KR101344168B1 - Polyimide Removing compositions - Google Patents

Abstract

The present invention is a polyimide remover comprising (A) a quaternary ammonium hydroxide, (B) a glycol ether solvent, (C) at least one component selected from the group consisting of sugars and sugar alcohols, and (D) water. It relates to a composition.

The present invention provides a polyimide remover composition which not only has excellent removal performance of the polyimide film but also has no aluminum corrosion resistance and, in addition, does not affect the elasticity of the column spacer and minimizes corrosion.

Polyimide Membrane, Aluminum Corrosion, Ammonium Hydroxide

Description

Polyimide Removing Compositions

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide remover composition, and more particularly, to a remover composition for removing a cured polyimide film from a substrate in a manufacturing process of a semiconductor device and a liquid crystal display device.

BACKGROUND ART Alkaline cleaners have been widely used in the production of electronic parts, metal parts, ceramic parts, etc. because of their superior ability to remove organic matter, inorganic matter, particles, etc., compared to neutral detergents. However, since the alkali cleaners easily corrode nonferrous metals such as aluminum, it is a reality that aluminum cannot be used for cleaning electronic parts and the like in which part or all of the parts are used.

For example, the polyimide alignment film of an electronic component, especially a liquid crystal panel, has been a horizontal alignment type until now, but as the demand of a wide viewing angle liquid crystal panel becomes stronger, the vertical alignment type polyimide alignment film is increasing. If the horizontal orientation type polyimide alignment film glass substrate is in a semi-fired state (a semi-hardened film desolvated at about 80 ° C.) before complete firing (firing temperature: about 180 ° C.), the defective product may be a solvent such as N-methylpyrrolidone. The alignment film can be peeled off without corrosion of the aluminum thin film (wiring). However, in the case of the vertical alignment type polyimide alignment film, even if the semi-baked state is used, the solvent cannot peel off the polyimide alignment film (semi-fired). It is using, and aligning film peeling is performed (refer Unexamined-Japanese-Patent No. 6-306661). At this time, since the aluminum thin film (wiring) of the glass substrate is corroded, the aluminum thin film portion is protected by wax or the like, and then the wax is removed with a solvent such as hydrocarbon to regenerate the substrate, or the aluminum thin film is completely cleaned simultaneously with the alignment film. The method of regenerating only a glass substrate after peeling and dissolving easily is taken, and it causes the waste of raw materials and the fall of productivity.

Accordingly, an object of the present invention is to provide a polyimide remover composition which is not only excellent in the removal performance of the polyimide film but also free of aluminum corrosion, in order to solve the problems of the prior art as described above. It is an object of the present invention to provide a polyimide remover composition which does not affect and minimizes corrosion.

In order to achieve the above technical problem, the present invention provides at least one component selected from the group consisting of (A) quaternary ammonium hydroxide, (B) glycol ether solvent, (C) sugars and sugar alcohols, and ( D) A polyimide remover composition comprising water is provided.

As an example of the (A) quaternary ammonium hydroxide used for the polyimide remover composition of this invention, the compound of following General formula (1) is mentioned.

(N- (R) ₄ ] ⁺ OH ^-

In said formula, R is a C1-C4 alkyl group.

Specific examples of the compound of Formula 1 include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and the like. Among these, tetramethylammonium hydroxide (hereinafter referred to as 'TMAH') is preferable.

In the composition of the present invention, the quaternary ammonium hydroxide may be used alone or in combination of two or more thereof.

The quaternary ammonium hydroxide (A) in the composition of the present invention is preferably contained in 0.1 to 20% by weight, more preferably 0.1 to 10% by weight relative to the total weight of the composition. When it contains less than 1 weight%, the peeling speed of a polyimide is slow, and when it exceeds 20 weight%, corrosion of a wiring material cannot be prevented.

As an example of the (B) glycol ether solvent used by the composition of this invention, the compound of following General formula (2) is mentioned.

R-O- ( CH ₂ CH ₂ O ) _n H

In said formula, R is a C1-C4 alkyl group and n is an integer of 1-3.

Specific examples of the compound of Formula 2 include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. And dietelin glycol monomethyl ether (hereinafter referred to as 'MDG') are preferable.

In the composition of this invention, a glycol ether solvent can be used 1 type or in combination of 2 or more types.

In the composition of the present invention, the (B) glycol ether solvent is preferably included in an amount of 50 to 95% by weight, and more preferably 80 to 95% by weight, based on the total weight of the composition. When included in less than 50% by weight, the removability of the polyimide is lowered, when contained in excess of 95% by weight increases the corrosion of the wiring material.

Examples of the sugars used in the composition of the present invention include sugars such as monosaccharides and polysaccharides, and specific examples thereof include glycerol having 3 to 6 carbon atoms, aldehyde, threose, arabinose, xylose, ribose, ribose, xylose, glucose, Mannose, galactose, tagatose, allose, altrose, gloss, idose, talos, sorbose, sicose, fructose and the like.

Examples of sugar alcohols include traceol, erythritol, adonitol, arabitol, xylitol, talitol, sorbitol, mannitol, iditol, dulcitol and the like.

Among these, glucose, mannose, galactose, sorbitol, mannitol, and the like are particularly preferable in view of solubility and corrosion resistance to wiring materials.

The at least one component selected from the group consisting of (C) sugars and sugar alcohols used in the composition of the present invention is preferably contained in 0.1 to 5% by weight based on the total weight of the composition, more preferably 0.1 to 3 It is preferably included in weight percent. If it is included in less than 0.1% by weight, it is not possible to sufficiently prevent the corrosion of the wiring material, when contained in more than 5% by weight, the removability of the polyimide is lowered, there is no economic benefit.

The remover composition of the present invention may further include a surfactant and the like as an additive commonly used in the art.

Although the dipping method is common as a method of removing a polyimide membrane using the polyimide remover composition of this invention, other methods, for example, the method by a spraying method, can also be used. In addition, as a cleaning agent after treating with the remover composition of the present invention, it is not necessary to use an organic solvent such as alcohol, and only washing with water is sufficient.

The polyimide remover composition of the present invention can be usefully used in the process of removing a polyimide film of a semiconductor or electronic product, in particular, a liquid crystal panel.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples and the like.

Example  1 to 8 and Comparative Example  1 to 4: polyimide Remover  Preparation of the composition

Each component was mixed according to the composition ratio shown in Table 1 below to prepare polyimide remover compositions of Examples 1-8 and Comparative Examples 1-4.

(A) Quaternary Ammonium Hydroxide (B) Glycol Ether Solvent (C) sugars and / or sugar alcohols Kinds weight% Kinds weight% Kinds weight% room
city
Yes One Tetramethylammonium
Hydroxide
(TMAH) 2 Diethylene glycol
Monomethyl ether
(MDG) 85 Sorbitol 2 2 TMAH 2 MDG 80 Sorbitol 1.5 3 TMAH 2 MDG 85 Sorbitol One 4 TMAH 2 MDG 90 Sorbitol 0.5 5 TMAH 2 Ethylene glycol
Monomethyl ether
(MG) 80 Sorbitol 2 6 Tetraethylammonium
Hydroxide
(TEAH) 2 MG 80 Sorbitol 1.5 7 TMAH 2 MG 85 Sorbitol One 8 TMAH 2 MG 90 Sorbitol 0.5 ratio
School
Yes 9 TMAH 2 Butyl Diclicol
(BDG) 85 Mannitol 2 10 TMAH 4 BDG 80 Sorbitol 0.5 11 Tetraethylammonium
Hydroxide
(TEAH) 2 MDG 85 Catechol 0.5 12 TMAH 2 MDG 90 -

* The composition of Examples and Comparative Examples in Table 1 contains the residual amount of (D) water.

Test Example .

A test piece in which a polyimide thin film was formed on a glass substrate and a test piece in which an aluminum thin film was formed were prepared, respectively, which were immersed in each of the polyimide remover compositions of Examples 1 to 8 and Comparative Examples 1 to 4 for 10 minutes, and then dried and observed with an optical microscope. did.

Table 2 shows the results of evaluating the peelability of the polyimide film and the residue and the corrosiveness of the aluminum wiring.

<Evaluation Criteria for Peelability by Optical Microscopy>

(Circle): It removed completely.

(Triangle | delta): Some residual was confirmed.

X: Most remained.

<Evaluation of Corrosion by 4 Point Prove and Optical Microscope>

(Circle): Corrosion was not confirmed at all.

(Triangle | delta): Partial corrosion was confirmed.

X: Severe corrosion was confirmed

<Column spacer elasticity evaluation criteria using PSIS-5001 (SNU) CS elasticity measuring instrument>

(Circle): The elasticity of the column spacer remained similar within 0.1% compared with the pretest.

(Triangle | delta): Elasticity fell 0.5% compared with the test.

X: Elasticity fell 1% or more compared with the test.

Treatment condition Peelability Aluminum corrosive Column spacer
Shout Temperature (℃) Immersion time (minutes) room
city
Yes One 50 10 O O O 2 50 10 O O O 3 50 10 O O O 4 50 10 O O O 5 50 10 O O O 6 50 10 O O O 7 50 10 O O O 8 50 10 O O O ratio
School
Yes 9 50 10 △ △ △ 10 50 10 O △ △ 11 50 10 O △ △ 12 50 10 O X X

The polyimide film remover composition of the present invention can not only easily peel off the polyimide film applied on the substrate or the polyimide film that has been cured at a high temperature after application at a low temperature in a short time, but also has no aluminum corrosion resistance. The organic matter remaining on the polyimide film or the substrate can be effectively removed. In addition, the polyimide membrane remover composition of the present invention has an excellent characteristic of minimizing corrosion without affecting the elasticity of the column spacer.

Claims (7)

(A) 0.1-20 wt% of quaternary ammonium hydroxide, (B) ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether 50 to 95% by weight of one or more glycol ether solvents selected from the group consisting of: (C) 0.1 to 5% by weight of one or more components selected from the group consisting of sugars and sugar alcohols, and the remaining amount of (D) water Polyimide remover composition comprising. The polyimide remover composition of claim 1, wherein (A) the quaternary ammonium hydroxide is represented by the following Chemical Formula 1:

(One) In said formula, R is a C1-C4 alkyl group. The polyimide remover composition of claim 2, wherein the compound of Formula 1 is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. delete delete The method according to claim 1, wherein (C) at least one component selected from the group consisting of sugars and sugar alcohols is glycerol, aldehyde, throse, arabinose, xylose, ribose, ribose, xylulose having 3 to 6 carbon atoms , Glucose, mannose, galactose, tagatose, allose, altrose, gloss, idose, talos, sorbose, sicose, fructose, tracer, erythritol, adonitol, arabitol, xylitol, thalitol , Sorbitol, mannitol, iditol, and dulcitol. delete