KR20030030364A - Developing aqueous solution for Photoresist - Google Patents

Abstract

PURPOSE: Provided is an aqueous developer solution for photoresist which can rapidly disperse or dissolve a pigment for coloring or shielding and a photocurable resin component, and has broad acceptable ranges of exposure and developing condition, as well low foaming and excellent anti-foaming properties. CONSTITUTION: The aqueous developer solution consists of 0.1-10 parts by weight of any one alkaline compound selected from the group consisting of inorganic alkaline compound, organic alkaline compound, and mixture thereof; 1-25 parts by weight of non-ionic surfactant(formula 1) formed by adducting an alkylene oxide to aromatic alcohol; and 0.5-15 parts by weight of non-ionic surfactant(R1-O-£AO|p-R2) having polyoxy alkylene ether group, which is formed by adducting an alkylene oxide to hydrocarbon alcohol. The aqueous developer solution also shows developability and reproducibility of pattern.

Description

Developing aqueous solution for photoresist

The present invention relates to a developer used in the production of negative photoresists, color filter photoresists, and the like, and in particular, it is possible to disperse or dissolve pigments and photocurable resin components for coloring or shading quickly, It is related with the aqueous developing solution which shows developability and reproducibility of a pattern, and can eliminate the problem at the time of image development by foaming.

In general, a color liquid crystal display forms a color filter on which a black matrix resin and red, green, and blue pixels are formed on a transparent substrate such as glass, and a transparent conductive film such as ITO is formed on the transparent substrate by sputtering. It is manufactured by the method of forming an alignment film again on this and injecting a liquid crystal. Although the method of forming the color filter used for a color liquid crystal display varies, the pigment dispersion method which apply | coats the photosensitive composition which disperse | distributed organic pigment and inorganic pigment on a transparent substrate, and then irradiates and develops is mainly used.

Alkaline developer is generally used in the developing process for forming the color filter. The developing solution is used to rapidly disperse or dissolve organic pigments and inorganic pigments and photocurable resin components for coloring or shading contained in the photosensitive composition in the developing process. It should be possible. In addition, a change in developing performance over time should not occur due to repetition of developing treatment or absorption of carbon dioxide gas in the air. Although a tetramethyl ammonium hydroxide aqueous solution is widely used as an alkaline developer generally used, this developer is not able to sufficiently remove an unnecessary coating film, not only scum occurs in the obtained pixel, but also it is difficult to form a pixel having excellent pattern edges.

Therefore, efforts have been made to improve such a problem. Japanese Patent Application Laid-Open No. 7-120935 discloses an alkaline developer having an aqueous solution containing an alkaline compound and a nonionic surfactant having a pH of 9 to 13 and a content of 0.01 to 1.0% by weight of the nonionic surfactant. In addition, Japanese Patent Laid-Open No. 9-171261 discloses a developer consisting of a buffered aqueous solution prepared by combining a nonionic surfactant, a strong base material and a weak base material. However, the alkaline developer disclosed in this document also does not have sufficient stability over time in developing performance. In particular, when using the developer disclosed in US Pat.

Japanese Unexamined Patent Application Publication No. Hei 6-109916 discloses a developing solution containing, as a main component, an anionic surfactant having sodium carbonate and sodium sulfonate base. However, it is necessary to add an antifoaming agent in order to suppress this since the foaming rate increases when developing with this developer, but the added antifoaming agent not only causes the deterioration of developability, but also causes many problems in the developing process.

Accordingly, the technical problem to be solved by the present invention is to solve the above problems, to quickly disperse or dissolve pigments and photocurable resin components for coloring or shading, as well as a wide range of exposure to light exposure and development conditions and stability over time The present invention provides an aqueous developer for photoresists that can exhibit excellent developability and reproducibility of a pattern, and has a low foaming rate and excellent antifoaming property, which can eliminate problems in developing by foaming.

In order to achieve the above technical problem, the present invention is an inorganic alkaline compound, an organic alkaline compound and any one of the alkaline compounds selected from the group consisting of 0.1 to 10 parts by weight; 1 to 25 parts by weight of a nonionic surfactant represented by Formula 1; And an aqueous solution containing 0.5 to 15 parts by weight of a nonionic surfactant represented by Formula 2 below.

In Formula 1, R is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group and a styrene group, m is an integer of 1 to 3 as the number of substituents , AO is at least one selected from the group consisting of oxyethylene group, oxypropylene group and polyoxyethylene polyoxypropylene block copolymer, n is an integer of 0 to 4, o is an integer of 1 to 20.

In Formula 2, R 1 and R 2 are each independently selected from a hydrogen atom, an alkyl group having 4 to 18 carbon atoms and an alkenyl group having 4 to 18 carbon atoms, and AO is an oxyethylene group, an oxypropylene group, and At least one selected from the group consisting of polyoxyethylene-polyoxypropylene block copolymers, and p is an integer of 1 to 20.

Hereinafter, the present invention will be described in more detail.

The developer of the present invention contains 0.1 to 10 parts by weight of an inorganic alkaline compound, an organic alkaline compound or a mixture thereof. These alkaline compounds improve the developability of the developing solution and shorten the developing time. If the content is less than 0.1 part by weight, there is a limit in improving the developability. If the amount exceeds 10 parts by weight, pixels may be missing or peeled off during development. . The preferred content of the alkaline compound is 1 to 10% by weight, more preferably 1 to 8% by weight.

As the inorganic alkaline compound, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide and the like can be used. It is preferable to use potassium carbonate and sodium carbonate among inorganic alkaline compounds, and these compounds are less affected by carbon dioxide gas contained in the air even when used for a long time, so that there is little risk of deterioration of the developer and excellent stability over time. Because of this. In particular, potassium carbonate may be preferred because it does not contain sodium, which causes trouble in the electronic driving circuit of the liquid crystal display device equipped with the color filter, so that problems due to corrosion can be prevented.

Moreover, as an organic alkaline compound contained in the developing solution of this invention, Tetra alkyl ammonium hydroxide compounds, such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, and 2-hydroxyethyl trimethyl ammonium hydroxide; Alkylamine compounds such as monomethylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine and diisopropylamine; Alkanol amine compounds, such as ethyl alcohol amine, 2-dimethylamino ethyl alcohol, 2-diethyl amino ethyl alcohol, and 2-diisopropyl amino ethyl alcohol, etc. can be used.

These alkaline compounds can be used individually or in mixture of 2 or more types.

The developing solution of the present invention contains 1 to 25 parts by weight of a nonionic surfactant represented by the following formula (1), in which an alkylene oxide is added to an aromatic alcohol.

<Formula 1>

In Formula 1, R is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group and a styrene group, m is an integer of 1 to 3 as the number of substituents , AO is at least one selected from the group consisting of oxyethylene group, oxypropylene group and polyoxyethylene polyoxypropylene block copolymer, n is an integer of 0 to 4, o is an integer of 1 to 20.

In the general formula (1), examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, isopropyl group, butyl group, isobutyl group, amyl group and nonyl group. Examples of the alkenyl group having 2 to 5 carbon atoms include vinyl group, 1-propenyl group, aryl group, 1-butenyl group, 2-pentenyl group and the like. The carbon number of the alkyl group and the alkenyl group is preferably 5 or less, more preferably 3 or less, in consideration of solubility and developability in water. In addition, when n exceeds 4, the water solubility decreases and the rinsing property decreases, so it is kept below 4. In addition, AO is an oxyethylene group, an oxypropylene group, or a polyoxyethylene polyoxypropylene block copolymer, and if o is 1-20, AO may be same or different.

In the developer of the present invention, the nonionic surfactant in which alkylene oxide is added to the aromatic alcohol of Formula 1 has excellent penetration effect on the coating film of the non-exposed part during development and has excellent solubility selectivity so that it can be developed in a shorter time. .

Examples of the nonionic surfactant compound represented by the formula (1) include phenolic alcohols such as phenol, methylphenol, ethylphenol, isopropylphenol, vinylphenol and styrene, benzyl alcohol, methylbenzyl alcohol, ethylbenzyl alcohol and iso Compounds in which ethylene oxide or propylene oxide is added to various aromatic alcohols such as benzyl alcohol such as propylbenzyl alcohol, and the like, and more specifically, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Glycol styrenated phenyl ether and the like. Such nonionic surfactant can be used individually or in mixture of 2 or more types.

The content of the nonionic surfactant represented by the formula (1) is 1 to 25 parts by weight, preferably 3 to 25 parts by weight, and more preferably 3 to 20 parts by weight. If the content is less than 1 part by weight, it is difficult to disperse or dissolve the photosensitive composition of the non-exposed part quickly in the alkaline developer in the developing step of the coating film formed from the photosensitive composition, and there is a problem that scum, developing residues, etc. are reattached. In addition, when the content exceeds 25% by weight, the entire photosensitive resin is peeled off the substrate, making it difficult to form a selective pattern, and the degree of foaming of the developing solution is increased, leading to a problem of deterioration in developing workability.

The developer of the present invention contains 0.5 to 15 parts by weight of a nonionic surfactant represented by the following formula (2) having a structure in which an alkylene oxide is added to a hydrocarbon alcohol.

<Formula 2>

In Formula 2, R 1 and R 2 are each independently selected from a hydrogen atom, an alkyl group having 4 to 18 carbon atoms and an alkenyl group having 4 to 18 carbon atoms, and AO is an oxyethylene group, an oxypropylene group, and At least one selected from the group consisting of polyoxyethylene-polyoxypropylene block copolymers, and p is an integer of 1 to 20.

In Formula 2, R1, R2 may be the same or different from each other. Representative examples of the alkyl group having 4 to 18 carbon atoms include octyl group, 2-ethylhexyl group, decyl group, lauryl group, cetyl group, stearyl group, isodecyl group, tridecyl group, isotridecyl group, and the like. In particular, it is preferable to use octyl group, decyl group, lauryl group and tridecyl group in consideration of solubility and developability in water. Moreover, a nonyl group is mentioned as a typical example of the alkenyl group which has 4-18 carbon atoms. AO is an oxyethylene group, an oxypropylene group, or a polyoxyethylene polyoxypropylene block copolymer, and if p is 1-20, AO may be same or different. In particular, p is preferably an integer of 4 to 12 in consideration of the rinsing property, viscosity, and foamability of the developer.

Examples of the nonionic surfactant represented by the formula (2) include octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, undecyl alcohol having 11 to 15 carbon atoms, dodecyl alcohol, cetyl alcohol, stearyl alcohol, and the like. Examples of the hydrocarbon alcohol having a bivalent or divalent hydroxyl group include adducts of ethylene oxide or propylene oxide having a linear or branched alkyl or alkenyl group, and methyl ether, acyl ether, etc. of such a compound. These can be used individually or in mixture of 2 or more types.

In the developing solution of the present invention, the content of the nonionic surfactant represented by the formula (2) is 0.5 to 15 parts by weight based on the total weight of the developing solution, preferably 1 to 10 parts by weight, and more preferably 1 to 8 parts by weight. to be. If the content is less than 0.5 parts by weight, the effect according to the present invention is insignificant, and if the content is more than 15% by weight, the degree of foaming of the developer is increased, making it difficult to form a pattern, and the surfactant itself remains as a residue on the substrate, causing surface staining. Becomes

The developing method to which the developing solution according to the present invention consisting of an aqueous solution containing the above-described components is applied is not particularly limited, and can be applied to methods such as immersion developing method, rocking developing method, shower spray developing method, paddle developing method and the like. have. The developer of the present invention is very useful when developing a coating film formed by using a photosensitive composition in which fine particles such as negative photoresist, organic pigment, and inorganic pigment are dispersed, and is not only excellent in development stability over time, but also a black matrix. Even in the case of a color filter photoresist formed using a photosensitive composition having a low transmittance to irradiated light such as a resin, unnecessary fine particles and a resin component can be sufficiently dispersed and dissolved. In addition, development residues do not occur, organic pigments, inorganic pigments or resins are not re-adhered onto the substrate, and pixels with excellent adhesion to the substrate without missing or peeling off the film can be formed. . In addition, the foaming rate is low and excellent in the antifoaming can eliminate the problem during development by foaming.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Examples 1-16

Potassium carbonate, polyethylene glycol styrene phenyl ether of formula 1, and lauryl alkoxy compound of formula 2 are sequentially added to the mixing tank equipped with a stirrer according to the components and contents shown in Tables 1 and 2 below, Ultra pure water was added so as to be 100% by weight, and then stirred at a speed of 200 to 600 rpm for 0.5 to 1 hour at room temperature to prepare a developer stock solution. Subsequently, the developer according to the present invention was prepared by diluting the prepared developer stock solution 100 times with ultrapure water.

Comparative Examples 1 to 8

A developing solution was prepared in the same manner as in Example except that the composition components and contents thereof were changed as shown in Table 3 below.

The pH, storage property, foamability, antifoaming property, resolution, and developability of the developer according to each of the Examples and Comparative Examples prepared as described above were evaluated according to the following criteria, and are shown in Table 1, Table 2, and Table 3.

<pH measurement>

The temperature of the developing solution was kept at 25 degreeC, and it measured using the pH meter made from WTW.

<Preservation evaluation>

After storing the developer stock solution at room temperature (20 ℃ / 1 month) and high temperature (40 ℃ / 7 days), the appearance of the developer stock solution was visually evaluated. As a result, it was evaluated as 'excellent'.

<Evaluation of foaming and antifoaming>

The foaming property and the anti-foaming property were evaluated for the developer which received the 'good' evaluation in the preservation evaluation. 1 mL of developer was added to a 10 mL glass tube, and the nitrogen gas was bubbled for 1 minute at a predetermined pressure. Then, the height of the bubbles generated was measured and foamability was evaluated in three steps as follows.

◎: 0-5mm

ｏ: 0 ~ 10mm

×: 11 mm or more

In addition, the anti-foaming property of the developer was allowed to stand for 10 minutes after the generated foam was evaluated for the height of the foam in accordance with the foamability evaluation criteria.

<Resolution and Developability>

In the preservation evaluation, the resolution and the developability were evaluated for a developer that received a 'good' evaluation and some developers that received a 'poor' evaluation. The color filter photoresist was spin-coated on the glass substrate so that the thickness of the coating film was 1.0 μm, and then pre-baked at 120 ° C. for 2 minutes. Subsequently, the board | substrate with which the color filter photoresist coating film was formed was exposed at 30mJ / cm <^2> exposure amount using the test pattern mask for evaluation. Subsequently, using a developer sample at 28 ° C., the development time was developed according to the shower development method. Then, after rinsing with ultrapure water, the resolution was evaluated as follows.

A: The pixel of 10 micrometers or less can be obtained.

B: What can obtain the pixel of 15-20 micrometers.

C: What can obtain the pixel of 30-40 micrometers.

D: Poor development.

E: The pattern is peeled off.

The developability was evaluated as 'excellent' for having three or more A's between 40 and 80 seconds of development time, and 'poor' below.

Example number One 2 3 4 5 6 7 8 Composition ratio of developer solution (wt%) Alkaline compounds Sodium carbonate One One One One One One One One Potassium carbonate 4 4 4 4 4 4 4 4 Nonionic surfactant 1-polyethylene glycol styrene phenyl ether (EO) ₁₂ 5 5 5 5 10 10 10 10 2-Polyethyleneglycollauryl ether (EO) ₇ One 5 10 15 One 5 10 15 Ultrapure water to 100% by weight Properties pH (100-fold dilution) 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 Preservation Room temperature Great Great Great Great Great Great Great Great High temperature Great Great Great Great Great Great Great Great Effervescent ◎ ◎ ◎ ○ ◎ ◎ ◎ ○ Antifoam ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

Example number One 2 3 4 5 6 7 8 Resolution (development time / second) 10 D D D D D D D D 20 D D D D D D D D 30 D D D D D D B B 40 B B B B A A A A 50 A A A A A A A A 60 A A A A A A A A 70 A A A A A A A A 80 A A A A A A A A 90 B B B B B B A A 100 B B B B B B B B 110 C C C C C C B B 120 E E C C C C C C Developability Great Great Great Great Great Great Great Great

Example number 9 10 11 12 13 14 15 16 Composition ratio of developer solution (wt%) Alkaline compounds Sodium carbonate One One One One One One One One Potassium carbonate 4 4 4 4 4 4 4 4 Nonionic surfactant 1-polyethylene glycol styrene phenyl ether (EO) ₁₂ 15 15 15 15 20 20 20 20 2-Polyethyleneglycollauryl ether (EO) ₇ One 5 10 15 One 5 10 15 Ultrapure water to 100% by weight Properties pH (100-fold dilution) 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 Preservation Room temperature Great Great Great Great Great Great Great Great High temperature Great Great Great Great Great Great Great Great Effervescent ◎ ◎ ◎ ○ ◎ ◎ ◎ ○ Antifoam ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example number 9 10 11 12 13 14 15 16 Resolution (development time / second) 10 D D D D D D D D 20 D D D D D D D D 30 A B B B D D D D 40 A A A A A A A A 50 A A A A A A A A 60 A A A A A A A A 70 A A A A A A A A 80 A A A A A A B B 90 B B B B B B B B 100 B B B B B B C B 110 C C C C C C C B 120 C C C C C C E E Developability Great Great Great Great Great Great Great Great

Comparative example number One 2 3 4 5 6 7 8 Composition ratio of developer solution (wt%) Alkaline compounds Sodium carbonate One One One One 5 5 Potassium carbonate 4 4 4 4 5 5 Nonionic surfactant 1-polyethylene glycol styrene phenyl ether (EO) ₄ 0.5 0.5 30 30 0.5 0.5 30 30 2-Polyethyleneglycollauryl ether (EO) ₄ 20 20 20 20 0.1 0.1 0.1 0.1 Ultrapure water to 100% by weight Properties pH (100-fold dilution) 11.5 11.5 11.5 11.5 11.5 11.5 12.5 12.5 Preservation Room temperature Inadequate Inadequate Inadequate Inadequate Inadequate Inadequate Inadequate Inadequate High temperature Inadequate Inadequate Inadequate Inadequate Inadequate Inadequate Inadequate Inadequate Effervescent - - - - - - - - Antifoam - - - - - - - - Comparative example number One 2 3 4 5 6 7 8 Resolution (development time / second) 10 - - D D - - D D 20 - - D D - - B D 30 - - D B - - B D 40 - - D B - - A D 50 - - D A - - B B 60 - - D A - - B B 70 - - D B - - B C 80 - - D B - - C C 90 - - D B - - C C 100 - - D B - - E C 110 - - D C - - E E 120 - - D C - - E E Developability - - Inadequate Inadequate - - Inadequate Inadequate

Referring to Tables 1, 2 and 3, it can be seen that the developer containing the components according to the content of the present invention (Examples 1 to 16) not only has excellent storage properties at room temperature and high temperature, but also has a low foaming phenomenon. . In addition, it can be seen that the allowable range for developing conditions is wide and the developability is very excellent.

On the other hand, the developing solution deviated from the content of the present invention is not only poor storage stability due to poor storage stability (Comparative Examples 1 to 8), but also poor resolution for the development conditions are narrow (Comparative Examples 3, 4, 7 and 8) can be seen.

As described above, the developer of the present invention not only has excellent stability over time for storage and development performance, but also has a color filter photoresist formed using a photosensitive composition having a low transmittance to irradiated light such as a black matrix resin. Even in this case, unnecessary fine particles and resin components can be sufficiently dispersed and dissolved. In addition, development residues are not generated, organic pigments, inorganic pigments or resins are not re-adhered onto the substrate, and pixels with excellent adhesion to the substrate without the problem of missing pixels or peeling films can be formed. . In addition, the foaming rate is low and excellent in the antifoaming can eliminate the problem during development by foaming.

Claims (3)

0.1 to 10 parts by weight of any one alkaline compound selected from the group consisting of inorganic alkaline compounds, organic alkaline compounds and mixtures thereof; 1 to 25 parts by weight of a nonionic surfactant represented by Formula 1; And an aqueous solution containing 0.5 to 15 parts by weight of a nonionic surfactant represented by Formula 2 below. <Formula 1> In Formula 1, R is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group and a styrene group, m is an integer of 1 to 3 as the number of substituents , AO is at least one selected from the group consisting of oxyethylene group, oxypropylene group and polyoxyethylene polyoxypropylene block copolymer, n is an integer of 0 to 4, o is an integer of 1 to 20. <Formula 2> In Formula 2, R 1 and R 2 are each independently selected from a hydrogen atom, an alkyl group having 4 to 18 carbon atoms and an alkenyl group having 4 to 18 carbon atoms, and AO is an oxyethylene group, an oxypropylene group, and At least one selected from the group consisting of polyoxyethylene-polyoxypropylene block copolymers, and p is an integer of 1 to 20. The aqueous developing solution for photoresist according to claim 1, wherein the inorganic alkaline compound comprises at least one selected from the group consisting of sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide and potassium hydroxide. The method of claim 1, wherein the organic alkaline compound is a tetra alkyl ammonium hydroxide compound selected from the group consisting of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and 2-hydroxyethyltrimethyl ammonium hydroxide; Alkylamine compounds selected from the group consisting of monomethylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine and diisopropylamine; For photoresist comprising any one or more selected from alkanol amine compounds selected from the group consisting of ethyl alcohol amine, 2-dimethylaminoethyl alcohol, 2-diethylaminoethyl alcohol and 2-diisopropylaminoethyl alcohol Aqueous developer.