KR101621088B1 - Cleaning composition - Google Patents

Abstract

The present invention relates to a detergent composition containing no sulfamic acid compound,

The present invention provides a detergent composition comprising 0.1 to 20% by weight of a chlorine-based oxidizing agent, 0.1 to 10% by weight of a basic compound and water in a residual amount based on the total weight of the composition.

Cleaner, bacteria, slime, chlorine oxidizer, wet process equipment

Description

Cleaning composition

The present invention relates to a detergent composition for removing contaminants generated in a wet equipment. More particularly, the present invention relates to a detergent composition used for manufacturing semiconductor and panel display (hereinafter referred to as FPD).

In the semiconductor and FPD manufacturing processes, ultrapure water, which is prepared so as to have a theoretical electrical conductivity of 18.25 mega-ohms, is mostly used as a cleaning agent by removing organic substances, minerals, microparticles, and microorganisms dissolved in water to a maximum extent . In addition to the cleaning agent, a wet chemical such as a release agent and an etching solution is used. Although the ultrapure water minimizes the bacteria and the washing process is not in the open circulation state, even if the microorganisms are extremely small in the ultrapure water, the slime and the bacteria body are fixed in the inner wall of the tank or the pipe. In addition, if the chemicals used in the wet process in the semiconductor and FPD manufacturing process do not completely dissolve the target object (particles, heavy metals, photoresist metal film, etc.) and only peel off, the floating substances are immersed in the tank or pipe joint . If the thus generated contaminants are partially flowed out by the fluid and are adhered to the cleansing film and the subsequent process is carried out, pinholes, pits, wirings, bridges, and the like of the film are generated.

Therefore, in order to remove such contaminants, cleaning is periodically performed for maintenance of equipment. However, in the case of piping installed for process, it is difficult to remove contaminants unless it is separated and washed. In addition, if the physical force is not applied to the inside of the tank or the equipment for removing the contaminants, the effect is not satisfied. As a result, in order to remove such contaminants, it is necessary to stop the operation of the production facility, and the economic loss due to this is inevitable.

Accordingly, in order to avoid the economic loss as described above, various detergents with enhanced washing power have been developed. For example, in Japanese Patent Publication No. 41-15116, as a method for suppressing the growth of microorganisms in the treatment water, a solution of hypochlorite and sulfamate is mixed and reacted to prepare a reaction product solution of N-chlorosulfamate, Is supplied to the aqueous treatment stream. However, such a composition disadvantageously separates and removes a certain amount of contaminants adhering to the inner wall of the tank or the piping, but has a weak solubility to such contaminants, thereby causing secondary contamination of the separated contaminants to re-adhere to the inner wall of the tank or piping.

As a similar composition, Korea Patent Publication No. 10-2005-0004163 discloses a composition for preventing slime, which contains a chlorine-based oxidizing agent, a sulfamic acid compound, and an anionic polymer or a phosphonic acid compound, 41-15116, it is impossible to provide a sufficient contaminant removing power and there is a fear of occurrence of secondary contamination.

The present invention solves the above-mentioned problems of the prior art, and it is an object of the present invention to effectively remove and remove the contaminants existing or fixed in slime form in a wet equipment without applying physical force, And to provide a detergent composition which minimizes the occurrence of the detergent.

The present invention relates to a detergent composition containing no sulfamic acid compound,

The present invention provides a detergent composition comprising 0.1 to 20% by weight of a chlorine-based oxidizing agent, 0.1 to 10% by weight of a basic compound and water in a residual amount based on the total weight of the composition.

The detergent composition of the present invention not only efficiently removes and removes various contaminants present in the form of slime in the equipment, but also completely dissolves it, thereby providing an excellent effect of minimizing the secondary pollution.

In addition, it is composed of simple composition and exhibits strong washing power, so it is excellent in economic suitability, and it is easy to handle because it contains a large amount of water.

Therefore, when used in a manufacturing process of a semiconductor and a flat panel display, it is expected that not only the productivity can be improved but also the economic loss due to the pollutant can be greatly reduced.

The present invention relates to a detergent composition containing no sulfamic acid compound,

The cleaning composition comprising 0.1 to 20% by weight of a chlorine-based oxidizing agent, 0.1 to 10% by weight of a basic compound and water in a residual amount based on the total weight of the composition.

The detergent composition of the present invention is characterized in that it does not contain a sulfamic acid compound. When a sulfamic acid compound is included, the stability of the chlorinated oxidizer can be improved, but it is difficult to improve the detergent solubility of the detergent composition. On the other hand, since the basic compound contained in the detergent composition of the present invention not only stabilizes the chlorine-based oxidizing agent but also has excellent solubility to contaminants, it provides a very favorable effect to the detergent composition of the present invention. The detergent composition of the present invention is characterized by exhibiting a strong detergency with a very simple composition.

In the detergent composition of the present invention, the chlorine-based oxidizing agent serves to separate and remove contaminants by removing the chlorine-based oxidizing agent. Alkali metal hypochlorite such as sodium hypochlorite, potassium hypochlorite and the like; Alkaline earth metal hypochlorite such as calcium hypochlorite and barium hypochlorite; Alkali metal chlorites such as sodium chlorite and potassium chlorite; Alkaline earth metal chlorides such as calcium chlorite and barium chlorite; Alkali metal chlorates such as ammonium chlorate, sodium chlorate and potassium chlorate; Alkaline earth metal chlorides such as calcium chlorate and barium chlorate; And other metal chlorites such as nickel chlorite and the like. These may be used singly or in combination of two or more.

Among them, hypochlorite which is easy to handle can be more preferably used.

The content of the chlorine-based oxidizing agent is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight based on the total weight of the composition. When the concentration of the chlorine-based oxidizing agent is less than 0.1% by weight, it is difficult to effectively remove the contaminants, and when it exceeds 20% by weight, the irritation is large and the handling becomes difficult.

In the detergent composition of the present invention, the basic compound plays a role of solubilizing the contaminants and stabilizing the chlorine-based oxidizing agent. Examples of such basic compounds include inorganic bases such as ammonium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; And organic bases such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline hydroxide. These may be used singly or in combination of two or more.

Of these, sodium hydroxide and potassium hydroxide are the most preferable among the inorganic bases, and teriramethyl ammonium hydroxide is the most preferable among the organic bases.

The content of the basic compound is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight based on the total weight of the composition. When the basic compound is contained in an amount of less than 0.1% by weight, the solubility of the contaminants is lowered, and the stability of the chlorine-based oxidizing agent is also drastically reduced, so that it is difficult to expect a cleaning effect. When the amount exceeds 10% by weight, Which is difficult to control.

In the cleaning agent of the present invention, water is not particularly limited, but it is preferable to use deionized water. It is more preferable to use deionized water having a specific resistance of water of 18 M? / Cm or more to show the extent of removal of ions in water.

Further, the detergent composition of the present invention may further include a multifunctional additive. When the detergent composition of the present invention is used in a device made of a metal material such as SUS, the multifunctional additive has a pH buffering effect that prevents surface discoloration or corrosion of a material and suppresses pH change of the cleaning liquid.

Examples of the multifunctional additive include alkanolamine salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt and triisopropanolamine salt, Or two or more of them may be used in combination.

These alkanolamine salts are commercially available products such as AB RUST CM (product of LABEMA Co.), AB RUST A4 (product of LABEMA Co.), EMADOX-NA (product of LABEMA Co.), EMADOX-NB EMADOX-103 (manufactured by LABEMA Co.), EMADOX-D520 (manufactured by LABEMA Co.), AB Rust at (manufactured by LABEMA Co.), EMADOX- .) Can be used.

The content of the multifunctional additive is preferably 0.001 to 5.0% by weight, more preferably 0.01 to 2.0% by weight based on the total weight of the composition.

When the content of the multifunctional additive is within the above range, it is possible to avoid the problem of poor corrosion inhibiting ability due to insufficient coating effect for protecting the metal surface, and it is possible to prevent the pH buffering effect There is no problem of dropping.

The detergent composition of the present invention preferably has a pH of 8 to 14, more preferably 10 to 14. If the pH of the composition is less than 8, the stability of hypochlorous acid lowers and is easily decomposed. As a result, sterilization and detergency deteriorate, so that the removability of foreign matters may be significantly deteriorated.

The detergent compositions of the present invention may further comprise any additive known in the art to improve cleaning performance. Examples of the additives include pH adjusters, corrosion inhibitors, and the like, but are not limited thereto.

The components contained in the detergent composition of the present invention can be prepared according to known methods, and preferably have a purity of more than industrial grade.

Hereinafter, the present invention will be described in detail through examples and the like. However, the following examples are provided to further illustrate the present invention, and the scope of the present invention is not limited thereto.

Examples 1-5 and Comparative Examples 1-6.

(1) Preparation of cleaning agent composition

The cleaning agent compositions of Examples 1 to 5 and Comparative Examples 1 to 6 were prepared by mixing the ingredients shown in the following Table 1 according to the specified composition ratios.

(2) Evaluation of removability of plastic pipe material

The plastic piping to which the bacterial foreign matter was fixed was immersed in the detergent compositions of Examples 1 to 5 and Comparative Examples 1 to 6, respectively, and stirred at a constant speed for 30 minutes. The state of the contaminants was checked before and after the immersion and stirring, and the state of the surface of the pipe and the transparency of the cleaning agent were visually confirmed. The results are shown in the following Table 1 and Fig. 1 (using the cleaning agent of Example 1).

One 2 3 Removability Solubility ingredient content
(weight%) ingredient content
(weight%) ingredient content
(weight%) Example 1 NaClO 7 NaOH 5 - - O O Example 2 NaClO 7 NaOH 3 - - O O Example 3 NaClO 5 NaOH 3 - - O O Example 4 NaClO 5 TMAH 3 - - O O Example 5 NaClO 5 NaOH 3 *One) 0.5 O O Comparative Example 1 NaClO 7 - - - X X Comparative Example 2 - - NaOH 10 - - X X Comparative Example 3 NaClO 5 NaOH 3 *2) 0.05 △ X Comparative Example 4 NaClO 5 NaOH 3 * 3) 2 X X Comparative Example 5 *4) - - - - - X X Comparative Example 6 * 5) - - - - - X X

Note) NaClO: Sodium hypochlorite

NaOH: Sodium hydroxide

TMAH: tetramethylammonium hydroxide

* 1) Multifunctional additives: EMADOX NA

* 2) Surfactant: polyoxyethylene / polyoxypropylene ethylenediamine condensate

* 3) Chlorine compound stabilizer: sulfamic acid

* 4) Rust and Scale Remover: Hellotil

* 5) Rust and Stain Remover: SR-100

As can be seen from the results of Table 1, the detergent compositions of Examples 1 to 4 of the present invention showed excellent effects not only in peeling off the contaminants of the pipe but also in dissolving the contaminants by adding a basic compound to the chlorine-based oxidizing agent. Further, even when the multifunctional additive is additionally contained as in Example 5 of the present invention, the effect of preventing the detachment and solubility of contaminants is not deteriorated.

However, in the case of Comparative Examples 1 and 2 using a chlorine-based oxidizing agent or a basic compound alone; In the case of adding a surfactant (Comparative Example 3) or adding a sulfamic acid stabilizer (Comparative Example 4) to a composition composed of a chlorine-based oxidizing agent and a basic compound for the purpose of improving the removal performance of a foreign substance (Comparative Example 4) Results are shown. In addition, it was shown that the bacterial foreign matter was not removed even when the commercially available water-removing agent (Comparative Example 5 or Comparative Example 6) was used.

(3) Equipment combined with oil / minerals

In the flat panel display manufacturing process, in particular, the foreign matter in the tank used in the etching process was sampled with a cleaner wiper, the wipers were cut to a predetermined size, and then immersed in each of the detergent compositions prepared in Example 3 and Comparative Examples 1 to 6 And stirred for 30 minutes. The state of the wiper before and after the immersion, the transparency of the detergent composition and the precipitate were visually observed. The results are shown in the following Table 2 and FIG. 2 (using the cleaning agent of Example 3).

One 2 3 Removability Solubility ingredient content
(weight%) ingredient content
(weight%) ingredient content
(weight%) Example 3 NaClO 5 NaOH 3 - - O O Comparative Example 1 NaClO 7 - - - X X Comparative Example 2 - - NaOH 10 - - X X Comparative Example 3 NaClO 5 NaOH 3 *2) 0.03 △ △ Comparative Example 4 NaClO 5 NaOH 3 * 3) 5 △ X Comparative Example 5 *4) - - - - - X X Comparative Example 6 * 5) - - - - - X X

As can be seen from the results in Table 1, in the case of the detergent composition of Example 3, not only the foreign matter collected from the equipment was separated from the wiper but completely melted, so that secondary contamination of the beaker wall due to the separated foreign matter did not occur . However, in the case of the detergent compositions of Comparative Examples 3 and 4, a part of the foreign matter adhered to the wiper was separated, but it could not be dissolved, resulting in contamination of the beaker wall with secondary contamination (see FIG. 3). The detergent compositions of Comparative Examples 1, 2, 5, and 6 exhibited a failure to properly separate a part of the foreign matter adhered to the wiper.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing the result of cleaning a plastic pipe to which a bacterial foreign matter is adhered by immersing it in the detergent composition of Example 1 of the present invention.

FIG. 2 is a photograph showing the results of cleaning a foreign substance in a tank used in an etching process during the manufacturing process of a flat panel display with a cleaner wiper and immersing the wiper in the cleaning composition of Example 3 of the present invention.

FIG. 3 is a view showing a state in which a foreign matter in a tank used in an etching process during the manufacturing process of a flat panel display is collected with a cleaner wiper, and the wiper is dipped in the cleaning agent composition of Comparative Example 4 of the present invention, .

Claims (9)

A detergent composition that does not comprise a sulfamic acid compound and a surfactant, 0.1 to 20% by weight of a chlorine-based oxidizing agent, 0.1 to 10% by weight of a basic compound and water in a residual amount, based on the total weight of the composition, At least one multifunctional additive selected from the group consisting of a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, a monoisopropanolamine salt, a diisopropanolamine salt and a triisopropanolamine salt, lt; RTI ID = 0.0 > 10-14. < / RTI > The chlorine-based oxidizing agent according to claim 1, wherein the chlorine-based oxidizing agent is selected from the group consisting of chlorine, alkali metal hypochlorite, alkaline earth metal hypochlorite, alkali metal chlorite, alkali chlorite alkali metal chloride, alkaline earth metal chlorate and nickel hypochlorite ≪ / RTI > wherein the detergent composition comprises one or more of the following detergent compositions. The detergent composition according to claim 2, wherein the chlorine-based oxidizing agent is composed of at least one selected from the group consisting of chlorine, alkali metal hypochlorite and alkaline earth metal hypochlorite. The process according to claim 1, wherein the basic compound is selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline hydroxide Wherein the detergent composition comprises at least one type of detergent composition. delete delete  The detergent composition according to claim 1, wherein the multifunctional additive is included in an amount of 0.001 to 5.0% by weight based on the total weight of the composition. delete The detergent composition according to any one of claims 1 to 4 and claim 7, wherein said detergent composition is used for cleaning semiconductor and flat panel display wet process equipment.

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