KR20130057046A - Inhibiting redeposition and low foaming aqueous cleaner composition - Google Patents

Abstract

PURPOSE: An aqueous cleaning composition is provided to prevent redepostion and to provide excellent cleaning and washing performance and low bubble foaming. CONSTITUTION: An aqueous cleaning composition comprises one or more organic solvent selected from water, alcohols, or glycols; one or more polymer dispersant selected from homopolymers and salts thereof, represented by chemical formula 1, and copolymers and salts thereof, represented by chemical formula 2; polyalkylene oxide-based surfactant represented by chemical formula 3; polyglucoside-based surfactant represented by chemical formula 4; and an alkali agent with pH of 12 or more.

Description

Inhibiting redeposition and low foaming aqueous cleaner composition

The present invention relates to a cleaning composition for cleaning contaminated sources contaminated with glass, metals, plastics, and the like, more specifically, to excellent rinsing performance with high cleaning performance and low foaming properties, and to prevent contamination due to reattachment after removing contaminants. It is related with the cleaning composition which can be performed.

Chlorofluorocarbon-113, 1,1,1-trichloroethane and tetrachloroethylene, methylene chloride (MC), perchloroethylene with the advantages of solubility, workability, flammability, and dryness to contaminants in wet cleaning processes Chlorine-based solvents such as (PCE) and trichloroethylene (TCE) have long been used. The cleaners have been widely used in the industrial field because of their excellent cleaning properties, flammability and excellent volatility. However, the above-mentioned cleaning agents are poor in material safety for the object to be cleaned and their use is gradually reduced due to international environmental regulations due to the ozone layer destruction. In particular, the cleaning agents such as MC, PCE, TCE, etc. among the cleaning agents are classified into toxic substances and carcinogenic substances have various problems that can seriously affect the safety and health of field workers.

As a cleaner that can replace this, alcohol- and hydrocarbon-based cleaners, water-based cleaners, semi-detergent cleaners and the like are known.

The alcohol-based and hydrocarbon-based cleaners do not contain water and are similar in dryness to chlorine-based cleaners, so they can be used without changing the conventional cleaning system significantly. Has the economic problem of additional costs. Some chemicals, such as isopropyl alcohol, are defined as volatile organic compounds (VOCs), requiring cleaning device supplementation or limited use.

In consideration of work safety such as human safety and flammable safety, compliance or water based cleaner technology is spotlighted as an environmentally friendly cleaner. This type of cleaning agent is basically a cleaning agent containing water and has excellent work safety, and has the advantage of increasing the cleanability by adding various surfactants and builders. In particular, alkaline cleaners containing KOH, NaOH, inorganic builders and the like show excellent cleaning power and can be efficiently used in various cleaning areas. However, since the corrosion of metal materials such as gold, silver, copper, aluminum, and zinc in the material to be cleaned occurs according to the alkali property, there is a disadvantage in that the scope of cleaning is limited. In addition, the problem of re-contamination of the object to be cleaned after the removal of contaminants during the cleaning process is a factor that reduces the cleaning performance.

The compliant cleaner is highly soluble and has excellent cleaning ability, and has been evaluated as an alternative cleaner for ozone depleting substances and carcinogenic substances. However, in the case where the main composition of the cleaning agent is an oil, in particular, an oil having 14 to 20 carbon atoms, since the continuous phase of the cleaning composition is an oil, the mixing property with water is poor in the rinsing step, and a macro emulsion is formed. Therefore, this causes the rinsing property to be inferior to that of the aqueous system, and the cleaning composition remains in the object to be cleaned after cleaning. In particular, if the cast product of the detergent is limonene oil, poor mixing properties with water, the rinsing performance is reduced in the rinsing process, so that the pollutant remains and its unique scent is avoided in the field due to odor problems.

Accordingly, the present inventors have conducted research to develop an alternative cleaning agent that can solve the above problems. As a result, (a) a polymer dispersant selected from homopolymers, copolymers and salts thereof of a specific structural formula in a solvent consisting of water and alcohols, (b The present invention has been completed by discovering that the cleaning composition comprising a) polyalkylene oxide surfactant, (c) polyglucoside surfactant, and (d) alkali agent is very effective in preventing reattachment of a pollutant.

Accordingly, the present invention provides a cleaning agent that can prevent recontamination due to reattachment of the removed contaminant in cleaning to remove contaminants contaminated with glass, metal or plastics, and can provide low foaming and excellent rinsing properties. It is for that purpose.

In the present invention for solving the above problems, in one or more solvents selected from the group consisting of water, alcohol or glycol,

(a) at least one polymer dispersant selected from homopolymers represented by formula (1) and salts thereof, and copolymers represented by formula (2) and salts thereof; (b) a polyalkylene oxide-based surfactant represented by Formula 3 below; (c) a polyglucoside surfactant represented by the following formula (4); And (d) an alkaline agent of pH 12 or higher; It is characterized by a water-soluble detergent composition containing a.

[Formula 1]

(Q in Formula 1 is an integer of 60 to 600)

[Formula 2]

(In Formula 2, l and m are the same as or different from each other and are an integer of 80 to 400, and the molar ratio of m / L is 0.4 to 1.0.)

(3)

(In the above formula (3), R is an alkyl group of C ₁ to C ₁₅ , x and y are the same or different and are integers of 1 to 20, and the molar ratio of x / y is 0.5 to 2).

[Formula 4]

(In the formula (4), k and n are the same as or different from each other, an integer of 5 to 20, m is an integer of 5 to 20)

In the water-soluble detergent composition of the present invention, contaminants contaminated with glass, metal, or plastics are used in the removal process to prevent reattachment of the contaminants and suppress bubble generation, thereby exhibiting excellent cleaning performance. It can be applied in various ways.

1 is a photograph showing the object to be cleaned before and after washing with the composition of Example 1.
2 is a result of measuring the surface state before and after washing with the composition of Example 1 by FT-IR.

The water-soluble detergent composition of the present invention comprises (a) 0.01 to 5% by weight of a polymer dispersant in an organic solvent consisting of water and alcohols; (b) 0.01 to 10 wt% of a polyalkylene oxide surfactant; (c) 0.01 to 10% by weight of a polyglucoside surfactant; And (d) 1 to 20% by weight of an alkali agent.

Hereinafter, the components of the water-soluble detergent composition according to the present invention will be described in more detail.

(A) Polymer Dispersing Agent in the present invention is effective in preventing precipitation of inorganic salts, improving dispersibility of inorganic salts and particles, removing power of contaminants, isolating polycations, and improving dispersibility of pollutants, and is generated by using hard water. It serves to prevent the reattachment of contaminants by eliminating incineration. The polymer dispersant includes at least one member selected from homopolymers represented by the following Chemical Formula 1, copolymers represented by the following Chemical Formula 2, and salts thereof. In this case, the salt may be representatively included alkali metal salts. The alkali metal salt may be formed by combining a carboxylic acid group included in the polymer structure of Formula 1 or Formula 2 with an alkali metal.

[Formula 1]

(Q in Formula 1 is an integer of 60 to 600, preferably an integer of 100 to 500)

[Formula 2]

(In Formula 2, l and m are the same as or different from each other and are an integer of 80 to 400, preferably an integer of 100 to 300.)

The homopolymer represented by Formula 1 is a polymer dispersant having a weight average molecular weight (Mw) in the range of 4,500 to 40,000, and specifically, may include polyacrylic acid or sodium salts and potassium salts thereof. The copolymer represented by Formula 2 is a polymer dispersant having a weight average molecular weight (Mw) in the range of 2,500 to 70,000, and specifically, may include maleic acid-acrylic acid copolymer or sodium salts and potassium salts thereof. In the copolymer represented by the formula (2), it is more advantageous to improve the re-adhesion property of the molar ratio of the repeating unit of maleic acid and the mono unit molar ratio of acrylic acid, that is, m / L, in the range of 0.4 to 1.0. The polymer dispersant in the water-soluble detergent composition of the present invention may be included in the range of 0.01 to 5% by weight, preferably 0.1 to 3% by weight.

In the present invention, non-ionic surfactants having low foaming properties such as (b) polyalkylene oxide surfactants and (c) polyglucoside surfactants are used as the surfactant. The surfactant used in the present invention serves to increase the penetration of the cleaning agent between the object to be cleaned and the contaminant in the cleaning process, and in the rinsing step, micelles are removed from the object to be reattached to the object to be cleaned by forming micelles. It serves to prevent.

The polyalkylene oxide-based surfactant (b) is a nonionic surfactant in which ethylene oxide and propylene oxide are added to an alkyl group, as shown in the following general formula (3). The polyalkylene oxide-based surfactant in the water-soluble detergent composition of the present invention may be included in the range of 0.01 to 10% by weight, preferably 0.1 to 3% by weight.

(3)

(In the above formula (3), R is a C ₁ to C ₁₅ alkyl group, x and y are the same or different and are integers of 1 to 20, and the ratio of x / y is 0.5 to 2).

In addition, the (c) polyglucoside surfactant is a nonionic surfactant composed of alcohol and glucose, as shown in the following Formula 4. The polyglucoside-based surfactant in the water-soluble detergent composition of the present invention may be included in the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

[Formula 4]

(In Formula 4, k and n are the same as or different from each other, an integer of 5 to 20)

On the other hand, in the present invention, in addition to the nonionic surfactants represented by the formula (3) and formula (4) as the surfactant may be further included a conventional surfactant used in the manufacture of the detergent. Typical detergent surfactants include polyoxyalkylene alkyl phenol ethers, polyoxyalkylene aryl phenol ethers, polyoxyalkylene fatty acid esters, polyalkyl glucosides, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene alkyl amines , Sorbitan fatty acid esters, alkyl alcohol amines, aryl alcohol amines, or any mixture thereof. In the water-soluble detergent composition of the present invention, the conventional detergent for detergent may be included in the range of 0.01 to 10% by weight, preferably 1 to 5% by weight.

(D) Inorganic alkali in the present invention serves to dissolve contaminants. In the present invention, the alkali agent selection is not particularly limited, and any alkali compound having a pH of 12 or more may be used. The alkali agent may be selected from alkali metal, alkaline earth metal, ammonium, tetra (C _1-6 alkyl) ammonium, hydroxide of choline and the like. Specific examples of the alkali agent include one or two or more selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, butylammonium hydroxide and choline hydroxide. It is good to use. The alkaline agent in the water-soluble detergent composition of the present invention may be included in the range of 1 to 20% by weight, preferably 1 to 10% by weight.

In the present invention, water and alcohols are used together as a solvent. (e) Alcoholic solvents serve to increase the phase stability of the detergent and to improve the solubility of the inorganic substances. The alcohol solvent may be a monohydric alcohol having 1 to 15 carbon atoms, glycols having 2 to 15 carbon atoms, or an ether including the monohydric alcohol or glycols as a functional group. Specifically, the alcohol solvent is ethanol, propanol, butanol, hexanol, isopropanol, heptanol, decanol, isohexanol, isooctanol, isotecanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol methyl ether Diethylene glycol methyl ether, triethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol ethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, One or a mixture of two or more selected from ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, and triethylene glycol monohexyl ether may be used. Preferably, the alcohol solvent may be diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, or a mixture thereof. In the water-soluble detergent composition of the present invention, these alcohol solvents may be included in the range of 0.1 to 10% by weight, preferably 1 to 5.

(F) water used as a solvent in the present invention may be included in the range of 70 to 98% by weight, preferably 85 to 95% by weight in the water-soluble detergent composition of the present invention.

In addition, the water-soluble detergent composition of the present invention may further contain a conventional additive in addition to the components described above. These additives are components commonly used in the detergent manufacturing field, and the present invention places no particular limitation on the selective use of these additives. The additive may serve to improve the cleaning performance of the cleaning agent, to prevent corrosion of the cleaned object, to chelate for cleaning the metal, and the like. Examples of the additive include potassium pyrophosphate, calcium carbonate, sodium carbonate, sodium silicate, sodium gluconate, 4Na-EDTA, citric acid, salicylic acid, malonic acid, succinic acid, glutaric acid, pyrophosphoric acid, polyphosphoric acid, benzotriazole, sorbitol, glucose, One or more selected from the group consisting of carboxylic benzotriazole, tolytriazole, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and the like can be used. In the water-soluble detergent composition of the present invention, the additive may be included in the range of 0.001 to 10% by weight, preferably 0.1 to 5% by weight, but the blending amount may be changed depending on the type and purpose of the object to be cleaned and the cleaning method.

The water-soluble detergent composition of the present invention having the above composition has a physical property in the range of 25 to 35 dyne / cm (25 ° C) and specific gravity of 1.05 to 1.07 (25 ° C).

Although the manufacturing method of the water-soluble detergent composition of this invention can be obtained by mixing by a conventional method, it is preferable to mix with water in order of a polymeric dispersing agent, an alkali chemicals, an adjuvant, an alcoholic solvent, and surfactant. However, the preparation of the cleaning composition of the present invention is not limited thereto, and may be mixed in any order, all at the same time, or some may be mixed at the same time.

The cleaning composition of the present invention can be used for cleaning to remove contaminants of glass, metal, and plastics, and various cleaning methods such as simple deposition cleaning, ultrasonic cleaning, spray cleaning, vibration cleaning, and bubbling cleaning can be applied. . In addition, it is possible to apply the optimum cleaning conditions by adjusting the cleaning time, cleaning temperature, hem time, rinsing temperature and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only to illustrate the present invention, it should be understood that it does not limit the present invention.

[Example]

Examples 1 to 6.

1) Preparation of the object to be cleaned and the pollutant

Glass specimens of 7.5 cm × 2.5 cm × 0.1 cm size coated with an amide-based contaminant used as a release agent of the protective film were prepared. The object to be cleaned was heated at 100 ° C. for 10 minutes after application of a contaminant, and then allowed to stand at room temperature for 30 minutes and stored in a desiccator for at least 30 minutes to be used as a test specimen.

2) Preparation of Cleaning Composition

Each of the cleaning compositions was prepared in the following composition ratios.

Ingredient (wt%) Example One 2 3 4 5 6 Polymer dispersants Sodium salt of maleic acid-acrylic acid copolymer ¹⁾ 0.05 0.50 0.55 - 0.50 0.50 Sodium salt of polyacrylic acid ²⁾ - - - 0.50 0.50 0.50 Surfactants EO-PO ³⁾ 0.10 0.50 - 0.50 0.50 - EO-PO ⁴⁾ - - 0.10 0.50 - 0.50 Glucosides of C _6-8 ⁵⁾ 2.00 1.00 2.00 0.05 1.50 2.00 Decyl glucoside ⁶⁾ - 0.50 - 0.05 1.00 - Alkali Sodium hydroxide - 2.00 - - - - Potassium hydroxide 5.50 3.50 5.50 5.55 3.85 4.15 additive 4Na-EDTA 0.50 0.50 0.50 0.50 0.50 0.50 Na-Gluconate 1.20 0.85 0.70 1.20 1.00 1.20 Alcohol / glycol 0.50 0.50 0.50 1.00 0.50 0.50 water 90.15 90.15 90.15 90.15 90.15 90.15 1) Polymeric dispersant of Formula 2, weight average molecular weight 4,500, solid content 45% by weight, molar ratio of maleic acid / acrylic acid repeat unit 0.4 ~ 1.0
2) Polymeric dispersant of Chemical Formula 1, weight average molecular weight 70,000, solid content 40 wt%
3) Surfactant of Formula 3, weight average molecular weight 1,150, EO / PO molar ratio 0.5-2.0, R = C ₁₂ alkyl
4) Surfactant of Formula 3, weight average molecular weight 3,200, EO / PO molar ratio 0.5-2.0, R = C ₁₄ alkyl
5) Surfactant of Formula 4, weight average molecular weight 260 ~ 300, solid content 75% by weight
6) Surfactant of formula 4, weight average molecular weight 320, solid content 50% by weight

3) Performance Evaluation Method of Cleaning Composition

Performance evaluation of the prepared detergent composition may be applied to a variety of methods depending on the type and characteristics of the object to be cleaned, the type and characteristics of the pollutant in the present invention was evaluated as shown in Table 2 below to evaluate the performance of the cleaning composition, the results are shown in the following table 3 is shown. In addition, the photograph of the to-be-cleaned object before and after washing | cleaning with the cleaning composition which comprises the composition of Example 1 is shown in FIG.

Phase stability ◎: There is no sediment in the cleaner, and the color is clear (Circle): There is little sediment in a detergent, and a color is clear. (Triangle | delta): There are some deposits in a detergent, and a color is clear or normal Ｘ: Detergent in the detergent, blurry color, or forming a separate layer Cleaning performance (Double-circle): There is no contamination of a contamination source in a test specimen, and it is very favorable (Circle): The test specimen has little residue of a contamination source, and is favorable (Triangle | delta): There exists some residue of a contamination source in a test specimen, and is bad Ｘ: Poor source of test specimen remains Reattachment ◎: After cleaning, test specimens do not reattach contaminants and are very good (Circle): There is little reattachment of a source of contamination to a test specimen after washing | cleaning, and it is favorable (Triangle | delta): There exists a little reattachment of a source of contamination to a test specimen after washing | cleaning, and it is rather bad Ｘ: Reattachment of contaminant to test specimen after cleaning Bubble ◎: Bubble completely disappears within 1 minute ○: bubbles disappear completely within 3 minutes △ bubble completely disappears within 5 minutes Ｘ: bubbles remain for more than 5 minutes

division Example One 2 3 4 5 6 Phase stability ◎ ◎ ○ ○ ◎ ○ Cleaning performance ◎ ◎ ◎ ◎ ○ X Reattachment ◎ ◎ ○ ○ ○ △ Bubble ◎ ○ ○ ◎ ○ ○

As shown in Table 3, all of the compositions of Examples 1 to 6, which are the cleaning composition of the present invention, were excellent in phase stability, cleaning performance, and foaming. In addition, as shown in FIG. 1, contaminants before cleaning did not remain or reattach by cleaning.

On the other hand, the spectrum measured by the FT-IR surface conditions before and after cleaning is shown in Figure 2, as a result, all the peaks for the contaminants disappeared.

Therefore, it was confirmed through the above experiment that the cleaning performance of the cleaning composition of the present invention is excellent.

Claims (6)

In at least one organic solvent selected from the group consisting of water and alcohols or glycols,
(a) at least one polymer dispersant selected from homopolymers represented by formula (1) and salts thereof, and copolymers represented by formula (2) and salts thereof;
(b) a polyalkylene oxide-based surfactant represented by Formula 3 below;
(c) a polyglucoside surfactant represented by the following formula (4); And
(d) alkaline agents of pH 12 or higher;
A water-soluble detergent composition comprising a.
[Formula 1]

(Q in Formula 1 is an integer of 60 to 600)
(2)

(In Formula 2, l and m are the same as or different from each other and are an integer of 80 to 400.)
(3)

(In the above formula (3), R is an alkyl group of C ₁ to C ₁₅ , x and y are the same or different and are integers of 1 to 20, and the molar ratio of x / y is 0.5 to 2).
[Chemical Formula 4]

(In Formula 4, k and n are the same as or different from each other, an integer of 5 to 20)
The method of claim 1,
(a) 0.01 to 5% by weight of a polymeric dispersant;
(b) 0.01 to 10 wt% of a polyalkylene oxide surfactant;
(c) 0.01 to 10% by weight of a polyglucoside surfactant;
(d) 1 to 20% by weight of an alkaline agent;
(e) 0.1 to 10% by weight of alcohols; And
(f) 70 to 98% by weight of water
A water-soluble detergent composition comprising a.
3. The method according to claim 1 or 2,
Additionally polyoxyalkylene alkyl phenol ethers, polyoxy alkylene aryl phenol ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxy alkylene alkyl amines, sorbitan fatty acid esters, poly alkyl glucosides, A water-soluble detergent composition comprising 0.01 to 10% by weight of at least one conventional detergent for detergents selected from the group consisting of alkyl alcohol amines and aryl alcohol amines.
3. The method according to claim 1 or 2,
Additionally potassium pyrophosphate, calcium carbonate, sodium carbonate, sodium silicate, sodium gluconate, 4Na-EDTA, citric acid, salicylic acid, malonic acid, succinic acid, glutaric acid, pyrophosphoric acid, polyphosphoric acid, benzotriazole, sorbitol, glucose, carboxyl Further comprising 0.01 to 10% by weight of at least one conventional detergent adjuvant selected from the group consisting of cyclic benzotriazole, tolytriazole, diethanolamine, triethanolamine, monoisopropanolamine and diisopropanolamine A water-soluble detergent composition, characterized in that.
3. The method according to claim 1 or 2,
(D) the alkali agent is at least one hydroxide compound selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, butylammonium hydroxide and choline hydroxide A water-soluble detergent composition.
3. The method according to claim 1 or 2,
The alcohols (e) are ethanol, propanol, butanol, hexanol, isopropanol, heptanol, decanol, isohexanol, isooctanol, isotecanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol methyl ether Diethylene glycol methyl ether, triethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol ethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, A water-soluble detergent composition, characterized in that at least one alcohol or glycol selected from the group consisting of ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, and triethylene glycol monohexyl ether.

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