KR20030069688A - Thinner composition for removing photosensitive resin - Google Patents

Abstract

PURPOSE: A thinner composition for removing a photosensitive resin composition is provided, to effectively remove the black resist adhered to the edge and back face of a glass substrate in short time and to reduce the step of interface. CONSTITUTION: The thinner composition comprises 1-50 parts by weight of propylene glycol monoalkyl ether; 50-99 parts by weight of alkyl ethanoate; 1-10 parts by weight of γ -butyrolactone; and 0.001-1 parts by weight of polyethylene oxide condensate of alkyl phenol as a surfactant. Also the thinner composition comprises 1-50 parts by weight of propylene glycol monoalkyl ether; 50-99 parts by weight of alkyl ethanoate; 1-10 parts by weight of γ -butyrolactone; and 0.001-1 parts by weight of linear-chained alkyl benzenesulfonic acid. Also the thinner composition comprises 1-50 parts by weight of propylene glycol monoalkyl ether; 50-99 parts by weight of alkyl ethanoate; 1-10 parts by weight of γ-butyrolactone; 0.001-1 parts by weight of polyethylene oxide condensate of alkyl phenol as a surfactant; and 0.001-1 parts by weight of linear-chained alkyl benzenesulfonic acid. Preferably the linear-chained alkyl benzenesulfonic acid is represented by the formula 1, wherein R is a linear alkyl group of C10-C14.

Description

Thinner composition for removing photosensitive resin composition {THINNER COMPOSITION FOR REMOVING PHOTOSENSITIVE RESIN}

The present invention relates to a resist cleaning liquid composition of a liquid crystal display device manufacturing process, and more particularly to a cleaning liquid thinner composition capable of effectively cleaning unnecessary resist after applying a resist in a liquid crystal display device manufacturing process.

In the case of manufacturing by lithography in order to form a fine circuit pattern such as a TFT LCD circuit or a semiconductor integrated circuit, a thin film such as an oxide film is generally formed on a substrate, and then a resist is uniformly applied on the surface thereof and exposed to this. And developing a resist pattern, and forming a pattern by selectively etching a thin film of the lower layer using the resist pattern as a mask, followed by a series of processes of completely removing the resist on the substrate. In the case of manufacturing a TFT-LCD or a semiconductor device by such a lithography method, after applying a resist to glass, a silicon wafer substrate, exposure and the like to remove unnecessary residues that may be formed under the substrate and remaining unnecessarily. Before the development process, a process of cleaning the substrate with a thinner is required.

Conventional thinner compositions include ether and ether acetates such as cellosolve, cellosolve acetate, propylene glycol ether, propylene glycol ether acetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; And esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate are used as thinners. As a prior art for such thinner compositions, Japanese Patent Application Laid-open No. Hei 4-49938 discloses the use of propyleneglycol monomethylether acetate (PGMEA) as a thinner. In addition, Japanese Patent Laid-Open No. 4-42523 discloses a method of using alkyl alkoxy propionate as a thinner.

However, the conventional methods use a single solvent such as ethyleneglycol monoethylether acetate (EGMEA), propyleneglycol monomethylether acetate (PGMEA) and ethyl lactate (EL). However, it has a problem with the following limitations.

That is, ethylene glycol monoethyl ether acetate has excellent dissolution rate but high volatility and flammability, and in particular, has a problem of reproductive toxicity such as leukopenia and induction of fetal abortion. The propylene glycol monomethyl ether acetate contains a material of beta (β) form in the manufacturing process, which also has a problem of causing teratogenicity and maternal toxicity. In addition, since ethyl lactate has a high viscosity and a low dissolution rate, a sufficient cleaning effect cannot be obtained by itself, and solvents such as acetone and methyl ethyl ketone have a low flash point, thereby degrading work safety.

In order to solve this problem, a method of mixing and using conventional single solvents has been researched and developed.

Japanese Patent Application Laid-Open No. Hei 4-130715 describes a method of using a mixed solvent consisting of an alkyl pyrufinic acid solvent and methyl ethyl ketone as a thinner. Japanese Patent Application Laid-Open No. 7-146562 uses a thinner composition composed of a mixture of propylene glycol alkyl ether and alkyl 3-alkoxypropionic acid. Japanese Patent Application Laid-Open No. 7-128867 describes a method using a thinner composition composed of a mixture of propylene glycol alkyl ether and butyl acetate and ethyl lactate, or a mixture of butyl acetate and ethyl lactate, and propylene glycol alkyl ether acetate. have. Japanese Patent Application Laid-Open No. 7-160008 uses a thinner composition composed of a mixture of propylene glycol alkyl ether propionate and methyl ethyl ketone, or a mixture of propylene glycol alkyl ether propionate and butyl acetate. U.S. Patent No. 4,983,490 uses a mixed solvent consisting of propylene glycol alkyl ether acetate and propylene glycol alkyl ether as a thinner composition, and U.S. Patent No. 4,886,728 uses a mixture consisting of ethyl lactate and methyl ethyl ketone as a thinner composition.

However, the above-described mixed solvents also have many difficulties in application to the manufacture of semiconductor devices and liquid crystal display devices, which are gradually becoming highly integrated and large diameters.

For example, a mixed solvent consisting of an alkyl pyrupin acid solvent and methyl ethyl ketone has poor solubility in 1,2-naphthoquinonediazide-based photosensitizer having a high esterification rate among the photosensitive agents which are important components of the photoresist film. When a highly volatile solvent, such as a mixed solvent of propylene glycol alkyl ether propionate and butyl acetate, is applied to the rear surface cleaning, the thickness of the photoresist film becomes severe as the substrate is cooled. In addition, when a low volatility solvent, such as a mixed solvent of ethyl lactate and methyl ethyl ketone, is used, the cleaning performance of the substrate edge region is poor. In particular, solvents such as methyl pyruvate and ethyl pyruvate are known to corrode metal parts in the photosensitive waste solution reservoir attached to the photosensitive film rotating coater for long term use.

In addition, when such a mixed solution is applied to a color large glass substrate used in a liquid crystal display device manufacturing process, there is a problem in that a black film is left unremoved and a thin black film is left unnecessarily removed. There is also a problem in that the interface between the remaining resist and the resist which is removed unnecessarily forms a band after development. That is, the interface between the remaining resist and the resist that is removed unnecessarily becomes thicker than the thickness of the actual resist and is not easily removed.

In view of the problems of the prior art as described above, the present invention is harmless to the human body, and a black resist used unnecessarily to be attached to the edges and the rear portion of a substrate used for manufacturing a liquid crystal display device, particularly a color large glass substrate, for a short time. An object of the present invention is to provide a thinner composition for removing a photosensitive resin composition that can be efficiently removed.

Another object of the present invention is to provide a thinner composition for removing the photosensitive resin composition having excellent cleaning property that can remove the thin black film, reduce the step difference of the interface, and clean the clean substrate after development.

In order to achieve the above object, the present invention provides a thinner composition for cleaning removal for removing unnecessary photoresist in the manufacturing process of a semiconductor device or a liquid crystal display device, a) propylene glycol monoalkyl ether; b) alkyl ethanoates; c) gamma butyrolactone; And d) a polyethylene oxide condensate surfactant of alkylphenols.

Preferably, the thinner composition of the present invention comprises a) 1 to 50 parts by weight of propylene glycol monoalkyl ether; b) 50 to 99 parts by weight of alkyl ethanoate; c) 1 to 10 parts by weight of gamma butyrolactone; And d) 0.001 to 1 part by weight of polyethylene oxide condensate surfactant of alkylphenols.

The present invention also provides a thinner composition for cleaning removal for removing unnecessary photoresist in the manufacturing process of a semiconductor device or a liquid crystal display device, comprising: a) propylene glycol monoalkyl ether; b) alkyl ethanoates; c) gamma butyrolactone; And d) straight chain alkylbenzene sulfonic acid.

Preferably, the thinner composition of the present invention comprises a) 1 to 50 parts by weight of propylene glycol monoalkyl ether; b) 50 to 99 parts by weight of alkyl ethanoate; c) 1 to 10 parts by weight of gamma butyrolactone; And d) 0.001 to 0.1 parts by weight of linear alkylbenzenesulfonic acid.

The present invention also provides a thinner composition for cleaning removal for removing unnecessary photoresist in the manufacturing process of a semiconductor device or a liquid crystal display device, comprising: a) propylene glycol monoalkyl ether; b) alkyl ethanoates; c) gamma butyrolactone; d) polyethylene oxide condensate surfactants of alkylphenols; And e) a straight chain alkylbenzene sulfonic acid.

Preferably, the thinner composition of the present invention comprises a) 1 to 50 parts by weight of propylene glycol monoalkyl ether; b) 50 to 99 parts by weight of alkyl ethanoate; c) 1 to 10 parts by weight of gamma butyrolactone; d) 0.001 to 1 parts by weight of polyethylene oxide condensate surfactant of alkylphenols; And e) 0.001 to 0.1 parts by weight of linear alkylbenzenesulfonic acid.

Hereinafter, the present invention will be described in detail.

The resist cleaning liquid thinner composition of the present invention is conventionally containing a compound such as ethylene glycol monoethyl ether acetate, methyl ethyl ketone, and flammability and storage problems which are harmful to human body, such as methanol, isopropyl alcohol, dimethyl sulfoxide, and the like. It is very stable in terms of human hazards and shelf life because it can replace the cleaning liquid used for.

In the thinner composition of the present invention, a) propylene glycol monoalkyl ether, b) alkyl ethanoate, and c) alkyl lactone (preferably gamma butyrolactone) used as the solvent are each selected to be extremely pure in semiconductor grade. It can be used in the VLSI grade, the filtered to 0.1 ㎛ level is used.

The a) propylene glycol monoalkyl ether may be used having an alkyl group having 1 to 5 carbon atoms, specific examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. It is preferably selected from the group consisting of. Among them, it is more preferable to use propylene glycol monomethyl ether having excellent solubility in polymers.

The propylene glycol monomethyl ether has been reported to have high safety for the human body when exposed to air, and in terms of metabolism, it is rapidly decomposed into propylene glycol and alcohol and is safe. In the toxicity test, LD ₅₀ (mouse) = 4.4 g / kg, which represents 50% lethal dose due to oral administration to mice, is rapidly degraded by hydrolysis. Its physical properties are boiling point 132.8 ° C., flash point (measured by closed cup method) 32 ° C., viscosity (at 25 ° C.) 1.86 cps, surface tension 26.5 dyne / cm 2, and solubility parameter 10.4.

The content of the propylene glycol monoalkyl ether is preferably used in 1 part by weight 50 parts by weight.

Further, in the thinner composition of the present invention, b) alkyl ethanoate having 1 to 4 carbon atoms of an alkyl group can be used, and specific examples thereof include methyl ethanoate, ethyl ethanoate, isopropyl ethanoate, It is preferable to select at least one from the group consisting of normal propyl ethanoate and butyl ethanoate. Among them, it is more preferable to use a solvent such as isopropyl ethanoate, normal propyl ethanoate, or butyl ethanoate, and these have a relatively low viscosity and moderate volatilization, which lowers the viscosity of the thinner composition upon use. It exhibits excellent solubility. It is preferable to use the usage-amount of such alkyl ethanoate 50-99 weight part.

In this case, butyl ethanoate, which is one of the alkyl ethanoates, has excellent solubility in various resins, and particularly has low surface tension and excellent volatility, so that even when only a predetermined content is added to the thinner composition, excellent interfacial properties can be exhibited. . The butyl ethanoate shows LD50 (mouse) = 7.0 g / kg 50% mortality due to oral administration to mice in the toxicity test, physical properties are boiling point 126.1 ℃, flash point (measured by closed cup method) 23 ℃, Viscosity (at 25 ° C.) 0.74 cps, surface tension 25 dyne / cm 2.

In the thinner composition of the present invention, c) alkyl lactone is used, and preferably gamma butyro lactone is used. The gamma butyrolactone content is used in an amount of 1 to 10 parts by weight.

In the thinner composition of the present invention, as the nonionic surfactant, d) polyethylene oxide condensates of alkylphenols, linear alkylbenzenesulfonic acids, or mixtures thereof are used. In the present invention, it is possible to remove the black residue of the resist-removed portion including the polyethylene oxide condensate surfactant of the alkylphenol, or to remove the black band after development including the alkylbenzenesulfonic acid, or to include both components. It has the feature to remove all black residue and black strip cleanly.

That is, the polyethylene oxide condensate of the alkylphenol serves to remove the black strip after development. The polyethylene oxide condensate surfactant of the alkyl phenol includes a condensation product obtained by condensation of an alkyl phenol having a linear or branched C ₆ to C ₁₂ alkyl group with 5 to 25 moles of ethylene oxide per mole of the alkyl phenol. Examples of alkyl substituents in the above-mentioned compounds may be those derived from polymerized propylene, diisobutylene, octene or nonene. Examples of this type of compound include nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol, dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol, and about 15 moles of ethylene oxide per mole of phenol. Diisooctylphenol and the like. They have excellent solubility in water and various solvents, and serve to reduce the step difference at the interface when the thinner meets the photosensitive resin, and commercialized products include nonionic monopole series surfactants of Southeast Synthetic. It is preferable that the content of the nonionic surfactant is 0.001 to 1 parts by weight, and if the content of the nonionic surfactant is less than 0.001 parts by weight, the volatility and cleaning power of the thinner at the end of the substrate are significantly reduced, and more than 1 part by weight. If the foam is severely generated, it is inconvenient to use.

In addition, the linear alkylbenzenesulfonic acid slips the adhesion to the substrate interface (especially when removing the black matrix) to remove the black residual film of the portion where the resist is removed by the thinner. As the linear alkylbenzenesulfonic acid, it is preferable to use a compound represented by the following formula (1).

[Formula 1]

In Formula 1, R is a straight alkyl group having 10 to 14 carbon atoms.

Specific examples of the alkylbenzenesulfonic acid include decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, quaddecylbenzenesulfonic acid, and the like. Especially dodecylbenzenesulfonic acid is the most effective. The content of the linear alkylbenzenesulfonic acid is preferably used in 0.001 to 0.1 parts by weight.

As described above, the present invention is harmless to the human body and has excellent storage stability of the thinner composition having the composition and content as described above, and in particular, it can effectively remove unnecessary photoresist film when applied to the manufacturing process of semiconductor devices and liquid crystal display devices.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

The substrate specimens used in this example were prepared as follows.

A silicon oxide substrate 8 inches in diameter was used. These substrates were first washed in two baths, each containing a hydrogen peroxide / sulfuric acid mixture (soaked for 5 minutes in each bath) and then rinsed with ultrapure water. This process was carried out in a customized cleaning facility. These substrates were then spin-dried in a spin dryer (VERTEQ, model SRD 1800-6). Subsequently, each photosensitive film was coated with a predetermined thickness on the upper surface of the substrate. A rotary coating machine (Korea Semiconductor Co., Model EBR TRACK) was used to apply the photosensitive film.

In the rotation coating operation, 10 cc of the photosensitive film composition was added dropwise to the center of the stationary substrate. The photosensitive film was then distributed for 3 seconds at 500 rpm using a rotating coater. Thereafter, the substrate was accelerated at a rotational speed of about 2000 to 4000 rpm to adjust each photosensitive film to a predetermined thickness. The rotation time at this speed is about 20-30 seconds.

Examples 1-7 and Comparative Examples 1-3

Thinner compositions having the composition and content as shown in Table 1 were prepared, respectively.

Division (weight part) PGME ¹ PGEE ² n-PE ³ BE ⁴ GBL ⁵ OP-1015 ⁶ DDBSA ⁷ Example One 60 - 35 - 5 0.5 0.01 2 50 - - 45 5 0.5 0.01 3 40 - 55 - 5 0.5 0.01 4 - 30. - 63 7 0.5 0.01 5 50 - - 45 5 0.5 0.01 6 50 - 45 - 5 0.5 - 7 30 - 63 - 7 - 0.01 Comparative example One 60 - 35 - 5 - - 2 50 - 50 - - - - 3 - 20 - 80 - - - 4 5 - 90 - 5 0.5 0.01

week)

1.PGME: Propyleneglycol monomethyl ether,

2. PGEE: Propyleneglycol monoethyl ether,

3. BE: Butyl ethanoate,

4. i-PE: isopropyl ethanoate,

5. n-PE: n-propyl ethanoate,

6.GBL: gamma butyro lactone,

7. OP-1015: refers to the "monopol OP-1015" of Southeast Synthesis by condensation polymerization of 5 moles of ethylene oxide to 1 mole of octyl phenol,

8. DDBSA: dodecyl benzene sulfonic acid.

Unnecessary photoresist removal experiment of thinner composition with respect to photosensitive resin composition

After applying each photosensitive film composition to the 8-inch silicon oxide substrate experiment to remove the unnecessary photosensitive film of the edge portion with the thinner composition of Examples 1 to 7 and the thinner composition of Comparative Examples 1 to 4 conventionally used (Edge Bead Removing experiment) (Hereinafter referred to as EBR experiment). EBR experiments also used the same spin coater that was used to apply the photoresist to the substrate.

Each thinner composition shown in Table 1 was sprayed onto the photosensitive film-coated substrate of the photosensitive resin composition shown in Table 2 through an EBR nozzle to remove the spherical photosensitive material in the edge portion under the conditions shown in Table 3 below. Each thinner composition was supplied from a pressure vessel equipped with a pressure gauge and the pressurization pressure was 1.0 kgf, and the flow rate of the thinner composition from the EBR nozzle was 10-20 cc / min.

The EBR experimental evaluation for each photosensitive resin composition is shown in Table 4 below.

Photosensitive resin composition type and film thickness division Composition type Composition product name Film thickness (㎛) Photosensitive resin composition g-line type positive type DTFR-2000 1.8 Resin Black Matrix FFO Corp 2 Red 2 Green 2 Blue 2

EBR experimental conditions division Rotation speed (rpm) Time (sec) Distribution conditions 500 3 Spin coating Adjustable according to the photoresist thickness EBR condition 1000 6 Drying conditions 1 1000 3 Drying conditions 2 0 0

EBR Experimental Evaluation on Photosensitive Resin Compositions division Example Comparative example One 2 3 4 5 6 7 One 2 3 4 g-line positive photosensitive resin, Red, Green, Blue EBR Drying Conditions 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ △ ○ △ EBR Drying Condition 2 ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ △ △ × EBR end residue ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ △ △ × Resin Black Matrix EBR Drying Conditions 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ △ EBR Drying Condition 2 ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ △ △ × With or without EBR assay radish radish radish radish radish U radish U U U U Black belt after development radish radish radish radish radish radish U U U U U

In Table 4, the term "developing" means spraying a 100-dilution solution of JSR developer for 60 seconds on the substrate after the resist coating and thinner process and until the soft bake.

Evaluation symbol '◎' indicates that the shape of the edge area after EBR is clear, and '○' indicates that the shape of the edge area after EBR is more than 80% good, and evaluation symbol '△' indicates the edge area after EBR. The shape of is shown to be distorted by the dissolution of the thinner, 'x' indicates that the tailing of the film occurs in the edge portion after the EBR.

As shown in Table 4, the thinner compositions according to the present invention exhibited excellent EBR performance (clean edge shape) for all photoresist films, and removed black bands from the color resist after development. Also, no black film was formed on the substrate to which the thinner liquid was introduced. That is, in Examples 1 to 5 including both the polyethylene oxide condensate surfactant of the alkylphenol and the alkylbenzenesulfonic acid, neither the black residual film nor the black band was formed. In addition, as shown in Example 6, even if only the polyethylene oxide condensate surfactant of the alkylphenol was included, the black residual film of the portion where the resist was removed did not occur, and in the case of containing the alkylbenzene sulfonic acid as in Example 7, the black band after development Did not appear. Thus, it can be seen that the photoresist removal performance is excellent in the case of including the polyethylene oxide condensate surfactant of the alkyl phenol, alkylbenzene sulfonic acid, or a mixture thereof as in the present invention.

On the other hand, in Comparative Examples 1 to 4 without the two additives (monopol OP-1015, DDBSA), both the black film and the black band remained. This acts as a factor to lower the production yield of semiconductor devices and liquid crystal display devices due to equipment contamination, etc. during the subsequent process.

In addition, the thinner compositions according to the invention maintained an equally good cross-sectional shape even when changing the EBR rpm conditions. This means that the thinner composition according to the present invention exhibits the same performance under various conditions, not only in specific conditions, but is more stable than a conventional thinner composition against changes in process conditions. Moreover, the thinner composition of the present invention shows that the black film and the black strip can be removed cleanly even when the color filter resist is removed, which can be used in various processes.

As described above, the thinner composition for removing the photosensitive resin composition according to the present invention is used on the edges and rear portions of substrates used in the manufacture of liquid crystal display devices, especially color large glass substrates, without being harmful to the human body. The attached black resist can be removed efficiently in a short time, and the thin black film can be removed, and the step difference of the interface can be reduced to clean the clean substrate after development so that it can be applied to various processes. There is an effect to simplify and improve the production yield.

Claims (10)

In the cleaning removal thinner composition for removing the unnecessary photosensitive film in the manufacturing process of a semiconductor element or a liquid crystal display element, a) propylene glycol monoalkyl ether; b) alkyl ethanoates; c) gamma butyrolactone; And d) polyethylene oxide condensate surfactants of alkylphenols Thinner composition comprising a. The method of claim 1, a) 1 to 50 parts by weight of propylene glycol monoalkyl ether; b) 50 to 99 parts by weight of alkyl ethanoate; c) 1 to 10 parts by weight of gamma butyrolactone; And d) 0.001 to 1 parts by weight of polyethylene oxide condensate surfactant of alkylphenols Thinner composition comprising a. In the cleaning removal thinner composition for removing the unnecessary photosensitive film in the manufacturing process of a semiconductor element or a liquid crystal display element, a) propylene glycol monoalkyl ether; b) alkyl ethanoates; c) gamma butyrolactone; And d) straight chain alkylbenzene sulfonic acids Thinner composition comprising a. The method of claim 3, wherein a) 1 to 50 parts by weight of propylene glycol monoalkyl ether; b) 50 to 99 parts by weight of alkyl ethanoate; c) 1 to 10 parts by weight of gamma butyrolactone; And d) 0.001 to 0.1 parts by weight of linear alkylbenzenesulfonic acid Thinner composition comprising a. In the cleaning removal thinner composition for removing the unnecessary photosensitive film in the manufacturing process of a semiconductor element or a liquid crystal display element, a) propylene glycol monoalkyl ether; b) alkyl ethanoates; c) gamma butyrolactone; d) polyethylene oxide condensate surfactants of alkylphenols; And e) straight chain alkylbenzene sulfonic acid Thinner composition comprising a. The method of claim 5, a) 1 to 50 parts by weight of propylene glycol monoalkyl ether; b) 50 to 99 parts by weight of alkyl ethanoate; c) 1 to 10 parts by weight of gamma butyrolactone; d) 0.001 to 1 parts by weight of polyethylene oxide condensate surfactant of alkylphenols; And e) 0.001 to 0.1 parts by weight of linear alkylbenzenesulfonic acid Thinner composition comprising a. The method according to any one of claims 1 to 6, Thinner composition wherein the propylene glycol monoalkyl ether is selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. The method according to any one of claims 1 to 6, Wherein said alkyl ethanoate is selected from the group consisting of methyl ethanoate, ethyl ethanoate, isopropyl ethanoate, normal propyl ethanoate, and butyl ethanoate. The method according to claim 1 or 5, Polyethylene oxide condensate surfactant is a straight-chain or alkylphenols having an alkyl group of a branched arrangement of a C ₆ - C ₁₂ and in which the alkyl phenol is thinner composition per mol of 5 to condensation which the condensation of ethylene oxide of 25 mol product of alkylphenol. The method according to claim 3 or 5, Thinner alkylene sulfonic acid is a compound represented by the formula (1). [Formula 1] In Chemical Formula 1, R is a C10-14 linear alkyl group.