JP2009114268A - Remover for polyimide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a remover for a polyimide having excellent washability while suppressing the corrosion of a metal (particularly aluminum and molybdenum). <P>SOLUTION: The remover for the polyimide contains water, an alkalizing agent [B], a water-soluble organic solvent [C] except a polyhydric alcohol, a polyhydric alcohol [D], and a silane-based compound [A] represented by general formula (1) below. In the remover, the content of the component [C] is 30-95 wt.%. [(X<SB>2</SB>N-(CH<SB>2</SB>)<SB>l</SB>-)<SB>m</SB>NH<SB>2-m</SB>-(CH<SB>2</SB>)<SB>k</SB>-]<SB>n</SB>Si(OR)<SB>4-n</SB>(1) [wherein k and l represent an integer of 1-4, m represents an integer of 0-2, n represents an integer of 1-3, R is hydrogen or a 1-4C alkyl group, and X is hydrogen or a 1-4C alkyl group]. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a release agent for polyimide used for peeling a polyimide-based photoresist or the like used for manufacturing a liquid crystal substrate having metal wiring (particularly aluminum and molybdenum), a polyimide alignment film on a semiconductor substrate, and a semiconductor element circuit. .

  Conventionally, alkaline cleaning liquids are excellent in the ability to remove oils and fats, resins, fine particles, resins, and the like, and are therefore often used for cleaning electronic parts, metal parts, and the like. However, a general alkaline cleaning solution has a strong action of dissolving aluminum and molybdenum, and is currently difficult to apply to cleaning of electronic parts using aluminum and molybdenum. For example, when the polyimide alignment film of the TFT side liquid crystal panel is to be peeled off, the molybdenum / aluminum laminated wiring of the TFT circuit is dissolved. Therefore, a method of protecting the wiring portion with wax or the like and cleaning it and removing the wax with a solvent such as hydrocarbon to regenerate the glass substrate is taken, but the process is complicated.

Moreover, as a kind of alkaline cleaner, an alkaline release agent has been conventionally used for the purpose of removing a photoresist residue in a manufacturing process of a semiconductor element circuit or the like. There are anhydrous and water-containing alkaline release agents, and water-containing ones are preferable from the viewpoint of releasability. However, the hydrous alkaline release agent has a problem of dissolving the metal wiring on the substrate. An aqueous solution containing various alcohols in a quaternary ammonium hydroxide has been proposed as a resist stripper that solves this problem and does not dissolve metal wiring or the like (see, for example, Patent Document 1). Moreover, the resist release agent containing the compound containing Si atom is known for the purpose of improving metal corrosion resistance (refer patent document 2). However, these resist removers have insufficient peelability for polyimide.
JP 2005-336470 A Japanese Patent No. 3410369

  Thus, even if these conventional techniques are used, the present situation is that both the peelability of the polyimide alignment film and the anticorrosion properties of metals (especially aluminum and molybdenum) are not compatible, and improvement of these problems has been demanded. .

  Accordingly, an object of the present invention is to provide a polyimide release agent having excellent cleaning properties while suppressing corrosion of metals (particularly aluminum and molybdenum).

The present invention comprises water, an alkali agent [B], a water-soluble organic solvent excluding polyhydric alcohol [C], polyhydric alcohol [D], and a silane compound [A] represented by the following general formula (1). And a release agent for polyimide having a content of the [C] component of 30 to 95% by weight.
_{[(X 2 N- (CH 2} ) l -) m NH 2-m - (CH 2) k -] n Si (OR) 4-n (1)
In the formula, k and l are integers of 1 to 4, m is an integer of 0 to 2, and n is an integer of 1 to 3. R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is hydrogen or an alkyl group having 1 to 4 carbon atoms.

  The polyimide release agent of the present invention is excellent in polyimide peelability and excellent in metal (particularly aluminum and molybdenum) corrosion resistance. Therefore, the polyimide alignment film can be easily peeled and cleaned without damaging the metal wiring on the TFT side of the liquid crystal panel glass substrate. Further, the polyimide release agent of the present invention does not damage the color filter, and the polyimide alignment film on the color filter side can be similarly peeled and washed. Furthermore, the polyimide release agent of the present invention is also excellent in oil, fingerprint, resin and fine particle detergency.

  The silane compound [A] is not particularly limited as long as it is a compound represented by the above general formula (1). Specifically, for example, γ-aminopropyltrihydroxysilane and its condensate, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (3-aminopropyl) aminopropyltrimethoxysilane and the like can be mentioned. Of these, γ- (2-aminoethyl) aminopropyltrimethoxysilane is particularly preferred. The silane compound [A] may be used alone or in combination of two or more.

  In the present invention, the content of the silane compound [A] is preferably 0.1 to 10% by weight. If the content of the silane compound [A] is less than 0.1% by weight, the corrosion resistance of aluminum and molybdenum may be insufficient, and if it exceeds 10% by weight, the polyimide peelability may be lowered. More preferably, it is 0.2 to 5% by weight.

  The alkali agent [B] used in the present invention is not particularly limited as long as it can be used for alkali cleaning, and a known alkali agent can be used, but a quaternary ammonium hydroxide [B1]. Suitable examples include alkanolamines [B2] having a boiling point of 150 ° C. or higher. The quaternary ammonium hydroxide [B1] and the alkanolamine [B2] having a boiling point of 150 ° C. or higher may be used alone or in combination. The quaternary ammonium hydroxide [B1] is represented by the following general formula (2).

In the formula, R represents an alkyl group having 1 to 3 carbon atoms or a hydroxy-substituted alkyl group having 1 to 3 carbon atoms, and R ₁ , R ₂ , and R ₃ are the same or different alkyl groups having 1 to 3 carbon atoms. Represents. Specific examples of the quaternary ammonium hydroxide [B1] include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, and trimethyl (2-hydroxyethyl) ammonium hydroxy. And tripropyl (2-hydroxyethyl) ammonium hydroxide, trimethyl (1-hydroxypropyl) ammonium hydroxide, and the like. Among these, tetramethylammonium hydroxide (hereinafter abbreviated as TMAH), tetraethylammonium hydroxide, and trimethyl (2-hydroxyethyl) ammonium hydroxide are particularly preferable. The quaternary ammonium hydroxide [B1] may be used alone or in combination of two or more.

  The alkanolamine [B2] preferably has a boiling point of 150 ° C. or higher. If the boiling point is less than 150 ° C., it is likely to scatter in the operating temperature condition of 40 to 80 ° C., which is not preferable in terms of odor. Examples of the alkanolamine [B2] having a boiling point of 150 ° C. or higher include compounds having an amino group and an alcoholic hydroxyl group in the same molecule, ethanolamines such as mono, di, and tri, and isopropanolamine. Of these, monoethanolamine, diethanolamine, and triethanolamine are particularly preferable. 1 type may be used for the said alkanolamine [B2], or 2 or more types may be used together.

  In the present invention, the content of the alkaline agent [B] is preferably 0.1 to 60% by weight, more preferably 0.2 to 50% by weight. When the content of the alkali agent is less than 0.1% by weight, the polyimide peelability may be insufficient, and when it exceeds 60% by weight, the viscosity may increase and the workability may decrease. The content of quaternary ammonium hydroxide [B1] is 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, and the content of alkanolamine [B2] having a boiling point of 150 ° C. or higher is 5%. It is -55 weight%, More preferably, it is 10-50 weight%. When the content of the quaternary ammonium hydroxide [B1] exceeds 10% by weight, the metal corrosivity cannot be suppressed and the quaternary ammonium hydroxide may not be dissolved.

  In the present invention, the water content is preferably 1 to 50% by weight, more preferably 5 to 30% by weight. If the water content is less than 1% by weight, the quaternary ammonium hydroxide does not dissolve, and if it exceeds 50% by weight, the metal anticorrosion property may be insufficient.

The water-soluble organic solvent [C] excluding the polyhydric alcohol in the present invention is not particularly limited as long as it is a water-soluble organic solvent and is not a polyhydric alcohol (dihydric or higher alcohol). Those having a solubility (g / 100 g H ₂ O) of 100 or more and a boiling point of 150 ° C. or more can be suitably used. If the boiling point is less than 150 ° C., it tends to scatter under the operating temperature conditions (40 to 80 ° C.), which is not preferable in terms of odor and safety. Specific examples include glycol ethers and polar solvents. As glycol ethers, ethyl cellosolve, butyl cellosolve, ethylene glycol monotertiary butyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, etc. as polar solvents Dimethyl sulfoxide (hereinafter abbreviated as DMSO), sulfolane, N-methyl-2pyrrolidone, γ-butyrolactam, furfural and the like. Among these, 3-methoxy-3-methyl-1-butanol, propylene glycol, diethylene glycol monobutyl ether, DMSO and the like can be preferably used. These water-soluble organic solvents may be used alone or in combination.

  In the present invention, the content of the water-soluble organic solvent [C] excluding the polyhydric alcohol is 30 to 95% by weight, preferably 40 to 90% by weight. If the content of the water-soluble polar solvent [C] is less than 30% by weight, the solubility in fats and oils and resins decreases, and if it exceeds 95% by weight, other components are reduced and both polyimide peelability and aluminum and molybdenum anticorrosive properties are achieved. May become difficult.

  The polyhydric alcohol [D] in the present invention is not particularly limited as long as it can be used for alkali cleaning, but is preferably a divalent to octavalent one. Specific examples include ethylene glycol, propylene glycol, glycerin, Examples include xylitol, sorbitol, mannitol and the like. Of these, ethylene glycol, glycerin and sorbitol are particularly preferred.

  In the present invention, the content of the polyhydric alcohol [D] is preferably 1 to 50% by weight, more preferably 3 to 20% by weight. If the content of the polyhydric alcohol [D] is less than 1% by weight, the corrosion resistance of aluminum and molybdenum may be insufficient, and if it exceeds 50% by weight, the polyimide peelability may be lowered.

  When the silane compound [A] and the divalent to octavalent polyhydric alcohol [D] are used in combination, the corrosion resistance against metals, particularly the corrosion resistance against molybdenum, is greatly improved.

In the present invention, the solubility (g / 100 gH ₂ O) in water, the above-mentioned [A], [B1] and / or [B2], water at 25 ° C. is 100 or more, and the boiling point is 150 ° C. or more [C And combinations of 2 to 8 valent [D] components are preferred.

  In the present invention, in addition to the above-mentioned water, [A], [B], [C], and [D] components, they are used for general alkaline cleaning liquids such as surfactants within the range not impairing the object of the present invention. Additives that have been added can be added as other components [E]. As said component [E], a C6-C12 branched fatty acid soap can be mention | raise | lifted, for example. The compounding quantity of these other components may be 0.01 to 10 weight% normally in a composition.

  The polyimide release agent of the present invention preferably has a pH of 12 or more. When pH is less than 11, sufficient polyimide peelability may not be obtained.

  The viscosity of the release agent for polyimide of the present invention is preferably 20 mPa · s (25 ° C.) or less from the viewpoints of workability and peelability.

  The release agent for polyimide of the present invention can be produced by mixing the above components. For example, it can be prepared by mixing [A], [B1] and / or [B2], [C], [D], and [E], and water if applicable.

  The usage method of the release agent for polyimides of this invention is illustrated below. However, the present invention is not limited to this example. First, a substrate (substrate such as glass) on which a polyimide alignment film is formed is prepared. Examples of the material for the polyimide alignment film include polyimide materials such as a polyimide alignment film material mainly composed of a polyimide resin, a coupling agent, ethylene glycol monobutyl ether, and N-methyl-2-pyrrolidone (NMP). Good. Next, the polyimide alignment film of this substrate is immersed in the release agent for polyimide of the present invention, for example, at room temperature to 80 ° C. for 1 to 10 minutes. At this time, if necessary, the release agent may be stirred or the substrate may be vibrated. Alternatively, the release agent of the present invention can be sprayed onto the substrate with a shower or spray. At this time, the polyimide alignment film removability can be improved by using brush cleaning together. After dissolving or peeling the polyimide alignment film, the release agent containing the dissolved polyimide alignment film is preferably washed away with pure water, and the polyimide alignment film is removed from the substrate. Thereafter, the liquid on the substrate is blown off with an air knife or the like, and the substrate is dried.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.

Examples 1-7, Comparative Examples 1-10
The component parts (parts by weight) shown in Table 1 (parts expressed by weight) were put in a 1 L beaker and sufficiently stirred at room temperature to prepare polyimide release agents for Examples and Comparative Examples.
Abbreviations in Table 1 are as follows.
A component (silane compound)
A1: γ- (2-aminoethyl) aminopropyltrimethoxysilane A2: 1,6-bis (trimethoxysilyl) hexane B component (alkali agent)
B1: Tetramethylammonium hydroxide B2a: Ethanolamine B2b: Triethanolamine C component (water-soluble organic solvent)
C1: DMSO
C2: Diethylene glycol monomethyl ether D component (polyhydric alcohol)
D1: Ethylene glycol D2: Glycerin D3: Sorbitol

The evaluation test method of the release agent for polyimides obtained in Examples and Comparative Examples is shown below, and the evaluation results are shown in Table 1.
1. Polyimide alignment film (hereinafter simply referred to as alignment film) releasability An alignment film material composed mainly of a polyimide resin, a coupling agent, ethylene glycol monobutyl ether and NMP is applied onto a glass substrate, and baked at 120 ° C. for 60 minutes. A polyimide film was an object to be peeled. The substrate was cut into 1 × 4 cm, and the substrate was dipped in an alkali cleaning solution at 40 ° C. for a predetermined time (1 minute, 2 minutes). Then, it took out, washed with pure water, blown off pure water with an air gun using N ₂ gas, and naturally dried. Each of the treated substrates was observed with a microscope, and the alignment film peelability was evaluated in the following five stages.
<Evaluation criteria>
5: There is no alignment film on the glass substrate 4: Traces of the alignment film remain on the glass substrate 3: A little alignment film remains on a part of the glass substrate 2: Most of the alignment film on the glass substrate The alignment film remains 1: The alignment film remains on the entire surface of the glass substrate

2. Aluminum Corrosion Resistance A pure aluminum plate of 3 cm × 4 cm was immersed in a release agent for polyimide at 70 ° C. for 24 hours, and the hydrogen gas generation status and weight reduction rate were measured. The calculation method is as follows.
Weight reduction rate (%) = 100 × (W0−W1) / W0
[W0: Original aluminum plate weight (g), W1: Aluminum plate weight after immersion for 24 hours at 70 ° C. (g)]
In addition to the weight reduction rate, the hydrogen gas generation status was also observed according to the following evaluation criteria.
<Evaluation criteria>
5: No generation of hydrogen gas 4: Little generation of hydrogen gas is observed slightly 3: Generation of hydrogen gas is slightly recognized 2: Generation of hydrogen gas is fairly recognized 1: Generation of hydrogen gas is observed violently Be

3. Molybdenum anticorrosive property A glass substrate 10 mm × 10 mm on which molybdenum was vapor-deposited and a polyimide release agent were placed in a 70 mL wide-mouth bottle, and kept at 70 ° C. with the molybdenum vapor-deposited surface facing up. The appearance change of the molybdenum deposition surface after 24 hours from the start of the treatment was observed according to the following evaluation criteria.
<Evaluation criteria>
○: No change Δ: Change to black ×: Molybdenum film dissolves and disappears.

  From the results in Table 1, the release agent for polyimide of the present invention using silane compound [A], alkali agent [B], water-soluble organic solvent excluding polyhydric alcohol [C], polyhydric alcohol [D], and water is as follows. Although the pH is 12 or more, it can be seen that the corrosion resistance of aluminum and molybdenum is extremely good, and both the alignment film peelability / aluminum and molybdenum corrosion resistance are compatible (Examples 1 to 7). On the other hand, the composition containing no [A] component and [D] component (Comparative Example 1) and the composition containing no [A] component and containing a large amount of [B] component (Comparative Example 8) have aluminum corrosion resistance and molybdenum. Corrosion protection is inferior. The composition containing [D] component but not containing [A] component (Comparative Example 2) and the composition containing [A] component but not containing [D] component (Comparative Examples 5 and 7) Although it is excellent in properties, it is inferior in the anti-corrosive properties of Morbden. A composition containing each component of [A], [B] and [D] but not containing the component [C] (Comparative Example 3) and each component of [A], [B], [C] and [D] The composition (Comparative Example 10) containing a small amount of the component [C] is excellent in aluminum corrosion resistance, but is inferior in molybdenum corrosion resistance, and the alignment film cannot be peeled off. The composition (Comparative Example 4) described in Prior Document 1 (Japanese Patent Laid-Open No. 2005-336470) is insufficient in both alignment film peelability and aluminum corrosion resistance. Compositions (Comparative Examples 6 and 9) containing a silane compound which is described in Prior Document 2 (Japanese Patent No. 3410369) but does not fall under the present invention are inferior in molybdenum corrosion resistance.

Claims (6)

Water, alkaline agent [B], water-soluble organic solvent excluding polyhydric alcohol [C], polyhydric alcohol [D], and silane compound [A] represented by the following general formula (1), The release agent for polyimides whose content of [C] component is 30 to 95 weight%.
_{[(X 2 N- (CH 2} ) l -) m NH 2-m - (CH 2) k -] n Si (OR) 4-n (1)
[Wherein, k and l are integers of 1 to 4, m is an integer of 0 to 2, and n is an integer of 1 to 3. R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is hydrogen or an alkyl group having 1 to 4 carbon atoms. ]   The release agent for polyimide according to claim 1, wherein the silane compound [A] is γ- (2-aminoethyl) aminopropyltrimethoxysilane.   Alkaline agent [B] is quaternary ammonium hydroxide [B1] and / or alkanolamine [B2] having a boiling point of 150 ° C. or higher, and water-soluble organic solvent [C] has a solubility in water at 25 ° C. of 100 or higher. And the release agent for polyimides of Claim 1 or 2 whose boiling point is 150 degreeC or more and whose polyhydric alcohol [D] is a 2-8 valent alcohol.   Silane compound [A] 0.1 to 10% by weight, alkali agent [B] 0.1 to 60% by weight, water-soluble organic solvent [C] 30 to 95% by weight, polyhydric alcohol [D] The release agent for polyimide according to any one of claims 1 to 3, comprising 1 to 50% by weight and 1 to 50% by weight of water.   pH is 12 or more, The release agent for polyimides in any one of Claims 1-4.   It is a release agent for polyimide alignment films on a liquid crystal substrate, The release agent for polyimides in any one of Claims 1-5.