KR20070109968A - Cleaning formulation comprising ethereal alcohols and its derivatives - Google Patents

Abstract

A semi-aqueous cleaning composition is provided to have excellent wettability, penetration, and rinsing properties, superior removability of oils and other stained materials, high safety, and low fire risk. A semi-aqueous cleaning composition comprises 50-92.5% by mass of the following organic compounds(i-iv) or a mixture thereof, and 7.5-50% by mass of ionic and non-ionic surfactants having an HLB value of 4-18, or a mixture thereof with other metal salt. The organic compounds(i-iv) are as follows: (i) C3-8 aliphatic alcohols(formula 1) comprising at least one ether functional group; (ii) the corresponding ester compounds(formula 2) produced by esterification of the alcohols(i) and C2-3 aliphatic carboxylic acids; (iii) other C3-8 aliphatic carboxylic acids(formula 3(a)) comprising at least one ether functional group, or all the corresponding esters(formula 3(b), 3(c)) that do not belong to the esters(ii); and alkyl pyrrolidones(formula 4).

Description

Cleansing Formulation Comprising Ethereal Alcohols and Its Derivatives

The present invention relates to a water-based / complementary detergent composition, which is an environmentally-friendly method that can be widely applied to the removal of oil and other contaminants in processes such as manufacturing, processing and post-treatment in the fields of electrical, electronic and precision instruments, metals and polymer materials. It is a low toxicity cleaner. The present detergent composition includes aliphatic alcohols containing ether functional group (-O-), corresponding ester compounds produced by esterification reaction of such aliphatic alcohols and aliphatic carboxylic acid, and other ether containing functional group (-O-). Aliphatic esters, heterocyclic alkylpyrrolidones, and combinations of water, ionic / nonionic surfactants, and metal salts. It has good penetration and wettability, lowers the interfacial tension of the contaminants, facilitates degassing of the contaminants from the substrate, and exhibits excellent cleaning ability by emulsifying the free contaminants. In addition, compared to the conventional chlorine-based cleaners, human toxicity is significantly lower, it is an environmentally friendly alternative cleaner with less fire risk.

Conventionally, 1,1,2-trichlorofluoroethane (1,1,2-trichlorofluoroethane, CFC-113), 1,1,1-trichloroethane (1,1,1-trichloroethane, 1,1, 1-TCE), trichloroethylene (hereinafter referred to as TCE) and methylene chloride (MC) have been widely applied to domestic and overseas industrial cleaning fields based on excellent cleaning properties. However, these are chlorine-based volatile organic compounds (VOCs) with relatively high vapor pressure, which are likely to enter the human body through the respiratory organs and skin of workers, and are known to have human toxicity such as carcinogenicity. . In addition, it has been found that it can be released into the atmosphere to cause smog by photochemical reactions, and furthermore, to destroy the ozone layer in the stratosphere, causing global climate change and extreme weather such as global warming. Each country is regulated in accordance with their cut, cut and abatement schedules set forth in the 1987 Montreal Protocol. In our case, the CFC-based compounds will be eliminated from 2010, 1,1,1-TCE from 2015, and chlorofluorocarbons from 2040. In recent years, opinions on the need for a shorter timeline have been raised in many countries. Therefore, it is time for further efforts to develop alternative materials. In addition, as some local governments in water supply protection areas are regulated in Korea, all MCs are classified as water pollutants. Therefore, the social demand for eco-friendly and low-toxic cleaners will increase.

These eco-friendly alternative cleaners are divided into water, organic, and non-aqueous based on the use of water / organic solvents.When using organic solvents compatible with water, use only organic solvents that are not compatible with water or organic solvents. Classify the case as non-aqueous. Generally, water-based and compliant cleaners have been developed and used as eco-friendly cleaners, but the cleaning ability for certain contaminants may be somewhat weak, and metal corrosion caused by the use of water is a problem. The reality is that there is still a need in the industry for non-aqueous and semi-aqueous cleaners other than detergents. Therefore, it is necessary to continuously develop cleaners that are safer, more environmentally friendly and have excellent cleaning ability. Organic compounds mainly used in environmentally friendly alternative cleaners include aliphatic hydrocarbon oils, limonene or terpine oil, but limonene is a natural substance, which is highly volatile in price and non-volatile, and remains on the substrate after cleaning. The disadvantage is that it is known to be toxic to aquatic organisms. The cleaning agents known at home and abroad are composed of a combination of additives such as aromatic compounds of ester oils of dibasic acids, hydrocarbon oils, silicone hydrocarbons, alkyl benzenes, and other surfactants.

The present invention is to provide a low toxicity, environmentally friendly alternative cleaning composition that can be applied to the water / compliant system depending on the contaminants and applications, the desired cleaning ability. First of all, by excluding chlorine-based VOCs including CFCs, 1,1,1-TCE, TCE, MC, etc., the risk of ozone layer destruction, human toxicity, and environmental damage is significantly reduced. In addition, the material to be used as the raw material for the cleaning agent is a material widely used in the industry and should be easily supplied and supplied, and also has low human toxicity and excellent compatibility with water, thus reducing the risk of fire and securing worker safety when applying the cleaning agent. You should be able to. This detergent, obtained by combining various kinds of ionic, nonionic surfactants, and various additives including metal salts, etc., is present in a stabilized mono phase, so that it has penetration, wettability, surfactant activity, emulsion stability, and high performance cleaning power. This should be exerted. All of the detergent compositions are easy to be biodegradable, and the intermediate or final material produced during the biodegradation process should be made of environmentally trouble-free materials.

In order to achieve the above object, the present invention uses the aliphatic alcohols, ester compounds, heterocyclic compounds alkylpyrrolidones that can be applied to the aqueous / compliant system to prepare a cleaning agent. Specifically, aliphatic alcohols containing an ether functional group (-O-), corresponding ester compounds produced by esterification of such aliphatic alcohols and aliphatic carboxylic acids, and other functional groups containing an ether functional group (-O-) are included. Aliphatic esters, alkyl pyrrolidones and water, ionic / nonionic surfactants, and metal salts in combination.

In general, organic solvents widely used in the detergent field include hydrocarbons, alcohols, ethers, esters, ketones, and the like. Hydrocarbons are nonpolar substances whose properties are governed by van der Waals force because they have only dipole moments of similar carbon and hydrogen, whereas alcohols, ethers, esters, and ketones have polarity in their molecules. Functional groups such as hydroxy group (-OH), ether group (-O-), ester group (-COO), carbonyl group (-CO), etc. are present, resulting in a different aspect from hydrocarbons. These materials have different properties depending on the size of the aliphatic hydrocarbons, that is, the length of the hydrocarbons. Alcohols, ethers, esters having a carbon number ranging from C1 to C2, such as methanol, ethanol, dimethyl ether, acetone, etc., are widely known. For example, ketones have limitations in removing various oil and other contaminants. In addition, organic compounds composed of potent elements such as carbon, hydrogen, oxygen, and nitrogen exist in a large number of isomers, and it is impossible to manufacture them one by one. However, it is possible to assume a material that exhibits the desired cleaning properties as a material that is industrially useful or easily synthesized. The present invention provides an aqueous / complementary cleaning agent having excellent cleaning power using such a material as a base material. Reaffirm that its main purpose is to do so.

Typically, iii) aliphatic alcohols containing at least one ether functional group (-O-) and consisting of C3 to C8 (Chemical Formula 1), ii) alcohols of iii) and aliphatic carboxylic acids consisting of C2 to C3 And other aliphatic carboxylic acids (C 3) containing at least one of the corresponding ester compounds produced by the esterification reaction (Chemical Formula 2) (a)) or esters (corresponding to all of the remaining esters not included in Formulas 3 (b), 3 (c), ie ii) above), i) alkyl pyrrolidones may be applied. As mentioned above, the meaning of aliphatic compound was used to mean that it is not an aromatic compound such as benzene, and it is again clarified to mean aliphatic compounds in a broad sense.

Formula 1

Formula 2

Formula 3

(a)

(b)

(c)

Formula 4

In Formula 1 to Formula 3, R and R "represent an alkyl group, R 'represents H or an alkyl group, l and m are 0 or a natural number, and n is a natural number. However, R, R', R ", l, m, n are interlocked in the C3-C8 carbon number, and the selection is fluid. The alkyl group R of the formula (4) is limited in scope to C1 to C3.

Substances belonging to the above-mentioned class (i) but which can be easily applied industrially include 2-methoxyethanol, 1-methoxy-2-propanol, 1-methoxy-2-propanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2-ethoxyethanol ( 2-ethoxyethanol), 2-butoxyethanol, 2-ethoxy-1-propanol, 3-methoxy-1-butanol ), 2- (2-n-butoxyethoxy) ethanol (2- (2-n-butoxyethoxy) ethanol), triethylene glycol, tetraethylene glycol and the like.

The material corresponding to ii) can be easily prepared by esterification of acetic acid or propionic acid with the material corresponding to iv), and specifically, 2-methoxyethanol acetate (2). -methoxyethanol acetate), 1-methoxy-2-propanol acetate, 2- (2-ethoxymethoxy) ethyl acetate, 2 2- (2-ethoxyethoxy) ethyl acetate, 2-ethoxyethanol acetate, 2-butoxyethanol acetate, 2 3-ethoxy-1-propanol acetate, 3-methoxy-1-butanol acetate, 2- (2-n-butoxy 2- (2-n-butoxyethoxy) ethanol acetate, triethylene glycol acetate, tetraethyleneglycol Acetate (tetraethylene glycol acetate), methoxyethanol propionate, 1-methoxy-2-propanol propionate, 2- (2-ethoxymeth 2- (2-ethoxymethoxy) ethyl propionate, 2- (2-ethoxyethoxy) ethyl propionate, 2-ethoxyethanol prop 2-ethoxyethanol propionate, 2-butoxyethanol propionate, 2-ethoxy-1-propanol propionate, 3-methoxy 3-methoxy-1-butanol propionate, 2- (2-n-butoxyethoxy) ethanol propionate, triethylene The glycol propionate (triethylene glycol propionate), tetraethylene glycol propionate (tetraethylene glycol propionate), etc. are mentioned.

The above-mentioned group (iii) includes 3-methoxy propionic acid, 3-methoxy propionic acid methyl ester, 3-ethoxy propionic acid (3 -ethoxy propionic acid, 3-ethoxy propionic acid methyl ester, methyl methoxy acetate, ethyl methoxy acetate, ethyl 3-ethoxy Ethyl 3-ethoxy propionate, 2-methoxyethyl acetate, 2-ethoxy ethyl acetate, 2-ethoxy ethyl isobutyrate isobutyrate, ethyl diethoxy acetate, diethoxymethyl acetate, and the like.

Alkyl pyrolidone is an example of a substance belonging to group (iii). Representative substances include N-methyl pyrolidone, N-ethyl pyrolidone, and N. N-propyl pyrolidone and the like.

The organic compounds listed above have dipole moments and molecular forces depending on the length of the number of carbons in the main chain, the number of carbons adjacent to the functional group, the position of the hetero atoms (here oxygen and nitrogen), and the steric arrangement (linear and cyclic here). Different results in differences in solubility parameters. The solubility index is a concept that introduces cohesive energy density from the interaction between the polymer material and the solvent in the polymer solution, and the interaction with the solvent corresponding to the force between the molecules, that is, the compatibility ( The presence of miscibility means that it can be dissolved and is a major factor that directly affects a series of processes such as penetration, wetting, surfactant activity, degassing, dissolution, dispersion and emulsification. In other words, in order to form a stable phase to maintain and express a certain level of cleaning ability, it means that at least a certain level of mutual solubility due to structural similarity between compositions should be ensured as much as possible. On the other hand, it can be considered that these materials are a series of compounds which are not only structurally similar but also derivable from each other by an esterification reaction as those substances belonging to iv), ii), and iii) as polar substances. All of the compounds (i), ii), iii) and iii) including the alkylpyrrolidones as compounds have mutual miscibility and solubility, and have very good compatibility with water. It can be applied as an aqueous or compliant cleaning base material or a cleaning raw material.

It is important to select and apply an appropriate surfactant to increase the cleaning power and to unify the discontinuous or discontinuous phase. In order to facilitate the penetration of the cleaning agent, a compound having a high density and low viscosity and surface tension is generally advantageous, and the surfactant contributes a great deal to this role. In addition, surfactants and other metal salts in the compliance-based cleaners provide a major technology that can increase the limit of the amount of dilutable water used, and thus can also increase the economics of the cleaner compared to expensive cleaning base materials. Surfactants are typically classified into ionic and nonionic surfactants, and in principle, both aqueous and non-aqueous surfactants can be applied. However, in the compliance system, the surfactants can be selectively used in consideration of phase stability, or other builders, It is desirable to apply a solubilizer, other metal salts, etc. to form a single phase at least at the micrometer level or below.

Nonionic surfactants applicable to the present invention include polyoxyethylene type, sorbitan type, glucose type, and hydroxyl type. The polyoxyethylene type includes polyoxyethylene alkyl ether, alkyl phenol ether, fatty acid ester and the like obtained by adding ethylene oxide (EO) to higher alcohols, alkyl phenols and higher fatty acids. They are widely used as emulsifiers because they can easily control the degree of hydrophilicity by controlling the number of moles of EO. However, in recent years, the use of alkyl phenyl ethers is considerably reduced because phenolic compounds are problematic. There is a trend. The sorbitan type is the sorbitol and aliphatic ester form of sorbitan, and the glucose type corresponds to alkyl glucoside obtained by condensation reaction of higher alcohol and glucose. As the hydroxyl group, aliphatic amides having fatty acids and esters in alkanol amines can be used.

Anionic surfactants include the most widely known alkyl benzene sulfuonates, alkyl sulfonates, alkyl polyoxyethylene sulfonates, and the like. It is obtained through sulfonation and post neutralization of fuming sulfuric acid or sulfur trioxide (SO ₃ ) on higher alcohols and alkylpolyoxyethylene ethers. Alkylbenzene sulfonates have also recently been slowed due to environmental problems.

Except for the surfactants containing the benzene and phenolic structural units mentioned above, they are industrially easy to manufacture and biodegradable. They are very suitable as eco-friendly cleaners. In particular, various levels of hydrophilic lipo can be adjusted by adjusting the amount of EO added. It is very useful in that it can implement a hydrophilic lipophilic balance (HLB). In the present invention, ionic and nonionic surfactants having a HLB value in the range of 4 to 18 are suitable, and in the range of 0.01 to 35% relative to the volume or mass of the material used as a base material, preferably 5 to 25%. It is suitable for use within the range. In addition, when the ionic and nonionic surfactants are used together, the stability of the phase may deteriorate a little, so that a suitable metal salt is added as a builder or a solubilizer in the composition to solve the problem. Representative metal salts that may be used include NaOH, KOH, NaHCO ₃ , Na ₂ CO ₃ and the like, and metal neutralizers of aliphatic carboxylic acids. However, it should be noted that if the amount of metal salts and water is excessively used, the pH of the detergent may be affected, and thus, phase separation of the aqueous detergent may occur, resulting in a decrease in the cleaning power.

Preferred embodiments and comparative examples of the present invention are as follows, which are intended only to present some examples showing the configuration of the invention and its effect, and do not limit or limit the entire contents of the present invention and claims.

In order to introduce ether functional groups into alcohols, they are generally manufactured industrially by adding EO, and alcohols having a more complicated structure are generally used by well-known Grignard synthesis or induction reaction. These possible hydrocarbons can also be obtained in the laboratory via air oxidation in the presence of a catalyst. In addition, the carboxylic acid which should be used for obtaining the compound belonging to group ii) can be obtained through oxidation of hydrocarbons or alcohols in the presence of a metal catalyst. The alcohols and carboxylic acids thus obtained are used as raw materials for synthesizing the esters of groups ii) and iii). The ester compounds applicable to the present invention can be obtained through the reaction of alcohols and carboxylic acids indicated above, and are selectively manufactured based on compounds having industrial utility value. It may be necessary to manufacture. However, since the esterification reaction is a well-known unit reaction, it is unnecessary to describe each of the synthesis methods and the synthesis conditions according to the combination of the reactants, and is replaced by a brief description.

After mixing 10-90 mass% of alcohols represented by Formula 1 and 10-90 mass% of carboxylic acids in a reactor, the temperature is raised to 80-90 degreeC primarily. Wherein the mixture of any one of the compounds of Formula 1 or a combination thereof may contain other moisture (H ₂ O) in the manufacturing process, preferably less than 0.5% compared to the reactants contained in the entire reactor. At this time, while maintaining the same temperature, the pressure is gradually lowered from atmospheric pressure to 0.2 atm to remove substances such as moisture mentioned above, and then the pressure is raised to atmospheric pressure again. For full-scale ester synthesis, a series of stepwise reactions including [heating-esterification reaction-decompression dehydration] are performed to increase the conversion to the corresponding ester compound. Preferred reaction temperatures are no lower than 100 ° C. and no higher than 220 ° C., more preferably in the range of 120-180 ° C.

Other matters relating to the synthesis follow the conventional ester synthesis method. The esterification reaction is a reversible reaction described by the equilibrium constants and reaction rates determined in thermodynamics and reaction kinetics, and as mentioned above, circulates water. The amount of water produced is determined by the equilibrium position, and in order to design an industrially high yield reaction system, it is common to proceed with dehydration using a method such as vacuum distillation. In order to speed up the esterification reaction, an acid catalyst is usually used, but it is necessary to pay attention to the reactor pH in consideration of the fact that the resulting ester may decompose under high temperature conditions in which an acid is present. The corresponding esterification conditions mentioned above correspond to some conditions of conventional esterification methods. For this reason, it is again noted that the scope of the synthesis method of the corresponding ester compound obtained under specific conditions is not limited or reduced.

Examples # 1 to # 16 and Comparative Examples # 1 to # 8

As shown in Table 1 and Table 2 below, a cleaning composition composed of compounds belonging to Groups iii), ii), iv), and iv) was prepared, and then the stability, washing ability, rinsability, and the like of the phases were evaluated. The stability of the well-known phase was determined by observing the presence of a single phase and the degree of clouding after stagnation in a separatory funnel for 24 hours. For the evaluation of the cleaning ability, contaminants were selected from silicone oil, grease and acrylic polymer residue surfaces for casting. In the case of silicone oil and grease, a thin coating was applied on the slide glass, and then stored in an oven at 70 ° C. for 6 hours before measuring the cleaning power. In the case of the acrylic polymer residue for casting, a monomer was injected between glass molds and cast in an oven at 120 ° C. for 12 hours. The cleaning experiment was carried out by ultrasonic treatment (40kHz) at room temperature, the cleaning time was fixed to 5 minutes. In order to indicate the reliability of the fine cleaning and cleaning process, after inspecting the whole glass after the cleaning, the presence of residual contaminants on the surface was confirmed by a microscope, indicating that the cleaning property was recorded as (all / surface). ◎ denotes the degree of no residue, ○ denotes the degree of almost no residue, and Δ means that some residue remains. The weight change of the contaminants before and after cleaning confirmed that the silicone oil, grease and acrylic monomer residue contaminants were removed through this cleaning process, which can be widely applied to cleaning contaminants in general industrial sites. Suggests.

Table 1.

compound Example Comparative Example #One #2 # 3 #4 # 5 # 6 # 7 #8 #One #2 # 3 #4 A 60 10 30 20 60 60 35 40 B 10 60 30 30 30 5 65 C 5 5 10 5 5 10 D 10 10 5 10 10 E 55 10 60 35 F 10 10 8 10 G 25 9 10 H 25 10 I 8 5 J 5 K 5 5 2.5 L 5 5 M 5 5 10 5 2.5 5 5 2.5 N 3 3 2 10 7.5 10 15 3.5 O 2 2 2 2 1.5 P 3 5 10 6 20 20 10 20 10 5 2.5 12.5 Sum 100 100 100 100 100 100 100 100 100 100 100 100 Stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Cleanability (All / Surface) ◎ / ○ ◎ / ◎ ◎ / ○ ◎ / ◎ ◎ / ◎ ◎ / ◎ ◎ / ◎ ◎ / ◎ ○ / ○ ○ / △ ○ / △ ○ / △ Rinseability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○

A: 2-Methoxy-propanol

B: 1-Methoxy-2-propanol acetate

C: Butyl acetate

D: 3-Ethoxypropionic acid methyl ester

E: N-methyl pyrolidone

F: 1-Amino-2-propanol

G: 2- (2-Methoxyethoxy) ethanol

H: 2- (2-Ethoxyethoxy) ethanol

I: 2- (2-n-Butoxyethoxy) ethanol

J: 3-Methoxy butyl acetate

K ': alkyl sulfonate anionic surfactant

L ': alkanolamine-based nonionic surfactant

M ': polyoxyethylene-based nonionic surfactant (HLB 4 to 10 range)

N ': polyoxyethylene-based nonionic surfactant (HLB 10.01 to 18 range)

O ': other salts

P: distilled water

Table 2.

compound Example Comparative Example # 9 # 10 # 11 # 12 # 13 # 14 # 15 # 16 #4 # 5 # 6 # 7 A ' 55 10 10 20 60 65 35 20 B ' 10 20 10 30 30 5 65 10 20 C ' 5 5 10 5 20 5 D ' 10 10 10 25 10 10 10 10 E ' 25 30 35 F ' 20 5 10 10 5 10 G ' 10 10 25 5 10 H ' 5 10 25 10 I ' 10 5 5 5 J ' 5 5 10 10 K ' 5 5 5 2.5 L ' 5 5 M ' 5 5 10 5 2.5 5 5 2.5 N ' 3 3 2 10 7.5 10 15 3.5 O ' 2 2 2 2 1.5 P ' 3 5 10 6 20 20 10 20 10 15 2.5 12.5 Sum 100 100 100 100 100 100 100 100 100 100 100 100 Stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Cleanability (All / Surface) ◎ / ◎ ◎ / ◎ ◎ / ◎ ◎ / ◎ ◎ / ◎ ◎ / ◎ ◎ / ◎ ◎ / ◎ ○ / ○ ◎ / ○ ○ / ○ ○ / ○ Rinseability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

A ': 1-Methoxyethanol acetate

B ': Diethoxymethyl acetate

C ': 2-Ethoxyethyl acetate

D ': N-ethyl pyrolidone

E ': 3-Ethoxy-1-propanol

F ': Triethylene glycol

G ': 2- (2-Methoxyethoxy) ethanol

H ': 3-Methoxy-1-butanol

I ': 2-Ethoxyethyl isobutyrate

J ': Tetraethylene glycol

K ': alkyl sulfonate anionic surfactant

L ': alkanolamine-based nonionic surfactant

M ': polyoxyethylene-based nonionic surfactant (HLB 4 to 10 range)

N ': polyoxyethylene-based nonionic surfactant (HLB 10.01 to 18 range)

O ': other salts

P: distilled water

Claims (4)

Iii) aliphatic alcohols containing at least one ether functional group (-O-) and consisting of C3 to C8 (Formula 1), Ii) the corresponding ester compounds produced by esterification of the alcohols of (i) above and aliphatic carboxylic acids having C 2 to C 3 (Chemical Formula 2), Iii) a corresponding ester which contains at least one ether functional group (-O-) and is not included in other aliphatic carboxylic acids (formula 3 (a)) or esters (ie ii) in the range of C3 to C8 Corresponding to all classes, Formula 3 (b), Formula 3 (c)) Iii) alkyl pyrrolidones (Formula 4) Ionic compounds containing 50 to 92.5% by mass, and an HLB value of 4 to 18, containing an organic compound corresponding to iv), ii), iii), and iv) above, or any mixture selected from the combinations of these compounds. And a non-ionic surfactant, or a mixture selected from a combination of other metal salts, in a mass-based detergent composition comprising 7.5 to 50% by mass. Formula 1

Formula 2

Formula 3

(a)

(b)

(c) Formula 4

In Formula 1 to Formula 3, R and R "represent an alkyl group, R 'represents H or an alkyl group, l and m are 0 or a natural number, and n is a natural number. However, R, R', R ", l, m, n are interlocked in the C3-C8 carbon number, and the selection is fluid. The alkyl group R of the formula (4) is limited in scope to C1 to C3. The organic compound of Group 1) in 2-methoxyethanol, 1-methoxy-2-propanol, 2- (2-methoxy) 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2-ethoxyethanol, 2-part 2-butoxyethanol, 2-ethoxy-1-propanol, 3-methoxy-1-butanol, 2- (2-n -Butoxyethoxy) ethanol (2- (2-n-butoxyethoxy) ethanol), triethylene glycol, tetraethylene glycol, and the like, Examples of organic compounds according to ii) include 2-methoxyethanol acetate, 1-methoxy-2-propanol acetate, and 2- (2-ethoxymeth 2- (2-ethoxymethoxy) ethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 2-ethoxyethanol acetate acetate), 2-butoxyethanol acetate, 3-ethoxy-1-propanol acetate, 3-methoxy-1-butanol acetate 1-butanol acetate), 2- (2-n-butoxyethoxy) ethanol acetate (2- (2-n-butoxyethoxy) ethanol acetate), triethylene glycol acetate, tetraethylene glycol acetate glycol acetate), 2-methoxyethanol propionate, 1-methoxy-2-propanol propionate, 2- ( 2- (2-ethoxymethoxy) ethyl propionate, 2- (2-ethoxyethoxy) ethyl propionate, 2 2-ethoxyethanol propionate, 2-butoxyethanol propionate, 2-ethoxy-1-propanol propionate 3-methoxy-1-butanol propionate, 2- (2-n-butoxyethoxy) ethanol propionate (2- (2-n-butoxyethoxy) ethanol propionate), triethylene glycol propionate, tetraethylene glycol propionate, and the like, The organic compounds corresponding to (iii), 3-methoxy propionic acid, 3-methoxy propionic acid methyl ester, 3-ethoxy propionic acid (3-ethoxy propionic acid), 3-ethoxy propionic acid methyl ester, methyl methoxy acetate, ethyl methoxy acetate, ethyl 3- Ethoxy 3-ethoxy propionate, 2-methoxyethyl acetate, 2-ethoxy ethyl acetate, 2-ethoxy ethyl isobutyrate ethoxy ethyl isobutyrate, ethyl diethoxy acetate, diethoxymethyl acetate, N-methyl pyrolidone, N-ethyl pyrolidone, N-propyl pyrolidone, etc. Aqueous / complementary cleaning composition comprising a combination of compounds belonging to alone or above iii), ii), iii) and iii) Aqueous detergent composition wherein the water content is added in the range of 0.01 to 70.01% based on the mass of the total detergent in the compliant detergent composition of claim 1 Cleaner composition wherein 7.5 to 30% of any water-based detergent composition selected from the compound combinations of iv), ii) and iii) other than iii) of claim 1 is added based on the total mass of the water-based detergent.