polyamine species is at least one of aliphatic polyamines or cyclic polyamines (see claim 1). Examples of cyclic polyamines include N-methylpiperazine, N-ethylpiperazine, N-isobutylpiperazine, N-aminomethylpiperazine, N-aminoethylpiperazine, N-aminopropylpiperazine, N-hydroxymethylpiperazine, N-hydroxyethylpiperazine, N-hydroxypropylpiperazine, 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,4-diisopropylpiperazine, 1,4-dibutylpiperazine, and 1-aminomethylpiperazine. Examples include nomethyl-4-methylpiperazine, 1-hydroxymethyl-4-methylpiperazine, 1-aminoethyl-4-ethylpiperazine, 1-hydroxyethyl-4-ethylpiperazine, 1,4-(bis-aminoethyl)-piperazine, 1,4-(bis-hydroxyethyl)piperazine, 1,4-(bis-aminopropyl)piperazine, 1,4-(bis-hydroxypropyl)piperazine, 1-aminoethyl-4-hydroxyethylpiperazine, and 1-aminopropyl-4-hydroxypropylpiperazine. Other cyclic polyamines include imidazolines and imidazole derivatives. See paragraph

[0033] .

[0007] Chinese Published Patent No. 102639686(A) (machine translation) discloses a cleaning solution composition for flat panel display devices comprising (a) 0.05 to 5% by weight of an amine compound, (b) 0.01 to 10% by weight of an additive comprising one or more components selected from the group consisting of azole compounds, alkanolamine salts and reducing agents, and (c) the remainder being water (see abstract). The amine compounds are N-(2-hydroxyethyl)piperazine, N-(2-hydroxypropyl)piperazine, N-(2-hydroxylbutyl)piperazine, 1-(2-hydroxyethyl)-4-N-methylpiperazine, 1-(2-hydroxypropyl)-4-N-methylpiperazine, 1-(2-hydroxylbutyl)-4-N-methylpiperazine, 1-(2-hydroxyethyl)-4-ethylpiperazine, 1-(2-hydroxyethyl)-4-propyl group piperazine, 1-(2-hydroxyethyl)-4-butylpiperazine, 1-(2-hydroxypropyl)-4-N-methylpiperazine, 1-(2-hydroxypropyl)-4-ethylpiperazine The 1-(N-methylpiperazine) group can be selected from those composed of 1-(2-hydroxypropyl)-4-propylpiperazine, 1-(2-hydroxypropyl)-4-butylpiperazine, 1-(2-hydroxylbutyl)-4-N-methylpiperazine, 1-(2-hydroxylbutyl)-4-ethylpiperazine, 1-(2-hydroxylbutyl)-4-propylpiperazine, 1-(2-hydroxylbutyl)-4-butylpiperazine, N-(2-hydroxyethyl)morpholine, N-(2-hydroxypropyl)morpholine, N-aminocarbonylpropylmorpholine, hydroxyethylpiperazine, hydroxypropylpiperazine, and ethanol. See claims 1 and 2.

[0008] U.S. Patent Application Publication No. 2022 / 0177814 discloses a cleaning solution for semiconductor substrates subjected to CMP, the cleaning solution comprising an amine compound selected from the group consisting of primary amines, secondary amines, tertiary amines, and salts thereof, a chelating agent, and water. See abstract. The amine compound content is 25.5% by mass or more and less than 90% by mass based on the total mass of the cleaning solution, and the water content is 10% to 60% by mass based on the total mass of the cleaning solution. See abstract. The amine compounds may be monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), 2-(methylamino)-2-methyl-1-propanol (N-MAMP), diethanolamine (DEA), diethylene glycolamine (DEGA), tris(hydroxymethyl)aminomethane (Tris), ethylenediamine (EDA), 1,3-propanediamine (PDA), diethylenetriamine (DETA), triethylenetetramine (TETA), N-(2-amino-ethyl)piperazine (AEP), 1,4-bis(2-hydroxyethyl)piperazine (BHEP), 1,4-bis(2-aminomethyl)-piperazine (BAEP), 1,4-bis(3-aminopropyl)piperazine (BAPP), bis(aminopropyl)ethylenediamine (BAPEDA), ethylamine, triethylamine, or propylamine. See paragraph

[0065] . See also paragraph

[0046] .

[0009] Korean Published Patent No. 20130007402(A) (machine translation) discloses a cleaning solution composition comprising, based on the total weight of the composition, 0.05 to 10% by weight of a cyclic amine compound, 0.1 to 20% by weight of a water-soluble glycol ether compound, and 79 to 99.5% by weight of water. See the abstract and claim 1. Examples of cyclic amine compounds represented by formula 1 as described in the above specification include N-methylmorpholine, N-ethylmorpholine, N-formylmorpholine, N-(2-hydroxylethyl)morpholine, N-(3-hydroxylpropyl)morpholine, N-(2-hydroxylethyl)-N'-methylpiperazine, N-(2-hydroxylethyl)-N'-ethylpiperazine, and N,N'-bis(2-hydroxyethyl)piperazine. These compounds can be used alone or in combination of two or more. See the section "Modes for Carrying Out the Invention".

[0010] Japanese Patent Publication No. 2003292993(A) (machine translation) discloses a detergent comprising an ethyleneamine compound and a cyclic amine such as a piperazine compound and / or a morpholine compound. Examples of piperazine compounds include piperazine, N-methylpiperazine, N,N'-dimethylpiperazine, hydroxyethylpiperazine, N-methyl-N'-hydroxyethylpiperazine, aminoethylpiperazine, N,N',N'-trimethylaminoethylpiperazine, bis-(hydroxyethyl)piperazine, hydroxypropylpiperazine, bis(hydroxypropyl)piperazine, N-methyl-N'-hydroxypropylpiperazine, aminopropylpiperazine, bis-(aminoethyl)piperazine, and bis-(aminopropyl)piperazine. Examples of morpholine compounds include morpholine, N-methylmorpholine, hydroxyethylmorpholine, aminoethylmorpholine, and N,N-dimethylaminoethylmorpholine. Examples of ethyleneamine compounds include ethylenediamine and diethylenetriamine. (Abstract and paragraph)

[0011] Please refer to the following.

[0011] Further compositions are disclosed in International Publication No. 2011 / 014027 (English abstract), Japanese Patent Publication No. 2016086094(A) (machine translation), Japanese Patent Publication No. 2015165561(A) (machine translation), and Japanese Patent Publication No. 2015165562(A) (machine translation).

[0012] However, as mentioned above, there is still a need for a metal cleaning composition that possesses excellent oil removal performance and low foaming properties without sacrificing solubility in alkaline formulations, and that can be used at low / ambient temperatures. This need has been met as described below. [Overview of the project]

[0013] At least the following components a) and b): a) At least one N-substituted piperazine selected from the following structures 1):

[0014] [ka] In the formula, R1 is a C1-C6 alkoxyl group, and R2 is H or A plurality of N-substituted piperazines, wherein R3 is an alkyl group and R3 is an H or C1-C6 alkoxyl group, b) A composition containing water. [Brief explanation of the drawing]

[0015] [Figure 1] This is a plot of the boiling point of 1,4-bis(2-hydroxyethyl)piperazine as a function of mmHg. The equation of the profile is y = 26.385ln(x) + 118.53 (R² = 0.9616). [Figure 2] This is a bar graph showing the percentage of oil removal for the described compositions. [Figure 3] This is a bar graph showing the percentage of oil removal for the described compositions. [Figure 4]A bar graph showing the percentage of oil removal for the described composition. [Figure 5] A bar graph showing the time for each of the described compositions to separate from oil and fill a volume of 5 mL or 10 mL.

Mode for Carrying Out the Invention

[0016] Compositions have been discovered that provide good cleaning performance, good alkali resistance, and low foaming properties. These compositions are suitable for cleaning at low or ambient temperatures and exhibit excellent oil removal performance and low foaming properties without sacrificing solubility in alkaline formulations. These properties are desirable for metal cleaning processes, particularly for cleaning at low / ambient temperatures.

[0017] As described above, at least the following components a) and component b): a) At least one N-substituted piperazine selected from the following structure 1):

[0018]

Chemical formula

[0019] The above composition may include a combination of two or more embodiments as described herein. Component a may include a combination of two or more embodiments as described herein. Component b may include a combination of two or more embodiments as described herein. The related processes may each include a combination of two or more embodiments as described herein. As used herein, with respect to structure 1) of component a, R1 = R1, R2 = R2, and R3 = R3.

[0020] In one embodiment, or in a combination of two or more embodiments described herein, the composition comprises, as component c, at least one alkali salt, and further a metal carbonate and / or a metal bicarbonate, and further a metal carbonate.

[0021] In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component c to component a is ≥2.0, or ≥2.5, or ≥3.0, or ≥3.5, or ≥4.0. In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component c to component a is ≤10, or ≤9.5, or ≤9.0, or ≤8.5, or ≤8.0, or ≤7.5, or ≤7.0, or ≤6.5, or ≤6.0.

[0022] In one embodiment, or in a combination of two or more embodiments, each of which is described herein, the composition comprises a total of component a and component b in an amount of ≥88% by weight, ≥89% by weight, or ≥90% by weight, or ≥91% by weight, or ≥92% by weight, or ≥93% by weight, or ≥94% by weight, or ≥95% by weight, or ≥96% by weight, or ≥97% by weight, or ≥98% by weight, based on the weight of the composition. In one embodiment, or in a combination of two or more embodiments, each of which is described herein, the composition comprises a total of component a and component b in an amount of ≤100% by weight, or ≤99% by weight, based on the weight of the composition.

[0023] In one embodiment, or in a combination of two or more embodiments, each described herein, R1 = R3 for structure 1 of component a.

[0024] In one embodiment, or in a combination of two or more embodiments, each described herein, R2 = H for structure 1 of component a.

[0025] Each embodiment, or combination of two or more embodiments, described herein, Regarding structure 1 of component a, R1 is a C2-C6 alkoxyl, further C2-C5 alkoxyl, further C2-C4 alkoxyl, further C2-C3 alkoxyl, and further C2 alkoxyl.

[0026] In one embodiment, or in a combination of two or more embodiments, each of which is described herein, R3 is a C2-C6 alkoxyl, a C2-C5 alkoxyl, a C2-C4 alkoxyl, a C2-C3 alkoxyl, or a C2 alkoxyl.

[0027] In one embodiment, or in a combination of two or more embodiments, each described herein, R3 is H in structure 1 of component a.

[0028] Each embodiment, or combination of two or more embodiments, described herein, Component a has the following structures 1a) to 1c): 1a)

[0029] [ka] (In the formula, n is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2, and m is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2, and further between n = m) 1b)

[0030] [ka] (In the formula, n is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2; m is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2; p is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 1 and 3, further between 1 and 2, and further between n = m), and It is at least one structure selected from the group consisting of a mixture of 1c)1a) and structure 1b).

[0031] In one embodiment, or in a combination of two or more embodiments, each of which is described herein, component c is a metal carbonate, and moreover, sodium carbonate.

[0032] In one embodiment, or a combination of two or more embodiments, each of which is described herein, component a is present in an amount of ≥0.01% by weight, or 0.02% by weight, or ≥0.05% by weight, or 0.10% by weight, or ≥0.20% by weight, or ≥0.30% by weight, or ≥0.40% by weight, or ≥0.50% by weight, or ≥0.70% by weight, or ≥1.0% by weight, based on the weight of the composition. In one embodiment, or a combination of two or more embodiments, each of which is described herein, component a is present in an amount of ≤20% by weight, or ≤15% by weight, or ≤10% by weight, or ≤8.0% by weight, or ≤6.0% by weight, or ≤5.5% by weight, or ≤5.0% by weight, or ≤4.5% by weight, or ≤4.0% by weight, or ≤3.5% by weight, or ≤3.0% by weight, based on the weight of the composition.

[0033] In one embodiment, or in a combination of two or more embodiments, each of which is described herein, component b is present in an amount of ≥70.0% by weight, or ≥72.0% by weight, or ≥75.0% by weight, or ≥78.0% by weight, or ≥80.0% by weight, or ≥82.0% by weight, or ≥84.0% by weight, or ≥86.0% by weight, or ≥88.0% by weight, or ≥90.0% by weight, or ≥92.0% by weight, or ≥95.0% by weight, based on the weight of the composition. In one embodiment, or in a combination of two or more embodiments, each of which is described herein, component b is present in an amount of ≤100.0% by weight, or ≤99.5% by weight, or ≤99.0% by weight, or ≤98.5% by weight, or ≤98.0% by weight, based on the weight of the composition.

[0034] In one embodiment, or in a combination of two or more embodiments, each of which is described herein, the sum of components a, b, and c is present in an amount of ≥95.0% by weight, or 95.5% by weight, or ≥96.0% by weight, or 96.5% by weight, or ≥97.0% by weight, or ≥97.5% by weight, or ≥98.0% by weight, or ≥98.5% by weight, or ≥99.0% by weight, based on the weight of the composition. In one embodiment, or in a combination of two or more embodiments, each of which is described herein, the sum of components a, b, and c is present in an amount of ≤100% by weight, or ≤99.8% by weight, or ≤99.6% by weight, based on the weight of the composition.

[0035] In one embodiment, or in a combination of two or more embodiments, each of which is described herein, the composition further comprises a metal chelate as component d.

[0036] In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component d to component a is ≥0.80, or ≥0.85, or ≥0.90, or ≥0.95, or ≥1.00. In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component d to component a is ≤1.20, or ≤1.15, or ≤1.10, or ≤1.05, or ≤1.02.

[0037] In one embodiment, or in a combination of two or more embodiments, each of which is described herein, the composition has an "oil removal percentage" of ≥60%, ≥62%, ≥65%, ≥67%, ≥70%, ≥72%, ≥74%, ≥76%, ≥78%, or ≥80%, determined by the formula [(W2-W3) / (W2-W1)] × 100 (wherein W1 = weight of a stainless steel specimen, W2 = weight of an oil-stained specimen, and W3 = weight of a dried specimen after being subjected to cleaning evaluation with the composition) (see Experiments section).

[0038] In one embodiment, or a combination of two or more embodiments described herein, the composition is shaken for 60 seconds using a high-throughput robot to produce a bubble height of ≤5 mm, or ≤4 mm, or ≤3 mm, or ≤2 mm, or ≤1 mm, or 0 mm (see Experiments section).

[0039] Furthermore, a process is provided for forming a composition of one embodiment, or a combination of two or more embodiments, each of which is described herein, the process comprising mixing at least component a and component b.

[0040] Furthermore, a process for cleaning a metal surface is provided, which includes applying a composition of any one embodiment, or a combination of two or more embodiments, each described herein, to the metal surface.

[0041] In one embodiment, or in a combination of two or more embodiments, each of which is described herein, the temperature of the composition is ≥18°C, or ≥19°C, or ≥20°C, or ≥22°C, and / or ≤30°C, or ≤29°C, or ≤28°C, or ≤27°C, or ≤26°C, or ≤25°C, or ≤24°C when applied to a metal surface.

[0042] Each embodiment, or combination of two or more embodiments, described herein, The process is an industrial cleaning process.

[0043] component a - structure 1 Component a is described herein as Structure 1. The synthesis of such N-substituted piperazines is well known in the art, and various piperazines are commercially available. For example, N-substituted piperazines can be produced by reacting the oxide of the interest with piperazine. As an example, 1,4-bis(2-hydroxyethyl)piperazine can be synthesized by reacting EO (ethylene oxide) with piperazine in a target ratio of 2:1. The resulting piperazine can be recovered using conventional techniques. Note that the term N-substituted piperazine as used herein refers to N-substituted and N,N'-substituted piperazines on the piperazine ring.

[0044] Component a may be in the form of a liquid composition added to an aqueous composition. Piperazine of Structure 1 itself may be in liquid form at room temperature (22°C), and therefore the "stock" composition may be in the form of undiluted piperazine (100% by weight). The stock composition may also be prepared with piperazine in one or more suitable solvents, for example, in an amount ranging from about 30% (by weight) to about 99% (by weight) of piperazine. The solvent may be water. Piperazine may be in the form of a solid composition, such as a powder or granules, which can be added to the aqueous composition.

[0045] Ingredients: c-alkali salts Alkali salts are products of a strong base and a weak acid, and can form basic solutions when dissolved in water. Examples of alkali salts include, but are not limited to, sodium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium chloride, and sodium sulfide. Alkali salts can be selected from metal bicarbonates, metal carbonates, metal chlorides, metal chlorates, metal nitrates, metal phosphates, metal sulfates, metal sulfides, or mixtures thereof. A composition may contain one or more alkali salts.

[0046] Component d-chelate Chelates are well known in the art. Chelates typically consist of at least two ligands bonded to a central metal atom. Examples of chelates include, but are not limited to, aminocarboxylate chelators such as salts and derivatives of ethylenediaminetetraacetic acid and salts of glutamic acid-N,N-diacetic acid, phosphate chelators, and phosphonate chelators such as ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate. These chelates may exist in either their acid form or as salts. Examples of biodegradable chelators include, but are not limited to, ethylenediamine N,N'-disuccinic acid, or its alkali metal or alkaline earth metal, ammonium or substituted ammonium salt, or mixtures thereof, and L-glutamic acid N,N-diacetic acid (GLDA), which is marketed by Akzo Nobel under the trademark name DISSOLVINE 47S.

[0047] Suitable aminocarboxylates or acids include ethylenediaminetetraacetate, ethylenetriaminepentaacetate, diethylenetriaminepentaacetate (DTPA), N-hydroxyethylethylene-diaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetramine-hexaacetate, ethanol diglycine, and methylglycine diacetic acid (MGDA), both of which are in acid form or alkali metal, ammonium, and substituted ammonium salt form. Particularly suitable aminocarboxylates or acids include, but are not limited to, salts of ethylenediaminetetraacetic acid (EDTA), EDTA, for example, propylenediaminetetraacetic acid (PDTA), methylglycine diacetic acid (MGDA), and diethylenetriaminepentaacetate (DTPA) from BASF, which are commercially available from BASF under the trademark name TRILON FS. Further carboxylate chelating agents include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid, or mixtures thereof.

[0048] In one embodiment, or in a combination of two or more embodiments, each of which is described herein, component d is ethylenediaminetetraacetic acid such as EDTA-4NaH2O or a salt thereof.

[0049] Other additives The compositions described in the present invention may optionally contain one or more additional additives. Examples of additives include, but are not limited to, solvents, surfactants, ethylene oxide / propylene oxide, butylene oxide / propylene oxide, ethylene oxide / butylene oxide blocks or random copolymers, waxes, silicone materials, and foam control compounds such as agents produced by alkoxylation of alcohols, alkyl polyglucosides, ketal foam control agents, and cellulose derivative foam control agents. Additives may be present in amounts of ≥0.01% by weight, or ≥0.02% by weight, or ≥0.05% by weight, or ≥0.10% by weight, or ≥0.20% by weight, or ≥0.40% by weight, or ≥0.60% by weight, or ≥0.80% by weight, and / or ≤20% by weight, or ≤10% by weight, or ≤5.0% by weight, or ≤3.0% by weight, or ≤2.0% by weight, or ≤1.0% by weight, based on the weight of the composition.

[0050] definition Unless otherwise stated, implied by the context, or customary in the art, parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0051] As used herein, the term “composition” includes a composition, as well as mixtures of materials including reaction products and decomposition products formed from the materials of the composition. Any reaction products or decomposition products are typically present in trace or residual amounts.

[0052] As used herein, the term “polymer” refers to a polymer compound prepared by polymerizing multiple monomers, whether of the same or different types. Thus, the general term polymer includes the terms homopolymer (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure) and interpolymer, as defined below. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. Typically, polymers are stabilized with one or more stabilizers in very small amounts ("ppm (parts per million)") of them.

[0053] As used herein, the term “interpolymer” refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the term interpolymer includes the term copolymer (used to refer to a polymer prepared from two different types of monomers) and polymers prepared from three or more different types of monomers.

[0054] As used herein, the term “water” refers to H2O or an H2O sample. Such a water (H2O) sample is substantially pure water and therefore may or may not contain one or more impurities, such as dissolved inorganic ions. Typically, impurities are present in amounts of ≤5000 ppm, preferably ≤2000 ppm, preferably ≤1000 ppm, preferably ≤500 ppm, more preferably ≤300 ppm, and more preferably ≤100 ppm, based on the weight of the water sample.

[0055] In relation to the process of cleaning a metal surface with the compositions described herein, the phrase "apply to a metal surface" means bringing the metal surface into contact with the composition. This contact may be achieved by wetting the metal surface with the composition using a spray, brush, or roller, or by immersing the metal in the composition, or by any other means well known in the art.

[0056] As used herein, the term “industrial cleaning process” refers to a process used to clean equipment surfaces and other surfaces used in industrial facilities, such as floors, walls, ceilings, the exterior and interior surfaces of equipment, and other surfaces.

[0057] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, processes, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term “comprising” may, unless otherwise stated, include any additional additives, adjuvants, or compounds, whether or not they are polymers. In contrast, the term “consisting essentially of” excludes any other components, processes, or procedures from any subsequent enumeration, except those not essential to operability. The term “consisting of” excludes any components, processes, or procedures not specifically specified or enumerated.

[0058] List of some characteristics of the composition and method A) At least the following components a) and b): a) At least one N-substituted piperazine selected from the following structures 1):

[0059] [ka] In the formula, R1 is a C1-C6 alkoxyl group, R2 is H or an alkyl group, and R3 is H or a C1-C6 alkoxyl group, comprising at least one N-substituted piperazine. b) A composition containing water. B) The composition is the composition according to A) above, further comprising at least one alkali salt as component c. C] The composition according to B) above, wherein component c is a metal carbonate and / or a metal bicarbonate, and furthermore a metal carbonate. D] The composition according to B] or C] above, wherein the weight ratio of component c to component a is ≥2.0, or ≥2.5, or ≥3.0, or ≥3.5, or ≥4.0. E) The composition according to any one of B) to D) above, wherein the weight ratio of component c to component a is ≤10, or ≤9.5, or ≤9.0, or ≤8.5, or ≤8.0, or ≤7.5, or ≤7.0, or ≤6.5, or ≤6.0. F) The composition according to any one of A] to E] above, wherein the composition comprises the sum of component a and component b in an amount of ≥88% by weight, or 89% by weight, or ≥90% by weight, or ≥91% by weight, or ≥92% by weight, or ≥93% by weight, or ≥94% by weight, or ≥95% by weight, or ≥96% by weight, or ≥97% by weight, or ≥98% by weight. G) The composition according to any one of A) to F) above, wherein the composition contains the sum of components a and b in an amount of ≤100% by weight or ≤99% by weight, based on the weight of the composition. H] The composition according to any one of A] to G] above, wherein the weight ratio of component b to component a is ≥ 5.0, or ≥ 6.0, or ≥ 7.0, or ≥ 8.0, or ≥ 9.0, or ≥ 10, or ≥ 12, or ≥ 14, or ≥ 16, or ≥ 18. I) The composition according to any one of A] to H] above, wherein the weight ratio of component b to component a is ≤300, or ≤250, or ≤200, or ≤150, or ≤100, or ≤90, or ≤80, or ≤70, or ≤60, or ≤50, or ≤40, or ≤35, or ≤30, or ≤25. J) A composition according to any one of A) to I) above, wherein R1 = R3 for structure 1 of component a. K] A composition according to any one of A] to J] above, wherein R2 = H for structure 1 of component a. L] The composition according to any one of A] to J] above, wherein the structure 1 of component a is R2 = alkyl, and further C1-C5 alkyl, further C1-C4 alkyl, further C1-C3 alkyl, further C1-C2 alkyl, and further C1 alkyl. The composition according to any one of A] to L] above, wherein, in the structure 1 of component a, R1 is a C1-C5 alkoxyl, further a C1-C4 alkoxyl, further a C1-C3 alkoxyl, and further a C1-C2 alkoxy. The composition according to any one of A] to L] above, wherein, in the structure 1 of component a, R1 is a C2-C6 alkoxyl, further a C2-C5 alkoxyl, further a C2-C4 alkoxyl, further a C2-C3 alkoxyl, and further a C2 alkoxyl. The composition according to any one of A] to N] above, wherein, in the structure 1 of component a, R3 is a C1-C5 alkoxyl, further a C1-C4 alkoxyl, further a C1-C3 alkoxyl, and further a C1-C2 alkoxy. P] The composition according to any one of A] to N] above, wherein, for structure 1 of component a, R3 is a C2-C6 alkoxyl, further a C2-C5 alkoxyl, further a C2-C4 alkoxyl, further a C2-C3 alkoxyl, and further a C2 alkoxyl. Q] The composition according to any one of A] to N] above, wherein R3 is H in structure 1 of component a. Component a of R is the following structure 1a)~1c): 1a)

[0060] [ka] (In the formula, n is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2, and m is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2, and further between n = m) 1b)

[0061] [ka] (In the formula, n is 1 to 6, and furthermore, 1 to 5, Furthermore, the integers are 1-4, 2-4, 2-3, and 2, and m is an integer between 1-6, 1-5, 1-4, 2-4, 2-3, and 2, and p is an integer between 1-6, 1-5, 1-4, 1-3, 1-2, and 1, and furthermore, n=m), and 1c) The composition according to any one of A] to Q] above, wherein the composition is at least one structure selected from the group consisting of a mixture of structure 1a) and structure 1b). S) The composition according to R) above, wherein component a is at least one structure selected from the structures 1a) shown above, and further n=m, further n=m=2 or 3, and further n=m=2. The composition according to R) above, wherein component a is at least one structure selected from the structures 1b) shown above, and further n=m, further n=m=2 or 3, and further n=m=2. The composition according to R) above, wherein component a is at least one structure selected from the structures 1c) shown above. V] Component a is the following structure shown below 2a)~2c): 2a)

[0062] [ka] (In the formula, n is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2.) 2b)

[0063] [ka] (In the formula, n is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 2 and 4, further between 2 and 3, and further between 2; and p is an integer between 1 and 6, further between 1 and 5, further between 1 and 4, further between 1 and 3, further between 1 and 2, and further between 1.) 2c) The composition according to any one of A] to Q] above, wherein the composition is at least one structure selected from the group consisting of a mixture of structure 2a) and structure 2b). The composition according to V) above, wherein component a is at least one structure selected from the structures 2a) shown above, and furthermore, n=2. X] The composition according to V) above, wherein component a is at least one structure selected from the structures shown in 2b) above, and furthermore n=2. The composition according to V) above, wherein component a is at least one structure selected from the structures shown in 2c) above. Z) The composition according to any one of A] to Y] above, wherein with respect to component a, structure 1) has a molecular weight of ≥80, or ≥90, or ≥100, or ≥110, or ≥120, or ≥125, or (r) ≥127, or ≥130 g / mol. A2) With respect to component a, structure 1) has a molecular weight of ≤500, or ≤450, or ≤400, or ≤350, or ≤300, or ≤250, or ≤200, or ≤180 g / mol, as described in any one of A] to Z] above. B2] With respect to component a, structure 1) has a molecular weight of ≤220, or ≤210, or ≤200, or ≤195, or ≤190, or ≤185, or ≤180, the composition according to any one of A] to A2] above. C2) With respect to component a, structure 1) has a boiling point (760 mmHg) of ≥200°C, or ≥205°C, or ≥210°C, or ≥215°C, or ≥220°C, or ≥230°C, or ≥240°C, or ≥245°C, or ≥250°C, or ≥255°C, or ≥260°C, or ≥265°C, or ≥270°C, as described in any one of A] to B2] above. D2] With respect to component a, structure 1) is the composition according to any one of A] to C2] above, having a boiling point (760 mmHg) of ≤400°C, or ≤380°C, or ≤360°C, or ≤340°C, or ≤330°C, or ≤320°C, or ≤310°C. E2] The composition according to any one of B] to D2] above, wherein component c is a metal carbonate, and moreover, sodium carbonate. F2] The composition according to any one of B] to E2] above, wherein the metal of component c has an atomic mass of ≥8, or ≥10, or ≥12, or ≥15, or ≥18, or ≥20, or ≥22. G2] The composition according to any one of B] to F2] above, wherein the metal of component c has an atomic mass of ≤60, or ≤58, or ≤55, or ≤52, or ≤50, or ≤48, or ≤46, or ≤44, or ≤42 g / mol. H2] The composition according to any one of B] to G2] above, wherein the metal carbonate or metal bicarbonate of component c has a molecular weight of ≥60, or ≥65, or ≥70, or ≥75, or ≥80, or ≥82, or ≥84, or ≥86, or ≥88, or ≥90, or ≥92, or ≥94, or ≥96, or ≥98, or ≥100 g / mol. I2] The composition according to any one of B] to H2] above, wherein the metal carbonate or metal bicarbonate of component c has a molecular weight of ≤250, or ≤200, or ≤150, or ≤140, or ≤130, or ≤120, or ≤115, or ≤110 g / mol. J2] The composition according to any one of B] to I2] above, wherein component c is present in an amount of ≥0.01% by weight, or ≥0.02% by weight, or ≥0.05% by weight, or ≥0.10% by weight, or ≥0.20% by weight, or ≥0.30% by weight, or ≥0.40% by weight, or ≥0.50% by weight, or ≥1.0% by weight, or ≥1.5% by weight, or ≥2.0% by weight. K2] The composition according to any one of B] to J2] above, wherein component c is present in an amount of ≤15% by weight, ≤12% by weight, or ≤10% by weight, or ≤9.0% by weight, or ≤8.0% by weight, or ≤7.0% by weight, or ≤6.0% by weight, or ≤5.0% by weight, based on the weight of the composition. L2] The composition according to any one of A] to K2] above, wherein component a is present in an amount of ≥0.01% by weight, or ≥0.02% by weight, or ≥0.05% by weight, or ≥0.10% by weight, or ≥0.20% by weight, or ≥0.30% by weight, or ≥0.40% by weight, or ≥0.50% by weight, or ≥0.70% by weight, or ≥1.0% by weight. M2] The composition according to any one of A] to L2] above, wherein component a is present in an amount of ≤20% by weight, or ≤15% by weight, or ≤10% by weight, or ≤8.0% by weight, or ≤6.0% by weight, or ≤5.5% by weight, or ≤5.0% by weight, or ≤4.5% by weight, or ≤4.0% by weight, or ≤3.5% by weight, or ≤3.0% by weight. N2] The composition according to any one of A] to M2] above, wherein component b is present in an amount of ≥70.0% by weight, or ≥72.0% by weight, or ≥75.0% by weight, or ≥78.0% by weight, or ≥80.0% by weight, or ≥82.0% by weight, or ≥84.0% by weight, or ≥86.0% by weight, or ≥88.0% by weight, or ≥90.0% by weight, or ≥92.0% by weight, or ≥95.0% by weight. O2] The composition according to any one of A] to N2] above, wherein component b is present in an amount of ≤100.0% by weight, or ≤99.5% by weight, or ≤99.0% by weight, or ≤98.5% by weight, or ≤98.0% by weight, based on the weight of the composition. P2] The composition according to any one of B] to O2] above, wherein the sum of components a, b, and c is present in an amount of ≥95.0% by weight, or 95.5% by weight, or ≥96.0% by weight, or 96.5% by weight, or ≥97.0% by weight, or ≥97.5% by weight, or ≥98.0% by weight, or ≥98.5% by weight, or ≥99.0% by weight. Q2] The composition according to any one of B] to P2] above, wherein the sum of components a and c is present in an amount of ≤100% by weight, or ≤99.8% by weight, or ≤99.6% by weight, based on the weight of the composition. R2] The composition further comprises a metal chelate as component d, according to any one of A] to Q2] above. S2] The composition of R2] above, wherein component d comprises an aminocarboxylate chelate, a phosphonate chelate, or a phosphate chelate. The composition according to R2] or K2] above, wherein component d comprises a metal salt of ethylenediaminetetraacetic acid, and further comprises ETDA-4Na·4H2O. The composition according to any one of the above R2] to T2], wherein component d is present in an amount of ≥0.01% by weight, ≥0.02% by weight, or ≥0.05% by weight, or ≥≤0.1% by weight, or ≥0.2% by weight, or ≥0.3% by weight, or ≥0.4% by weight, or ≥0.5% by weight, based on the weight of the composition. V2] The composition according to any one of R2] to U2] above, wherein component d is present in an amount of ≤10% by weight, or ≤8.0% by weight, or ≤6.0% by weight, or ≤5.0% by weight, or ≤4.0% by weight, or ≤3.0% by weight, or ≤2.0% by weight, or ≤1.5% by weight, or ≤1.0% by weight, or ≤0.8% by weight, or ≤0.6% by weight, based on the weight of the composition. The composition according to any one of the above R2] to V2], wherein the weight ratio of component d to component a is ≥0.80, or ≥0.85, or ≥0.90, or ≥0.95, or ≥1.00. X2] The composition according to any one of R2] to W2] above, wherein the weight ratio of component d to component a is ≤1.20, or ≤1.15, or ≤1.10, or ≤1.05, or ≤1.02. Y2] The composition according to any one of R2] to X2] above, wherein the sum of components a, b, c, and d is present in an amount of ≥98.0% by weight, or ≥98.5% by weight, or ≥99.0% by weight, or ≥99.5% by weight, based on the weight of the composition. Z2] The composition according to any one of R2] to Y2] above, wherein the sum of components a, b, c, and d is present in an amount of ≤100% by weight, or ≤99.9% by weight, or ≤99.8% by weight, based on the weight of the composition. A3] The composition according to any one of A] to Z2] above, wherein the composition contains, based on the weight of the composition, ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of a surfactant, and furthermore, the composition does not contain a surfactant. B3] The composition comprises, based on the weight of the composition, ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of glycol ether, and furthermore, the composition does not contain glycol ether, as described in any one of A] to A3] above. C3] The composition contains ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm or less, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of ethylamine based on the weight of the composition, and furthermore, the composition does not contain ethylamine, as described in any one of A] to B3] above. D3] The composition comprises, based on the weight of the composition, ≤1.0 ppm, or ≤0.50 ppm, or ≤0.20 ppm, or ≤0.10 ppm, or ≤0.05 ppm, or ≤0.02 ppm, or ≤0.01 ppm of alkylamine, and furthermore, the composition does not contain alkylamine, as described in any one of A] to C3] above. E3] The composition is one of the compositions described in any one of A] to D3] above, having an "oil removal percentage" of ≥60%, or ≥62%, or ≥65%, or ≥67%, or ≥70%, or ≥72%, or ≥74%, or ≥76%, or ≥78%, or ≥80%, determined from the formula [(W2-W3) / (W2-W1)] × 100 (wherein W1, W2, and W3 are each defined herein). (See the Experiments section.) F3] The composition is one of the compositions described in A] to E3] above, having 100% "oil removal%". G3] The composition according to any one of A] to F3] above, which, after shaking for 60 seconds as described herein, produces a foam height of ≤5 mm, or ≤4 mm, or ≤3 mm, or ≤2 mm, or ≤1 mm, or 0 mm (see Experiment section). H3] Composition, A composition according to any one of A] to G3] above, which produces a foam height of ≥0 mm after shaking for 60 seconds, as described herein. I3] The composition is one of the compositions described in any one of A] to H3] above, which fills a "10 mL" volume within a time of ≤10, ≤9, ≤8, or ≤7 seconds as determined by emulsification evaluation as described herein (see Experiment section). J3] The composition is separated from the oil and fills a volume of "10 mL" within a time of ≥2 seconds or ≥3 seconds, as described in any one of A] to I3] above. K3] The composition is separated from oil and fills a "5 mL" volume within a time of ≤ 5, ≤ 4, ≤ 3, ≤ 2, or ≤ 1 second as determined by emulsification evaluation as described herein (see Experiment section), as described in any one of A] to J3] above. L3] The composition is separated from oil and fills a volume of "5 mL" within a time of ≥0 seconds or ≥1 second, as described in any one of A] to K3] above. M3] A composition that is a transparent solution, and furthermore, one of the compositions described in A] to L3] above, which is a transparent solution at a temperature of 21°C to 23°C. N3) The composition according to any one of A] to M3] above, wherein the components of the composition are soluble in the composition, and furthermore, the components of the composition are soluble in the composition at a temperature of 21°C to 23°C. A4) A process for forming the composition described in any one of A) to N3) above, the process comprising mixing at least component a and component b. B4] The method according to A4], wherein the process comprises mixing at least component a, component b and component c. C4] The mixing is carried out at a temperature of 18°C, or ≥19°C, or ≥20°C and / or ≤27°C, or ≤26°C, or ≤25°C, or ≤24°C, or ≤23°C, as described in any one of A4] to B4] above. D4] Mixing is carried out in the ambient atmosphere, as described in any one of the processes described in A4] to C4]. E4) A process for cleaning a metal surface, comprising applying one of the compositions described in A) to N3) above to the metal surface. F4] The metal of the metal surface is selected from steel, stainless steel, brass, chromium, iron, cast iron, aluminum, aluminum alloy, copper, copper alloy, or gold, as described in E4 above. G4] The process according to E4] or F4] above, wherein when applied to a metal surface, the temperature of the composition is ≥18°C, or ≥19°C, or ≥20°C, or ≥22°C, and / or ≤30°C, or ≤29°C, or ≤28°C, or ≤27°C, or ≤26°C, or ≤25°C, or ≤24°C. H4] The process is an industrial cleaning process, one of the processes described in any one of E4] to G4] above. I4] A composition according to any one of A2] to N3] above, which is used to clean a metal surface. J4] The metal on the metal surface is selected from steel, brass, chromium, iron, cast iron, aluminum, aluminum alloy, copper, copper alloy, or gold, as described in I4] above. [Examples]

[0064] The reagents are shown in Table 1a below, and the boiling points of 1,4-bis(2-hydroxyethyl)-piperazine are listed in Table 1b (see also Figure 1). The test materials are shown in Table 2 below.

[0065] [Table 1] * Boiling point = 246℃ (760mmHg). ** Boiling point = 146℃ (760mmHg). *** Boiling point = 165℃ (760mmHg). **** Boiling point = 170℃ (760mmHg).

[0066] [Table 2] * Please refer to Figure 1. ** Average = [(Prediction + Extrapolation) / 2]

[0067] [Table 3]

[0068] composition The cleaning compositions are shown in Tables 3 and 4 below. Please also refer to Tables 5 and 6 below.

[0069] [Table 4] * Each weight percentage is based on the weight of the composition. For both Example 1 and Example 2, minimal foaming is expected.

[0070] [Table 5] * Each weight percentage is based on the weight of the composition.

[0071] Each of the compositions described herein was prepared by mixing the reagents listed at room temperature (RT, approximately 22°C). For each of the compositions in Tables 3 and 6, the amine was added to deionized water (DI water), and the solution was mixed to form a washing composition. For each of the compositions in Tables 4 and 5, sodium carbonate and EDTA-4Na·4H2O were added to DI water, and the resulting solution was mixed until the powder dissolved to form a first composition. Then, the amine was added to the first composition to form a final composition, which was mixed until a homogeneous suspension or complete dissolution was formed.

[0072] Tests and Results Metal cleaning evaluation (oil removal) Stainless steel (SS) specimens were washed under running DI water for approximately 10 seconds, and then rinsed by spraying acetone onto the specimens from a squeeze bottle until all surfaces were covered. The washed and rinsed specimens were blow-dried at room temperature and then weighed. The weight of the dried SS specimens was recorded as W1.

[0073] The cleaning composition (45 g, see Tables 3, 4, 5, and 6) was added to a 50 mL PP bottle.

[0074] A dry ss test specimen was weighed, and stamping oil (0.20 g + / - 0.01 g) was applied to the top surface of the specimen using a dropping tube. The specimen was carefully rotated to ensure that the oil was evenly distributed across the specimen surface. The weight of the soiled specimen was recorded as W2.

[0075] Using tweezers, the soiled test specimens were placed in the cleaning composition (50 mL bottle) at room temperature (RT, approximately 22°C), and the timer was immediately started. After 20 minutes (for the compositions in Table 3) or 10 minutes (for the compositions in Tables 4 and 5), the test specimens were removed from the composition and rinsed by immersing them in 200 mL of DI water (in a 250 mL beaker) for approximately 3–5 seconds.

[0076] The rinsed test specimens were placed on a metal tray (with the "top surface" facing upwards) on a laboratory benchtop, and the specimens were air-dried at room temperature for one day. The weight of the dried specimens was recorded as W3. The percentage of oil removed by the cleaning composition (or "oil removal %") was calculated using the formula [(W2-W3) / (W2-W1)] × 100. The results are shown in Figure 2 (compositions in Table 3) and Figure 3 (compositions in Table 4). In Tables 3 and 4, three test specimens were tested for each composition, and the average was reported. The results are also shown in Table 5. For each composition in Table 5, two test specimens were tested, and the average was reported.

[0077] As shown in Figure 2, for the compositions in Table 3, Example 1 (PIP2) exhibited the best oil removal efficacy compared to the comparative example and Example 2 (HEP).

[0078] As shown in Figure 3, for the compositions in Table 4, Examples 3 (PIP 2) and 4 (HEP) showed better cleaning performance than Comparative Example 4 (LFE-1410) and comparable cleaning performance to Comparative Example 6 (LF900).

[0079] As shown in Table 5, better oil removal was observed when the "c / a weight ratio" was 4.0 to 10.0. The applicant notes that at higher c / a ratios, especially with larger amounts of PIP (> 0.50 wt%), the solution may become turbid in appearance due to some insolubility of sodium carbonate.

[0080] [Table 6] * Each wt% is based on the weight of the composition. For each of Examples 5 to 10, minimal foaming was observed.

[0081] Additional oil removal data is shown in Table 6. Here, the soiled test piece is immersed in the cleaning solution at a temperature of 30°C.

[0082] The test piece was taken out after 5 minutes. As shown in Table 6, more oil removal was observed when the "b / a weight ratio" was 9.0 to 25. See also Figure 4.

[0083] [Table 7] * Each wt% is based on the weight of the composition. For each of Examples 11 to 15, minimal foaming was observed.

[0084] Foaming evaluation A high-throughput phase identification and characterization robot (see MCDCarter et al., Nonionic Surfactants Promote the Incorporation of Silicone-Acrylic Hybrid Monomers in Emulsion Polymerization, ACS Applied Polymer Materials 2022) was used to perform "shaking foaming" tests on each sample composition. This machine consists of an environmental chamber that maintains the sample at a constant temperature, a robotic arm that moves the vial from a temperature-controlled stage to an imaging chamber, and a high-resolution camera that takes photographs of the sample against a black background. The sample is illuminated with LED light directed at a 90° angle from the camera. Each test composition (see Table 4) was shaken using the same high-intensity, pre-set program and for a pre-set duration (60 seconds).

[0085] After shaking was complete, a photograph of the composition was taken and the foam height was recorded. For each composition, 3.0 g of the composition was added to a standard glass bottle (8 mL capacity). The "shaking foaming" test was performed at room temperature (RT, approximately 22°C). The amount of foaming was characterized as follows: a) high foaming - foam height ≥ 16 mm (typically 16-32 mm), b) foaming - foam height 6 mm to < 16 mm, c) low foaming - foam height > 0 mm to < 6 mm, d) no foaming - foam height 0 mm. The appearance of the composition was recorded as transparent or turbid (white). The results are shown in Table 7 below.

[0086] In Examples 3 (PIP2), 3 (HEP), Comparative Example 7 (PPZ), and 9 (AMP), no foam was generated, and each composition was transparent in appearance. The ability of a cleaning composition to generate a small amount of foam is an important consideration for metal cleaning compositions, especially those used in large-scale (or industrial-scale) metal cleaning processes. Excessive foaming can lead to insufficient rinsing of metal surfaces and / or overflow and spillage of the cleaning bath, resulting in product waste. Furthermore, as shown in the compositions of Examples 3 and 4, good foam control reduces or eliminates the need for additional foam control agents.

[0087] [Table 8] * The lower the boiling point of each amine, the more easily its respective cleaning solution evaporates and the more likely it is to produce an odor.

[0088] Emulsification evaluation A paraffin solution (see Table 2) was used as the oil phase. A cleaning composition (20 mL, see Table 4) was added to a graduated cylinder (100 mL), followed by the addition of 20 mL of oil. The cylinder was shaken up and down 10 times, each cycle being one. This up-and-down shaking was repeated for 5 cycles, with a 1-minute interval between cycles. After 5 cycles were completed, the time required for the aqueous phase to separate from the oil and reach the calibration marks of 5 mL, and then 10 mL, was recorded. Longer separation times indicated stronger emulsification of the cleaning composition and oil. The results are shown in Figure 5.

[0089] As shown in Figure 5, Examples 3 (PIP2) and 4 (HEP) had weaker emulsifying power (as indicated by faster oil separation) compared to the surfactants (Comparative Examples 4-6). Rapid oil separation is advantageous in the metal cleaning process because it is expected that the cleaning solution will quickly separate from the oil after cleaning the metal. Strong binding with oil can lead to a significant decrease in the effectiveness of the cleaning bath and, therefore, a shorter bath life. The results herein indicate that Examples 3 and 4 are optimal cleaning compositions for efficient oil separation and a longer bath life, respectively.

[0090] Overall, the compositions of the present invention provide excellent oil removal properties with little to no foaming. The weight ratio can be optimized to increase the amount of oil removed, as described above. Such compositions also provide rapid separation from oil, as described above. The results are obtained at room temperature. Furthermore, the components of each composition are completely soluble at room temperature.

Claims

1. At least the following components a and b): a) At least one N-substituted piperazine selected from the following structures 1), 【Chemistry 1】 In the formula, R1 is a C1-C6 alkoxyl group, R2 is H or an alkyl group, and R3 is H or a C1-C6 alkoxyl group, comprising at least one N-substituted piperazine. b) A composition comprising water.

2. The composition according to claim 1, further comprising a metal carbonate and / or a metal bicarbonate as component c.

3. The composition according to claim 2, wherein the weight ratio of component c to component a is ≥ 2.

0.

4. The composition according to claim 2 or claim 3, wherein the weight ratio of component c to component a is ≤ 10.

5. The composition according to any one of claims 1 to 4, wherein the composition comprises, based on the weight of the composition, a total of 88% to about 100% by weight of component a and component b.

6. The composition according to any one of claims 1 to 5, wherein R1 = R3 for structure 1 of component a.

7. The composition according to any one of claims 1 to 6, wherein R2 = H in the structure 1 of component a.

8. The composition according to any one of claims 1 to 7, wherein R1 is a C2-C4 alkoxyl group in structure 1 of component a.

9. The composition according to any one of claims 1 to 8, wherein R3 is a C2-C4 alkoxyl group in structure 1 of component a.

10. The composition according to any one of claims 1 to 5, wherein R3 is H in structure 1 of component a.

11. Component a has the following structures 1a) to 1c): 1a) 【Chemistry 2】 (In the formula, n is an integer from 1 to 6, and m is an integer from 1 to 6.) 1b) 【Transformation 3】 (wherein the formula, n is an integer from 1 to 6, m is an integer from 1 to 6, and p is an integer from 1 to 6), and The composition according to any one of claims 1 to 10, wherein 1c) is at least one structure selected from the group consisting of a mixture of structure 1a) and structure 1b).

12. The composition according to any one of claims 2 to 11, wherein component c is a metal carbonate.

13. The composition according to any one of claims 1 to 12, wherein component a is present in an amount of 0.01% to 20% by weight based on the weight of the composition.

14. The composition according to any one of claims 2 to 13, wherein the sum of components a, b, and c is present in an amount of 95.0% to 100% by weight, based on the weight of the composition.

15. The composition according to any one of claims 1 to 14, further comprising a metal chelate as component d.

16. The composition according to any one of claims 1 to 15, having an oil removal percentage of ≥60% as determined by the formula [(W2 - W3) / (W2 - W1)] × 100, where W1 = the weight of a stainless steel test piece, W2 = the weight of the oil-stained test piece, and W3 = the weight of the dried test piece after being subjected to cleaning evaluation with the composition (see the section on experiments).

17. The composition according to any one of claims 1 to 16, wherein the composition is shaken for 60 seconds using a high-throughput robot to produce a bubble height of ≤5 mm (see the section on experiments).

18. A process for forming the composition according to any one of claims 1 to 17, wherein the process comprises mixing at least component a and component b.

19. A process for cleaning a metal surface, the process comprising applying a composition according to any one of claims 1 to 17 to the metal surface.

20. The process according to claim 19, wherein the temperature of the composition is 18°C ​​to 29°C when applied to the metal surface.

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