KR20160016179A - Stripper composition for photoresist and organic layer - Google Patents

Abstract

The present invention relates to a cleaning composition for removing color resists, organic insulation films, and transparent resins. The cleaning composition of the present invention comprises, based on the total weight of the composition: (a) 1 to 10 wt% of a quaternary ammonium salt compound; (b) 40 to 80 wt% of a polar solvent; (c) 1 to 20 wt% of a primary amino alcohol having a structure represented by chemical formula 1 or 2; (d) 0.01 to 2 wt% of an inorganic base or a salt thereof; and (e) 1 to 40 wt% of water. The cleaning composition in the present invention can effectively remove all of color resists, organic insulation films and transparent resins of a color filter in a short period of time, and does not have extraction problems during processes at high temperature.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a color photoresist composition,

The present invention relates to a color resist, an organic insulating film, and a cleaning agent composition for removing a transparent resin.

A color filter can be embedded in a color imaging device of an image sensor, such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and can be used to actually obtain a color image (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and the application range thereof is rapidly expanding. Particularly, in recent years, the use of LCDs has been further expanded, and accordingly, color filters have been recognized as one of the most important components in reproducing color tones of LCDs.

On the other hand, the resist can be largely divided into a positive type resist and a negative type resist. Unlike the positive type resist, which is easily removed and removed within one minute at a temperature condition of 40 to 50 DEG C by an organic solvent- Resists have properties of a negative type resist which has a high degree of curing and is hardened by heat treatment and is difficult to peel off. Accordingly, in order to remove the color resist, a time of not less than 5 minutes is required under a temperature condition of 70 占 폚 or more, so that stronger peeling performance is required. In addition, in the case of RGBW transparent resist having a four-pixel structure for increasing the light efficiency of an OLED panel, there is a problem that it is more difficult to remove by using a resin having high thermal stability and chemical stability as well as a higher degree of curing than a color resist or an organic insulating film. Accordingly, in order to reuse the defective color filter generated during the color filter manufacturing process, a cleaning agent composition capable of effectively removing both the color resist, the organic insulating film, and the transparent resin is required.

Korean Patent Laid-Open No. 10-2003-0026664 discloses a color resist stripper composition comprising a hydroxide compound as a main component, Korean Patent Laid-Open No. 10-2009-0032640 discloses a composition comprising an alkylammonium hydroxide And an alkanolamine-based compound such as diethanolamine. However, the above-described conventional techniques have achieved desired results in color resist peeling, but do not show any effect of partially or totally removing the organic insulating film or the transparent resin. Further, there is a problem that precipitation of inorganic alkali is generated due to volatilization of the exfoliating liquid at the time of high temperature processing of the hydroxide compound base exfoliating liquid composition.

Therefore, it is necessary to develop a cleaning agent composition that has excellent cleaning effect for both color resist, organic insulating film, and transparent resin, and has no deposition problem even in a high-temperature process.

Korean Patent Publication No. 10-2003-0026664 Korea Patent Publication No. 10-2009-0032640

In order to solve the problems of the prior art, the present invention can effectively remove both the color resist of the color filter, the organic insulating film and the transparent resin in a short period of time for reuse of the color filter, The purpose is to provide.

In order to achieve the above object,

(A) 1-10% by weight of a quaternary ammonium salt compound, (b) 40-80% by weight of a polar solvent, (c) a primary amino alcohol having a structure represented by the following general formula An organic insulating film and a cleaner detergent composition for removing a transparent resin, which comprises (d) 0.01 to 2% by weight of (d) an inorganic base or salt thereof, and (e) to provide.

(Formula 1)

(2)

In the general formula (1), R1 is a linear or branched C2-C4 alkyl group, R2 in the general formula (2) is a C2-C4 alkyl group, and R3 is a methyl group or an ethyl group.

The detergent composition of the present invention can effectively remove both the color resist, the organic insulating film and the transparent resin in a short time, thereby improving the productivity of the color filter reuse. In particular, the cleaning composition of the present invention enables the reuse of a defective substrate by removing a cured color resist, an organic insulating film and a transparent resin having increased crosslinking degree from the substrate in a structure in which a color filter is integrated into an LCD color filter or a TFT substrate.

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

(A) a quaternary ammonium salt compound, (b) a polar solvent, (c) a primary amino compound having a structure represented by the following general formula (1) or (2) (D) an inorganic base or salt thereof, and (e) water as essential components, and (f) a hydroxylamine compound and (g) an alkylene glycol alkyl ether compound.

(Formula 1)

(2)

The detergent composition of the present invention can effectively remove both the color resist, the organic insulating film and the transparent resin in a short time by the composition as described above, thereby improving the productivity of the color filter reuse.

(a) a quaternary ammonium salt compound

The quaternary ammonium salt compound (a) of the present invention penetrates into the resist and promotes dissolution of the polymer resist.

The quaternary ammonium salt compound is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) Or more.

The quaternary ammonium salt compound of the present invention is preferably contained in an amount of 1-10% by weight based on the total weight of the composition. When the quaternary ammonium salt compound is contained in the detergent composition of the present invention in an amount of less than 1% by weight, the penetration ability of the hydroxide ion color resist polymer decreases. When the quaternary ammonium salt compound is contained in an amount of more than 10% by weight, There is a problem of being reduced.

(b) polar solvent

The polar solvent (b) of the present invention penetrates the resist to increase the swelling property, thereby increasing the peeling force from the surface of the substrate and facilitating permeation of resin ions and other components into the resin.

The polar solvent may be at least one member selected from the group consisting of dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, sulfolane, n-methylpyrrolidone, pyrrolidone and n-ethylpyrrolidone.

The polar solvent of the present invention is preferably contained in an amount of 40 to 80% by weight based on the total weight of the composition. When the polar solvent is contained in an amount of less than 40% by weight, the solubility of the polymer resin is lowered. When the amount of the polar solvent exceeds 80% by weight, the activity of the ammonium salt compound is impaired.

(c) a primary amino alcohol

The primary amino alcohol (c) of the present invention serves not only to improve the dissolution of the resin, but also to facilitate the separation of the resin from the substrate surface by increasing the interfacial penetration between the resin and the substrate, Structure.

(Formula 1)

(2)

In the general formula (1), R1 is a linear or branched C2-C4 alkyl group, R2 in the general formula (2) is a C2-C4 alkyl group, and R3 is a methyl group or an ethyl group.

Specifically, the primary amino alcohols of formula (1) may be selected from the group consisting of 2-amino-1-butanol, 2-amino-3-methyl-1-butanol, Amino alcohol compound is at least one selected from the group consisting of 3-amino-4-octanol, 3-amino-4-heptanol, Octanol, and 2-amino-3-hexanol.

The primary amino alcohol of the present invention is preferably contained in an amount of 1-20% by weight based on the total weight of the composition. If the detergent composition of the present invention contains less than 1% by weight of the aminoalcohol, the cured resin dissolves and the interfacial penetration between the lower substrate and the cured resist decreases to deteriorate the ability to remove the resist. When the amount exceeds 20% The solubility of the resist due to the relative reduction of the quaternary alkylammonium compound and dimethyl sulfoxide is lowered and is not economical.

(d) an inorganic base or salt thereof

The inorganic base (d) or its salt penetrates into the resin molecule to weaken the intermolecular bond to facilitate the dissolution by the solvent and improve the solubility in water by the saponification reaction, thereby facilitating the rinse removal .

The inorganic base or its salt may be selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium silicate, sodium silicate, sodium acetate, It may be at least one selected.

The inorganic base (d) or its salt of the present invention is preferably contained in an amount of 0.01 to 2% by weight based on the total weight of the composition. If the amount of the inorganic base or its salt in the detergent composition of the present invention is less than 0.01% by weight, the peeling force against the organic insulating film and the color resist is poor. If the amount is more than 2% by weight, the effect of increasing the amount is insignificant and not economical.

(e) Water

(E) Water of the present invention plays a role of facilitating the removal of the cured resin by controlling the activity of the alkali component.

Water (e) of the present invention may be included in the remaining amount relative to the other components contained in the composition of the present invention, and specifically, it may be contained in an amount of 1-40% by weight.

(f) Hydroxylamine compound

The hydroxylamine compound (f) of the present invention has a low-molecular structure to generate hydroxide ions in a short time, permeates the cured resin to break the bond and dissolve the dye component of the resist.

The hydroxylamine compound is not particularly limited and may be, for example, at least one selected from the group consisting of hydroxylamine, dimethylhydroxylamine and diethylhydroxylamine.

The hydroxylamine compound of the present invention is preferably contained in an amount of 1-5% by weight based on the total weight of the composition. When the amount of the hydroxylamine compound is less than 1% by weight, it is difficult to sufficiently dissolve the dye component of the resist. When the amount of the hydroxylamine compound is more than 5% by weight, the effect of increasing the amount of the hydroxylamine compound is not increased. The content of the radical organic ammonium hydroxide and the polar solvent is lowered, so that the solubility of the resist can be reduced.

(g) Alkylene glycol alkyl ether  compound

The alkylene glycol alkyl ether compound (g) of the present invention penetrates into the polymer chain and breaks and loosens the chains, so that the resist easily peels off and dissolves the peeled resist.

The alkylene glycol alkyl ether compound may be at least one selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether or diethylene glycol methyl ethyl ether Or a mixture of two or more of them.

The alkylene glycol alkyl ether compound of the present invention is preferably contained in an amount of 1 - 20 wt%, more preferably 1-15 wt%, based on the total weight of the composition. If the amount of the alkylene glycol alkyl ether is less than 1 wt%, the solubility of the quaternary ammonium salt is lowered, and the stability of the composition is deteriorated and it is not economical when the amount exceeds 20 wt% .

The cleaning agent composition of the present invention exhibits a very excellent cleaning effect for both the color resist, the organic insulating film and the transparent resin. The color resist may be a negative type photoresist, but the present invention is not limited thereto, and the organic insulating film may include an acrylic- But the present invention is not limited thereto. The transparent resin may be an ultraviolet ray curable composition including an alkali-soluble resin containing an epoxy group, but is not limited thereto.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example  And Comparative Example : Preparation of detergent composition

The cleaning agent compositions of Examples 1 to 16 and Comparative Examples 1 to 7 were prepared by mixing the ingredients shown in the following Table 1 according to the specified composition ratios.

Quaternary ammonium hydroxide Polar solvent Primary amino alcohol Inorganic bases or salts thereof Hydroxylamine compound Alkylene glycol alkyl ether water Kinds weight% Kinds weight% Kinds weight% Kinds weight% Kinds weight% Kinds weight% Example 1 TMAH 2 DMSO 72 A1 15 Sodium hydroxide 0.1 Balance Example 2 TMAH 4 DMSO 63 A2 15 Sodium carbonate 0.1 Balance Example 3 TMAH 6 DMSO 45 A3 8 Potassium hydroxide 0.05 Balance Example 4 TMAH 8 DMSO 45 A1 8 Potassium hydroxide 0.05 Balance Example 5 TMAH 2 DMSO 55 A2 15 Potassium carbonate 1.0 Balance Example 6 TMAH 4 DMSO 65 A3 12 Potassium carbonate 0.1 Balance Example 7 TMAH 6 DMSO 55 A1 8 Potassium acetate 0.1 Balance Example 8 TMAH 8 DMSO 45 A2 8 Potassium acetate 0.2 Balance Example 9 TEAH 4 DMSO 50 A3 10 Sodium nitrate 0.5 Balance Example 10 TEAH 6 DMSO 50 A3 10 Potassium sulfate 0.2 Balance Example 11 TMAH 6 DMSO 60 A4 15 Potassium hydroxide 0.5 Balance Example 12 TMAH 6 Sulfolane 60 A3 15 Potassium hydroxide 0.5 Balance Example 13 TMAH 6 NMP 60 A3 15 Potassium hydroxide 0.05 Balance Example 14 TMAH 4 DMSO 50 A3 10 Potassium hydroxide 0.5 HA One DMDG 15 Balance Example 15 TMAH 4 DMSO 55 A3 10 Potassium hydroxide 0.5 DMTG 10 Balance Example 16 TMAH 4 DMSO 55 A3 12 Potassium nitrate 0.5 HA One Balance Comparative Example 1 TMAH 0.5 DMSO 70 Sodium nitrate 0.5 Balance Comparative Example 2 TEAH 3 DMSO 25 A 1 8 - - Balance Comparative Example 3 TMAH 12 DMSO 35 A 3 25 - - Balance Comparative Example 4 TMAH 6 DMSO 60 - - Potassium carbonate 0.2 Balance Comparative Example 5 TMAH 6 DMSO 50 MEA 15 Potassium hydroxide 0.5 Balance Comparative Example 6 TMAH 6 DMSO 50 NMEA 15 Potassium hydroxide 0.5 Balance Comparative Example
7 TMAH 6.25 DMSO 40 MEA 30 Potassium acetate 0.05 HA 2 MDG 10 10.7

A1: 2-amino-1-pentanol,

A2: 2-amino-3-octanol,

A3: 3-amino-4-octanol

A4: 2-amino-1-butanol

Experimental Example  One: Color resist  Removal evaluation

In order to evaluate the color resist removal effect of the cleaning composition prepared in Examples and Comparative Examples, a color filter substrate coated with red, green, and blue (hereinafter RGB) was used. The color resist was applied after being prebaked at 90 ° C for 120 seconds after exposure, developed, and then hard baked in an oven at 220 ° C in an oven.

In order to confirm the removability of the color resist of the cleaning composition prepared in Examples and Comparative Examples, a color filter substrate coated with the RGB was immersed in a solution at 70 캜 for 3 minutes, 5 minutes and 10 minutes, . The results are shown in Table 2 below.

◎: 100% resist removal

○: Resist 80% or more removed

?: Less than 80% resist removal

X: No resist removal

RGB substrate Organic insulating film substrate WRGB substrate Rework time 3 minutes 5 minutes 10 minutes 5 minutes 10 minutes 7 minutes Example 1 ○ ◎ ◎ ○ ◎ ○ Example 2 ○ ◎ ◎ ○ ◎ ○ Example 3 ○ ◎ ◎ ○ ◎ ○ Example 4 ○ ◎ ◎ ○ ◎ ○ Example 5 ○ ◎ ◎ ○ ◎ ○ Example 6 ○ ◎ ◎ ○ ◎ ○ Example 7 ○ ◎ ◎ ○ ◎ ○ Example 8 ○ ◎ ◎ ○ ◎ ○ Example 9 ○ ◎ ◎ ○ ◎ ○ Example 10 ○ ◎ ◎ ○ ◎ ○ Example 11 ○ ◎ ◎ ○ ◎ ○ Example 12 ○ ◎ ◎ ○ ◎ ○ Example 13 ○ ◎ ◎ ○ ◎ ○ Example 14 ◎ ◎ ◎ ◎ ◎ ◎ Example 15 ◎ ◎ ◎ ◎ ◎ ◎ Example 16 ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 1 X X △ X △ X Comparative Example 2 X X △ △ △ X Comparative Example 3 X X X X X △ Comparative Example 4 X △ △ △ △ X Comparative Example 5 X △ △ △ △ X Comparative Example 6 X △ ○ △ ○ X Comparative Example 7 X ○ ○ △ ○ △

As shown in Table 2, the cleaning compositions of Examples 1 to 16 showed that 100% of the color resist was removed within 5 minutes, and the organic insulating film was removed within 10 minutes, showing a very excellent cleaning effect in a short time. In particular, the compositions of Examples 14 to 16 containing hydroxylamine compounds or alkylene glycol alkyl ethers as additional components can improve the removal speed of the transparent resist as well as the color resist and the organic insulating film, There are advantages.

On the other hand, the cleaning liquid compositions of Comparative Examples 1 to 4, in which (a) the quaternary ammonium salt compound or (b) the polar solvent were out of the content range of the present invention, showed very poor cleaning effect on both the color resist and the organic insulating film.

In addition, the cleaning liquid compositions of Comparative Examples 5 to 6 which do not contain the primary amino alcohol having the structure (c) of the present invention (1) or (2) or contain MEA, NMEA, etc. in place of the above- And the composition of Comparative Example 7 which is a composition of the prior art Korean Patent Laid-Open No. 10-2009-0032640 also had poor cleaning effect on both the color resist and the organic insulating film.

Therefore, the cleaning liquid composition having the composition of the present invention can sufficiently remove the color resist and the organic insulating film of the color filter in a short time, and thus the productivity of color filter reuse can be improved.

Claims (7)

With respect to the total weight of the composition,
(a) 1-10% by weight of a quaternary ammonium salt compound,
(b) 40 to 80% by weight of a polar solvent,
(c) 1 to 20% by weight of a primary amino alcohol having a structure represented by the following formula (1) or (2)
(d) 0.01-2% by weight of an inorganic base or salt thereof and
(e) from 1 to 40% by weight of water. The cleaning agent composition for removing a color resist, an organic insulating film and a transparent resin,
(Formula 1)

(2)

In the general formula (1), R 1 is a linear or branched alkyl group having 2 to 4 carbon atoms, and R 2 is an alkyl group having 2 to 4 carbon atoms. R3 is a methyl group or an ethyl group.
The method according to claim 1,
The quaternary ammonium salt compound (a) is composed of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) And a cleaning agent composition for removing a color resist, an organic insulating film, and a transparent resin.
The method according to claim 1,
The polar solvent (b) may be at least one selected from the group consisting of dimethylsulfoxide, diethylsulfoxide, dipropylsulfoxide, sulfolane, n-methylpyrrolidone, pyrrolidone and n- , A color resist, an organic insulating film, and a cleaning agent composition for removing a transparent resin.
The method according to claim 1,
(C) The primary aminoalcohol of formula (1) is at least one selected from the group consisting of 2-amino-1-butanol, 2-amino-3-methyl-1-butanol, Amino alcohol compound is at least one selected from the group consisting of 3-amino-4-octanol, 3-amino-4-heptanol, Octanol, and 2-amino-3-hexanol; and a cleaning agent composition for removing a color resist, an organic insulating film, and a transparent resin.
The method according to claim 1,
The inorganic base or its salt (d) may be prepared by reacting the compound of formula (I) with a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium silicate, An organic insulating film, and a cleaning agent composition for removing a transparent resin.
The method according to claim 1,
(f) a hydroxylamine compound, and (g) an alkylene glycol alkyl ether compound.
7. The composition of claim 6 wherein, relative to the total weight of the composition,
(f) 1-5% by weight of a hydroxylamine compound, and (g) 1-20% by weight of an alkylene glycol alkyl ether compound.