KR20170086965A - Liquid composition for stripping a color resist and an organic layer - Google Patents

Abstract

The present invention relates to a color resist having excellent peel strength and aging stability, comprising a quaternary ammonium salt compound, a polar organic solvent, an alkylene glycol alkyl ether, a hydrazine derivative compound having a specific structure, an inorganic base or a salt thereof, To an organic film peeling liquid composition.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color resist or an organic film removing liquid composition,

The present invention relates to a release liquid composition, and more particularly, to a color resist or organic film release liquid composition capable of effectively removing a cured color resist or an organic film.

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 . In addition, it is widely used in a photographic device, a plasma display panel (PDP), a liquid crystal display (LCD), a field emission display (FEL) and a light emitting display (LED). Particularly, in recent years, the use of a liquid crystal display (LCD) has been further expanded, and accordingly, a color filter has been recognized as one of the most important components in reproducing a color tone of a liquid crystal display (LCD).

The color filter substrate includes a red matrix (R), a green matrix (G), and a blue matrix (B), a black matrix for blocking leakage of light between each pixel and improving contrast, and a common electrode Consists of.

Defects of the color resist pattern may inevitably occur in such a color filter manufacturing process. However, once the resin constituting the color resist is hardened, it is almost impossible to repair only the erroneous portion, and since there is almost no solvent capable of removing the color resist, the color filter having a defect can not be reworked There is a problem that most of them are discarded and the productivity is lowered.

In addition, since an overcoat layer is used to compensate for the step difference due to the laminating process of the color filter, when the coating failure of the R, G, or B color filter of the color filter occurs or the coating failure of the organic film occurs, The process yield is improved and the cost is reduced. Therefore, there is a demand for a peeling liquid composition capable of removing an RGB color resist or an organic film for reuse of a color filter.

Korean Patent No. 10-1043397 includes an inorganic alkali hydroxide or alkyl ammonium hydroxide, dimethylsulfoxide, a water-soluble amine compound, N-methylpyrrolidone, a dialkylene glycol ether, an inorganic alkali acetate and a residual amount of water However, there is a problem in that deterioration is deteriorated during long-term use due to volatilization during a high-temperature process, and also there is a problem that the effect of rapidly removing the color resist and the organic film can not be exhibited.

Korean Patent No. 10-1043397

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art,

It is an object of the present invention to provide a release liquid composition having excellent peeling force without causing corrosion of a lower wiring when a cured color resist or an organic film is peeled. It is another object of the present invention to enable the reuse of a lower substrate before applying a color filter by providing a color resist or an organic film stripping liquid composition excellent in stability at a high temperature or with aging and excellent in resist peeling force.

According to an aspect of the present invention,

With respect to the total weight of the composition,

1 to 15% by weight of a quaternary ammonium salt compound,

20 to 70% by weight of a polar organic solvent,

1 to 20% by weight of an alkylene glycol alkyl ether,

0.1 to 5% by weight of at least one hydrazine derivative compound selected from the following formulas (1) to (3)

0.01 to 2% by weight of an inorganic base or a salt thereof, and

And 1 to 40% by weight of water.

≪ Formula 1 >

In the above formula (1), R ₁ is a C1-C6 hydroxyalkyl group.

(2)

In Formula 2, R ₂ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, an amino group, or -NHNH ₂ .

(3)

The peeling liquid composition of the present invention has excellent peeling force without causing corrosion of wirings, thereby effectively eliminating defects of the cured color resist pattern.

In addition, the releasing solution composition of the present invention has low volatility due to aging or high temperature, so that peeling force and detergency are not deteriorated even when used for a long period of time, and the performance retention time is long, thereby improving process efficiency and economical effect.

Generally, a color filter is manufactured by applying a resist to a substrate on which an array is formed by transparent glass or metal wiring, a protective film for protecting the resist is applied, and a color resist pattern is formed by a photolithography process, When a defect occurs in the resist pattern, the resist is removed and the lower substrate is again obtained to perform rework for reuse.

The material used in such a recoating process is a resist stripper composition. In the conventional resist stripper composition, peeling force is lowered depending on the number of treatments, and stability with time and detergency deteriorate due to volatilization due to a high temperature process and aging .

The releasing solution composition of the present invention can be used as a releasing agent for a releasing agent composition containing a quaternary ammonium salt compound, a polar organic solvent, an alkylene glycol alkyl ether, a hydrazine derivative compound having a specific structure, an inorganic base or a salt thereof, The peeling force provides an excellent effect.

The present invention relates to a composition comprising

1 to 15% by weight of a quaternary ammonium salt compound,

20 to 70% by weight of a polar organic solvent,

1 to 20% by weight of an alkylene glycol alkyl ether,

0.1 to 5% by weight of at least one hydrazine derivative compound selected from the following formulas (1) to (3)

0.01 to 2% by weight of an inorganic base or a salt thereof, and

And 1 to 40% by weight of water.

Hereinafter, each component will be described in detail.

Quaternary ammonium salt compound

The quaternary ammonium salt compound contained in the release agent composition of the present invention may preferably be a quaternary alkylammonium hydroxide, and may release hydroxide ion (OH < ^- & gt ^; ) to penetrate into the color polymer resist, It serves to promote dissolution.

Examples of the quaternary ammonium salt compound include, but are not limited to, tetramethyl ammonium hydroxide (TMAH), tetraethyl ammonium hydroxide (TEAH), tetrapropyl ammonium hydroxide hydroxide, TPAH) and tetrabutyl ammonium hydroxide (TBAH). One or more selected from these can be used.

The quaternary ammonium salt compound is contained in an amount of 1 to 15% by weight, and more preferably 7 to 15% by weight based on the total weight of the release agent composition of the present invention. If the content of the quaternary ammonium salt compound is less than 1% by weight, the ability to penetrate the polymer component constituting the color resist of the hydroxide ion is lowered and the removability of the resist decreases. When the content exceeds 15% by weight, .

Polar organic solvent

The polar organic solvent contained in the release liquid composition of the present invention is excellent in penetration and dissolving power to a color resist and penetrates into the polymer of the color resist to swell and dissolve the polymer.

It is preferable that the polar organic solvent is a polar aprotic organic solvent, but the present invention is not limited thereto.

Specific examples of the polar organic solvent include dimethylsulfoxide, diethylsulfoxide, dipropylsulfoxide, sulfolane, N-methyl-2-pyrrolidone ), Pyrrolidone, n-ethyl pyrrolidone, and the like can be used. Preferably, dimethylsulfoxide or sulfolane can be used.

The polar organic solvent is contained in an amount of 20 to 70% by weight, and more preferably 40 to 60% by weight based on the total weight of the release liquid composition of the present invention. If the content of the polar organic solvent is less than 20% by weight, penetration and swelling properties of the resist are insufficient, and it is difficult to completely remove the color resist, and the processing time becomes long. On the other hand, if it exceeds 70% by weight, the activity of the quaternary ammonium salt compound described above is inhibited and the removability is lowered.

Alkylene glycol alkyl ether

The alkylene glycol alkyl ether contained in the release liquid composition of the present invention penetrates into the polymer chain to release the chain and permeates the interface between the lower film and the cured polymer to easily peel the resist, And the like.

Specific examples of the alkylene glycol alkyl ether include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl Ethyl ether, and the like, but not limited thereto, and at least one selected from these may be used.

The alkylene glycol alkyl ether is contained in an amount of 1 to 20% by weight, preferably 5 to 15% by weight based on the total weight of the release agent composition of the present invention. If the content is less than 1% by weight based on the above-mentioned criteria, the resist stripping rate can not be improved. On the other hand, if the amount of the quaternary ammonium salt compound is more than 20% by weight, there is no increase in the effect due to the increase in the amount of the quaternary ammonium salt compound. Therefore, the solubility of the quaternary ammonium salt compound is lowered and the phase stability of the release agent composition may be lowered.

Hydrazine derivative compound

The removing solution composition of the present invention comprises at least one hydrazine derivative compound selected from the following Chemical Formulas 1 to 3, and the hydrazine derivative compound has a role of improving the peeling property of the composition. In addition, by including the hydrazine derivative, it is possible to provide an effect of improving the stability with time of the composition.

≪ Formula 1 >

In the general formula 1 R ₁ is a hydroxyalkyl group of C1 ~ C6,

(2)

In Formula 2, R ₂ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, an amino group, or -NHNH ₂ .

(3)

The hydrazine derivative compound may be contained in an amount of 0.1 to 5 wt%, more preferably 0.5 to 1.5 wt%, based on the total weight of the composition. When the content of the hydrazine derivative compound is less than 0.1% by weight, the peeling force is lowered. When the amount of the hydrazine derivative compound is more than 5% by weight, the effect of improving the peeling force is insufficient.

An inorganic base or Salt compound

The inorganic base or its salt compound contained in the release agent composition of the present invention has a role of improving the peeling force for the resist.

The inorganic base or its salt compound may include lithium, sodium or potassium, and more specific examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium nitrate, potassium nitrate, , Potassium sulfate, sodium silicate, potassium silicate, sodium acetate, potassium acetate and the like, but is not limited thereto.

The inorganic base or its salt compound is more preferably an alkali metal base or a salt compound thereof, more preferably a potassium base or potassium salt compound.

The inorganic base or its salt compound is contained in an amount of 0.01 to 2% by weight, more preferably 0.05 to 1.5% by weight based on the total weight of the release agent composition. When the content is less than 0.01% by weight, the peeling force against the resist and the organic film is poor. When the content exceeds 2% by weight, especially in the case of forming the color filter on the array, There is a problem of causing corrosion of the metal film.

water

The water contained in the release agent composition of the present invention enhances the activation and solubility of the inorganic base or its salt compound, thereby increasing the removal rate of the resist and preventing precipitation in the solution. In addition, it is possible to quickly and completely remove the organic contaminants remaining on the substrate and the resist stripping solution during rinsing with deionized water.

The water is contained in an amount of 1 to 40% by weight based on the total weight of the release liquid composition of the present invention. If the content of water is less than 1% by weight, the composition of the composition is changed at a process temperature to cause deterioration of the performance. If the content of the composition exceeds 40% by weight, the loss of the composition due to evaporation of water at the process temperature increases have.

The kind of the water is not particularly limited, but it is preferable to use deionized water. It is more preferable that the resistivity is 18 MΩ · cm or more as deionized water for semiconductor processing.

In addition, the releasing solution composition of the present invention may further comprise at least one selected from the above-mentioned components as well as a corrosion inhibitor, a chelating agent, a surfactant and a dispersing agent.

The corrosion inhibitor is included in the release liquid composition to prevent corrosion of metal wiring such as aluminum and / or copper.

Examples of the corrosion inhibitor include, but are not limited to, benzotriazole, tolythriazole, methyltolytriazole, 2,2 '- [[[benzotriazole] methyl] imino] bisethanol, - [[[methyl-1-hydrogen-benzotriazol-1-yl] methyl] imino] bist methanol, 2,2 ' ] - [[[methyl-1-hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol, 2,2 ' Yl] methyl] imino] bismethylamine, 2,2 '- [[[methyl-1-hydrogen-benzotriazol- Amine-1-hydrogen-benzotriazol-1-yl] methyl] imino] bis-ethanol and the like; Quinone compounds such as 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone, anthraquinone and the like; Catechol compounds such as catechol and the like; And alkyl gallate compounds such as pyrogallol, methyl gallate, propyl gallate, dodecyl galatate, octyl galatate, gallic acid and the like can be used.

The corrosion inhibitor is preferably contained in an amount of 0.1 to 5% by weight based on the total weight of the composition. If the content is less than 0.1% by weight, corrosion may occur in the metal wiring made of aluminum or aluminum alloy and copper or copper alloy in the peeling or deionized water rinsing process. On the other hand, if it is contained in an amount exceeding 5% by weight, secondary contamination due to adsorption of the surface and deterioration of the peeling force may occur.

The chelating agent, surfactant, dispersing agent and the like are not particularly limited, and those which are conventionally used in the art can be selected and used within a range that does not impair the characteristics of the present invention.

INDUSTRIAL APPLICABILITY The peeling liquid composition of the present invention can provide a good peeling force for a color resist, an organic film, and a transparent material, and is excellent in detergency due to volatilization under aged or high temperature conditions, have. Therefore, since the color filter in which a defect has occurred can be easily removed, the productivity and economical efficiency of the color filter can be remarkably increased.

Further, the method of using the release liquid composition of the present invention is not particularly limited. When the color resist pattern is defective during the manufacturing process of the color filter, the cured color resist substrate is immersed in the release liquid composition, To a substrate, or the like.

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

< Example  And Comparative Example >

Example  1 to 9 and Comparative Example  1 to 5. color Resist  or Organic film  Preparation of release liquid composition

A stripper composition was prepared containing the remaining amount of water in the components and contents shown in Table 1 below.

Quaternary ammonium salt
compound polarity
Organic solvent Alkylene glycol
Alkyl ether Hydrazine
derivative An inorganic base or
His salt corrosion
Inhibitor Kinds weight% Kinds weight% Kinds weight% Kinds weight% Kinds weight% Kinds weight% Example
One TMAH 10 DMSO 54.3 MEDG 5 A1 0.5 B1 0.2 Example
2 TMAH 8 DMSO 53.9 DMDG 10 A2 One B2 0.05 Example
3 TEAH 14 DMSO 58.0 DEDG 5 A1 One B1 One Example
4 TMAH 7 DMSO 55.4 MEDG 8 A3 1.5 B2 0.1 Example
5 TMAH 10 DMSO 47.5 DMDG 10 A4 One B1 1.5 BTA 3 Example
6 TMAH 7 sulfolane 56.3 DMDG 8 A1 0.5 B2 0.2 TTA 2 Example
7 TBAH 8 DMSO 47.0 DMDG 15 A2 One B3 One Example
8 TMAH 12 DMSO 43.0 MEDG 5 A4 One B3 1.2 Example
9 TEAH 10 DMSO 41.8 DMDG 10 A1 5 B1 0.2 BTA 3 Comparative Example
One TMAH 0.8 DMSO 91.0 MEDG 5 A1 0.5 B1 0.2 Comparative Example
2 TMAH 10 DMSO 59.3 - - A1 0.5 B1 0.2 Comparative Example
3 TMAH 10 DMSO 54.8 MEDG 5 - - B1 0.2 Comparative Example
4 TMAH 10 DMSO 54.1 MEDG 5 A1 0.5 - - Comparative Example
5 TMAH 8 DMSO 45.5 DMDG 10 A5 One B2 0.5 ATZ 3

week)

A1: 2-Hydrazinoethanol (2-hydrazinoethanol)

A2: 2-Hydrazinopropanol (2-hydrazinopropanol)

A3: Carbohydrazide

A4: 4-Aminomorpholine

A5: Hydrazine

BTA: benzotriazole

TTA; Tolythriazole

B1: Potassium nitrate

B2: Potassium hydroxide

B3: Potassium acetate

< Experimental Example > Performance test of release liquid composition

A color filter substrate on which a transparent material forming a column spacer CS and a red, green and blue (hereinafter referred to as WRGB) were applied to each pixel was used for evaluation of removal of the color resist.

After the color resist was applied to the glass substrate, it was pre-baked at 90 캜 for 120 seconds. After the exposure and development, the substrate having the pattern formed thereon was hard-baked in an oven at 220 ° C to prepare a specimen.

On the color filter substrate on which the color resist pattern was formed, an overcoat layer for solving the step between the materials was applied. The organic film layer was formed by hard baking in an oven at 220 캜 through exposure and development.

Experimental Example  One. Peel force  evaluation

In order to evaluate the peeling detergency of the peeling liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 5, the following experiment was conducted. After the release liquid composition was kept at a constant temperature of 75 캜, the above-mentioned specimen including the organic film and the transparent material on the color filter pattern substrate was immersed for 3 minutes, 5 minutes, 10 minutes or 15 minutes, Respectively. The results are shown in Table 2 below.

<Evaluation Criteria>

◎: 100% removal of resist or insulating film

○: Removal of resist or insulating film more than 80%

?: Less than 80% removal of resist or insulating film

X: No removal of resist or insulating film

Experimental Example  2. Evaluation of detachment persistence by high temperature aging

In order to evaluate the persistency of the peeling cleaning force of the resist stripping solution composition at a high temperature with time, the following experiment was conducted.

The peel solution compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 5 were stored in an open state at a temperature of 75 DEG C for 12 hours to evaluate the peelability at a high temperature with the same method as in Experimental Example 1 Respectively. The results are shown in Table 2 below.

<Evaluation Criteria>

◎: 100% resist removal

○: Resist 80% or more removed

?: Removal of resist 60% or more

×: Less than 60% of resist removal

××: No resist removal

Experimental Example  3. Metal wiring damage  evaluation

Experiments were conducted as follows to evaluate the degree of damage to the metal wiring of the peeling liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 5.

A Cu / Ti wiring and a passivation film were used. The temperature of the stripping solution composition was kept constant at 75 캜, and the substrate was immersed. Two sheets of the substrates were taken out one by one after the peeling point and after immersion, and the degree of occurrence of disconnection or corrosion of the wirings was observed with an optical microscope. The results are shown in Table 2 below.

<Evaluation Criteria>

&Amp; cir &amp;: The number of lower wiring damages is 10 or less

O: The number of lower wiring damage is more than 10 but not more than 30

?: The number of lower wiring damages was more than 30 but not more than 100

X: Number of lower wiring damage exceeds 100

Item WRGB substrate Upper organic film After a high temperature
Separation cleaning force (15 minutes) After 1 hour immersion
Lower wiring damage Rework time Rework time 5 minutes 10 minutes 15 minutes 3 minutes 5 minutes Example 1 △ ○ ◎ ○ ◎ ◎ ○ Example 2 △ ○ ◎ ○ ◎ ◎ ○ Example 3 ○ ◎ ◎ ◎ ◎ ◎ ○ Example 4 ○ ◎ ◎ ◎ ◎ ◎ ○ Example 5 ○ ◎ ◎ ◎ ◎ ◎ ◎ Example 6 ○ ◎ ◎ ◎ ◎ ◎ ◎ Example 7 ○ ◎ ◎ ◎ ◎ ◎ ○ Example 8 ○ ◎ ◎ ◎ ◎ ◎ ○ Example 9 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 1 X X △ △ △ X ○ Comparative Example 2 X X ○ △ △ △ ○ Comparative Example 3 X X X X △ X ○ Comparative Example 4 X X X X △ X ○ Comparative Example 5 ◎ ◎ ◎ ◎ ◎ △ ○

As is clear from the results shown in Table 2, the peeling liquid compositions of Examples 1 to 9 exhibited excellent peeling force without causing corrosion of the wiring during the peeling of the color resist or the organic film.

It was also found that the peeling force was kept the same in the peelability evaluation at a high temperature with time.

On the other hand, the compositions of Comparative Examples 1 to 4 were all inferior in peel strength and evaluation results of peel strength maintenance at high temperature with time. The composition of Comparative Example 5 was excellent in the peeling force of the color resist or the organic film, but the peeling force after the peeling at a high temperature was remarkably lowered, which was not suitable for use.

That is, the release liquid composition of the present invention is excellent in peeling ability of color resist and organic film, and excellent in stability at a high temperature or with aging, and thus has excellent peeling continuity even under these harsh conditions.

Claims (8)

About the total weight of the composition
1 to 15% by weight of a quaternary ammonium salt compound,
20 to 70% by weight of a polar organic solvent,
1 to 20% by weight of an alkylene glycol alkyl ether,
0.1 to 5% by weight of at least one hydrazine derivative compound selected from the following formulas (1) to (3)
0.01 to 2% by weight of an inorganic base or a salt thereof, and
And 1 to 40% by weight of water.

&Lt; Formula 1 >

In the general formula 1 R ₁ is a hydroxyalkyl group of C1 ~ C6,
(2)

In Formula 2, R ₂ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, an amino group, or -NHNH ₂ .
(3)

The method according to claim 1,
Wherein the quaternary ammonium salt compound is a quaternary alkyl ammonium hydroxide. The method according to claim 1,
The polar organic solvent preferably includes at least one selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, sulfolane, n-methylpyrrolidone, pyrrolidone and n-ethylpyrrolidone By weight based on the total weight of the composition. The method according to claim 1,
The alkylene glycol alkyl ether is 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 and diethylene glycol methyl ethyl ether Wherein the organic solvent is at least one selected from the group consisting of organic solvents and organic solvents. The method according to claim 1,
The inorganic base or its salt compound may be at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium silicate, Potassium, and the like. The method according to claim 1,
A color resist or an organic film stripping liquid composition, which further comprises a corrosion inhibitor. The method of claim 6,
Wherein the corrosion inhibitor is at least one selected from an azole compound, a catechol compound and an alkyl gallate compound. The method of claim 6,
Wherein the amount of the corrosion inhibitor is 0.1 to 5% by weight based on the total weight of the composition.