TW201814036A - Resist removal liquid - Google Patents

Abstract

In a production process for semiconductor devices, etc., curing occurs at a higher temperature than conventional production processes, in order to avoid resist curing defects. As a result, a removal liquid having stronger removal force than conventionally available is required. This resist removal liquid: includes a secondary amine, a 1, 3-dimethyl-2-imidazolidinone (DMI) as a polar solvent, and water; incudes hydrazine as an additive; is characterized by the water being at least 10.0% by mass and less than 31.0% by mass; is capable of removing a resist baked at high temperature; and does not corrode film surfaces or cross-sections.

Description

   Resist stripping solution   

The present invention relates to a peeling liquid used to peel off a resist used in the manufacture of display elements such as liquid crystals, organic ELs, and semiconductors. More specifically, the present invention relates to a resist film capable of removing the resist even after curing and baking It can also be said that it is a resist stripping solution that does not substantially corrode even an aluminum film and a copper film.

In a flat panel display (FPD) such as liquid crystal or organic EL (Electro-Luminescence), a large screen is required. On the other hand, as notebook PCs, desktop PCs, and smartphones, small and high-definition screens are required. As a large screen system, a TFT (Thin Film Transistor) is used (a Cu wiring or a Cu / Mo laminated wiring (hereinafter, also referred to simply as a "Cu wiring")). In addition, a TFT (using Al wiring) is used as a system for a small high-definition screen. In the following, Cu is also referred to as copper, Mo is molybdenum, and Al is aluminum.

Panel manufacturers also produce TFTs using Cu wiring and TFTs with mixed Cu wiring and Al wiring in one factory. If the TFT is mixed in a state where Cu wiring and Al wiring are produced and the resist film is peeled off, and the resist stripping solution is shared between the state where Al wiring is used and the state where Cu wiring is used, production cost and device.

Water-based positive photoresist stripping solutions are generally composed of an alkanolamine, a polar solvent, and water. The resist stripping device is heated and used at a temperature of 40 ° C to 50 ° C.

Alkanolamines are used to make the carbonyl group of a DNQ (diazonaphthoquinone) compound in a positive photoresist stripping solution become a base insolubilizer by nucleation. It can be dissolved in polar solvents and water. Become an essential ingredient. Alkanolamines are classified into primary, secondary, and tertiary by the number of substituents other than hydrogen bonded to the nitrogen element. Among them, it is known that the smaller the series and the stronger the basicity, the stronger the nucleation property.

Therefore, the smaller the number of alkanolamines, the greater the strength of the DNQ compound that becomes an alkali insolubilizer that can be dissolved in a polar solvent or water, and exert a strong resist peeling performance.

On the other hand, it is known that alkanolamines have a chelating effect on Cu. The chelation system for Cu can dissolve Cu, and therefore corrode the Cu film. The chelation of Cu is the same as basicity or nucleation. The smaller the order of alkanolamine, the stronger the chelation. Therefore, the smaller the number of alkanolamines, the more strongly the Cu film is corroded.

In so-called amorphous silicon (hereinafter, also referred to as "a-Si") or low-temperature polycrystalline silicon (hereinafter, also referred to as "LTPS"), oxide semiconductors (hereinafter, also referred to as "IGZO" "). In the production process of high-definition TFTs for semiconductors, in the dry etching process, the resist is damaged to denature and it is not easy to peel off the resist. This is considered to be because the polymerization between the DNQ compound and the phenol resin constituting the positive-type resist film proceeded excessively.

The Al wiring system is not subject to corrosion (chelation) caused by alkanolamine. Because of this, peeling denaturation inhibitors are generally used as primary alkanolamines having strong peeling properties.

On the other hand, in the state of the Cu wiring, when a primary or secondary alkanolamine is used, a large amount of corrosion of the Cu wiring occurs to a state that cannot be tolerated. Therefore, it is proposed to use a tertiary alkanolamine stripping solution. The tertiary alkanolamine system has a weaker chelation effect on Cu, and can suppress the corrosion of the Cu film to a range without practical problems. However, the alkalinity or nucleation system is also weaker in the same manner as chelation. Compared with the use of a primary or secondary alkanolamine barrier stripping solution, there is a disadvantage that the so-called barrier stripping force is weaker.

Under such a technical background, there is a demand for a resist peeling liquid composition having a peeling performance equal to or higher than that of an Al wiring resist peeling liquid using a primary alkanolamine, which can be used for both Cu wiring and Al wiring.

In addition, Patent Document 1 discloses a resist peeling liquid containing a compound represented by the chemical formula (1) and a solvent. This type of resist stripping solution can also be used in the resist stripping process for Cu wiring and Al wiring.

In addition, Patent Document 2 discloses a resist peeling solution that has a peeling force equivalent to that of an Al wiring resist peeling solution using a primary alkanolamine, regardless of whether a tertiary alkanolamine is used or not. The stripping liquid system includes a tertiary amine, a polar solvent, water, a cyclic amine, a sugar alcohol, and a reducing agent. The aforementioned five-membered cyclic amine system has a pyrrolidine or pyrrolidine having a substituent at the 3-position.

    [Previous Technical Literature]         [Literary Literature]    

Patent Document 1: Japanese Patent Application Publication No. 2012-514765 (Japanese Patent No. 5279921)

Patent Document 2: Japanese Patent Application Laid-Open No. 2016-085378 (Japanese Patent No. 5885041)

The peeling liquid system of Patent Document 2 can be used in common for Cu wiring (including Cu / Mo laminated wiring) and resist peeling process for Al wiring. In addition, it is assumed that the resist film can be peeled off even if hardening baking is performed on the resist film.

However, at the manufacturing site of a semiconductor device using a resist, a larger-scale substrate processing is performed once. Therefore, the failure of the photolithography process at one time is related to a large number of defective products at one time. Therefore, in the processes of photolithography, the operating parameters are used in terms of safety.

Specifically, in the hardening process of the resist, hardening at a higher temperature is performed to avoid the problem of poor hardening of the resist. However, at the same time, this system indicates that the peeling force needs to be stronger than the previous peeling liquid.

The present invention has been conceived in view of the foregoing problems, and provides a resist stripping solution capable of peeling even when the resist is baked at a higher temperature than before. Needless to say, it is needless to say that not only the peeling force becomes stronger, but also the so-called lowering of the corrosiveness to metals called Cu, Mo, and Al.

More specifically, the resist stripping solution of the present invention is characterized by comprising a secondary amine, 1,3-dimethyl-2-imidazolidinyl (DMI) as a polar solvent, and water, including hydrazine. As an additive, the aforementioned water system is 10.0% by mass or more and less than 31.0% by mass.

Since the barrier agent stripping solution of the present invention uses a secondary amine, the barrier agent can be reliably peeled even if the barrier agent is baked at a higher temperature than before. In addition, the resist stripping solution of the present invention contains 1,3-dimethyl-2-imidazolidinyl (DMI) as a polar solvent, and therefore suppresses the so-called Cu, Mo, and Corrosion of Al metal.

In addition, since the resist stripping solution of the present invention uses a secondary amine having a high boiling point, it can be recycled after use.

In addition, the resist stripping solution of the present invention has a good liquid bath life. Even if it is left in the open air for more than 12 hours, even if it is sealed for 4 days, the resist peeling ability is not changed.

1‧‧‧ substrate

2‧‧‧ membrane department

3‧‧‧ basal layer

4‧‧‧ (of the membrane) surface

5‧‧‧ taper angle

10‧‧‧ (between the Mo layer and Cu layer of the substrate)

FIG. 1 is a diagram illustrating a cone angle and a Mo cut of a Cu / Mo laminated film.

Hereinafter, the resist peeling liquid of this invention is demonstrated. In addition, the following description shows an embodiment of the photoresist stripping solution of the present invention, and the following embodiments and examples can be changed without departing from the spirit of the present invention. In addition, in the present specification, the terms "above" and "below" used to indicate a range have the meanings of "larger inclusive of their values" and "smaller inclusive of their values", and "underfilled" are so-called The meaning of "smaller without its value".

The stripped resist film of the resist stripping solution of the present invention is assumed to be a positive resist. The positive-type resist includes a phenolic resin as a resin, and a diazonaphthoquinone (DNQ) compound is used as a photosensitizer. In the state where the etching is performed, a resist film is formed on the substrate, and exposure is performed through the pattern.

By this exposure, the DNQ compound is changed to indenketene. When indenketene meets with water, it becomes indenecarboxylic acid and is dissolved in water. Phenolic resins originally have the property of dissolving in an alkaline solution, and the melting point is protected by a DNQ compound. The DNQ compound undergoes modification by exposure, is dissolved in a developer containing water, and also dissolves a phenolic inhibitor. The patterning of the resist film is completed in this manner.

The substrate patterned by the resist film is subjected to wet etching or dry etching after baking. Post-baking is performed to polymerize the phenol resin and DNQ compound in the resist film to some extent. The heat treatment is usually performed at 140 ° C for about 5 minutes. In the present specification, the term “hardening and baking” refers to heating conditions at 170 ° C. for 30 minutes or more. When the baking temperature rises, the phenolic resin and the DNQ compound are rapidly polymerized to be firmly fixed to the metal film on the substrate, and are not easily dissolved. The resist peeling liquid system of the present invention is also targeted for a resist film that has undergone such hardening and baking.

The resist stripping solution of the present invention includes a secondary amine, a polar solvent, and a reducing agent. The secondary amines have a higher boiling point than water, and are preferably azeotropic without water. It is because it is separated from water when the stripping liquid is recycled. As such, N-methylethanolamine (hereinafter, also referred to as "MMA". Boiling point is 155 ° C. CAS number 109-83-1), N-ethylethanolamine (hereinafter, also referred to as "MMA") "EEA". Boiling point is 170 ° C. CAS number 110-73-6). These lines can be mixed.

In addition, the total amount of these stripping solutions is preferably 0.5% by mass or more and 9.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less, and most preferably 2.0% by mass or more and 7.0% by mass or less. When the secondary amine decreases, the hardened and baked resist film cannot be peeled off. On the other hand, when there is too much, the metal damage will increase. In addition, it is confirmed that even if it contains 9.0% by mass, there is no problem with the required performance.

The polar solvent may be an organic solvent (also referred to as a water-soluble organic solvent) having an affinity for water. In addition, if the miscibility with the aforementioned secondary amine is good, it is more suitable.

As such a water-soluble organic solvent system, 1,3-dimethyl-2-imidazolidinyl group (hereinafter, also referred to as "DMI". CAS No. 80-73-9) can be suitably used. The polar solvent is composed of a water-soluble organic solvent and water.

The amount of the polar solvent is the amount of the secondary amine and the reducing agent described later with respect to the entire amount of the stripping solution. Specifically, it is 90.60 mass% or more and 99.47 mass% or less.

Various materials in polar solvents have the following ideal ranges. First, the water system is preferably 10.0% by mass or more and less than 31.0% by mass based on the total amount of the resist stripping solution. This is because the problem of so-called corrosion of Al occurs when the metal film is Al when there is too much water. 1,3-Dimethyl-2-imidazolidinyl (DMI) system can remain as a polar solvent. 1,3-Dimethyl-2-imidazolidinyl (DMI) only stabilizes hydrazine in this way, and alleviates the damage of secondary amines and hydrazines to the surface and cross-section of metal films.

As the additive system, hydrazine (hereinafter, also referred to as "HN". CAS No. 302-01-2) can be suitably used as a reducing agent. The addition of the reducing agent suppresses Mo undercutting due to the secondary amine. The reducing agent is preferably in a range of 0.03% by mass or more and 0.4% by mass or less with respect to the total amount of the resist stripping solution. The range is more preferably 0.06 mass% or more and 0.2 mass% or less. From the viewpoint of safe handling, a hydrazine can be used for the hydrazine system (hydrazine-hydrate: described as "HN.H ₂ O").

    Examples    

Examples and comparative examples of the resist peeling liquid of the present invention are shown below. The resist peeling liquid was evaluated based on three aspects: "resistive peelability", "corrosiveness of metal film" and "liquid bath life".

    <Resistant Peelability>    

A 100 nm silicon thermal oxide film is formed on a silicon substrate, and a 300 nm thick copper film is formed on the silicon thermal oxide film by a sputtering method. On this copper film, a positive resist liquid was applied by spin coating to produce a resist film. After the resist film is dried, exposure is performed using a mask of a wiring pattern. Then, the resist in the photosensitive portion is removed by a developing solution. That is, it is in the state where the resist film of a wiring pattern remains on a copper film, and the state which has a part which exposes a copper film. Then, the entire silicon substrate was baked at 170 ° C. for 30 minutes.

Next, the exposed copper film is etched and removed using a hydrolytic copper etchant. After the etching of the copper film is finished, the resist film on the remaining copper pattern is peeled off using a sample resist stripping solution. The processing time for peeling was 15 minutes, and the time until peeling was measured. The interference was applied by an optical microscope that can be peeled off, and the observation was performed to judge.

In the state where the residue of the resist film was confirmed on the copper film even after 15 minutes passed, it became "×" (fork. Defective), and in the state where the residue of the resist film was not confirmed, it became "○" (circle. good). In this state, the completion time of peeling is also recorded. In addition, "○" (circle. Good) indicates success or pass, and "×" (cross. Bad) indicates failure or fail. The same applies to the following evaluations.

    <Corrosiveness of metal film>    

The corrosion resistance of the metal film was evaluated as follows. First, a 100-nm-thick silicon thermal oxide film is formed on a silicon substrate. Next, a molybdenum film was formed on the thermal oxidation film of silicon on a silicon substrate to a thickness of 20 nm, and then a copper film was formed on the thermal oxidation film to a thickness of 300 nm to prepare a Cu / Mo laminated film sample. This system is described as "Cu / Mo". In addition, an aluminum film was formed on a thermal oxidation film of silicon on a silicon substrate to a thickness of 300 nm, and an aluminum film sample was produced. This department is recorded as "Al".

On these evaluation samples, a resist patterned in a wiring shape was formed to be a base material for corrosion evaluation. That is, the base material for corrosion evaluation is a resist layer formed of any one of a Cu / Mo film and an Al film on a thermally oxidized film of silicon formed on a silicon substrate and a wiring shape thereon. While composed.

These substrates for corrosive evaluation are immersed in an etchant for a copper film or an aluminum film for an appropriate amount of time and etched. Then, the sample resist peeling liquid was immersed in the base material for corrosion evaluation after etching for 4 minutes, and the resist film was peeled. The base material for corrosion evaluation was immersed in the sample resist stripping solution for 4 minutes, washed, and after drying, the surface of the film was observed. In addition, cut the wiring portion and observe the cut surface.

In addition, the judgment of an appropriate amount of etching is the time from the start of the etching to the time when the thermal oxide film of silicon can be visually confirmed.

The surface of the film and the cut surface were observed using a scanning electron microscope (SEM) (manufactured by Hitachi: SU8020) under conditions of an acceleration voltage of 1 kV and 30,000 to 50,000 times.

FIG. 1 is a conceptual diagram showing the shape of the cut surface. Fig. 1 (a) shows the state of the cut surface in the state of "Al". The shape of the cut surface of the portion to be etched at an appropriate amount is a tapered angle 5 that forms an angle of about 30 ° to 60 ° with respect to the substrate 1. The film portion 2 is an Al film.

The state of "Cu / Mo" is shown in FIG. 1 (b). The state of "Cu / Mo" is such that at least the upper film portion 2 (Cu) has a tapered angle 5. The underlayer 3 (Mo) is preferably etched along the tapered surface 6 of the film portion 2. However, as shown in FIG. 1 (b), there may be a residue of etching from the film portion 2.

The evaluation of the corrosiveness is judged to be a fork in a state where the corrosion is confirmed by observing the shape of the cross section on either the membrane portion 2 or the surface 4 of the membrane portion 2 or the base layer 3. Defective (×) was judged to be round when no corrosion was observed. Good (○).

In particular, in the "Cu / Mo" state, as shown in Fig. 1 (c), a state where corrosion occurs between the base layer 3 (Mo) and the film portion 2 (Cu) occurs. That is, the Mo of the base layer 3 starts to dissolve from the interface between the film portion 2 and the base layer 3, so that the Mo (base layer 3) can be etched more quickly than the copper layer (film portion 2). Therefore, in a state where a gap 10 can be confirmed between the base layer 3 and the membrane portion 2, the evaluation becomes a fork. Bad (×).

    <Liquid bath life>    

The resist stripping liquid is a mixed composition of an amine, an organic solvent, and a material called a reducing agent. Carbon dioxide in the air is dissolved in the stripping solution and becomes carbonic acid. The bicarbonate ions are either reacted with amines to form amine formate ions. As a result, the peeling force is reduced or the metal damage is increased.

Especially in large-scale factories, a large amount of resist stripping solution is used in open atmosphere. In addition, since the resist peeling liquid is used cyclically, there is more chance that the resist peeling liquid meets air. Therefore, as the life of the liquid bath becomes shorter, the resist stripping solution must be frequently replaced or replenished.

As a test method, after preparing each resist stripping solution, it was left to stand for 0 hours, 6 hours, and 12 hours in a normal-temperature atmosphere in the atmosphere, and a test was performed for the resist peelability. The "Cu / Mo" and "Al" surface and cross-section state. The evaluation method is the same as in the case of <resistance peelability> and <corrosiveness of metal>.

In addition, the resist peeling liquid was put into a container and carried in. However, if it cannot be stored in a container at normal temperature, the applicability in the factory is extremely poor. Therefore, investigations were also performed by storing the changes in the components at room temperature in a closed atmosphere.

The evaluation method was put in a closed container and left at room temperature for 4 days to measure the stability of hydrazine. In comparison, immediately after the preparation of hydrazine, the state of reduction by more than 1% is "×", and if it is less than 1%, it is "○".

    <Sample Resistant Stripping Solution>    

The sample resist stripping solution was prepared in the following manner.

    (Example 1)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was mixed with water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolyl (DMI): 74.9% by mass, and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist stripping solution of Example 1.

In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate. In all the examples and comparative examples below, the state of using hydrazine-hydrate has the same meaning.

    (Example 2)    

As the secondary amine, N-ethylethanolamine (N-ethylethanolamine (EEA): 5.0% by mass) was used. The polar solvent was mixed with water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolyl (DMI): 74.9% by mass, and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist peeling liquid of Example 2.

Example 2 changed the composition of N-methylethanolamine (MMA) as the secondary amine of Example 1 to N-ethylethanolamine (EEA). In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Example 3)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 70.9% by mass and water: 24.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist stripping solution of Example 3.

Example 3 changed the composition of the ratio of DMI and water of the polar solvent of Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 24.036% by mass, including a portion charged as a hydrazine-hydrate.

    (Example 4)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 68.9% by mass and water: 26.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist stripping solution of Example 4.

Example 4 changed the composition of the ratio of DMI to water of the polar solvent of Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 26.036% by mass as a part of the hydrazine-hydrate input.

    (Example 5)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 66.9% by mass and water: 28.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist stripping solution of Example 5.

Example 5 changed the composition of the ratio of DMI to water of the polar solvent of Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 28.036% by mass, including a portion charged as a hydrazine-hydrate.

    (Example 6)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 2.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 73.9% by mass and water: 24.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist stripping solution of Example 6.

Example 6 is a composition that reduces the amount of secondary amine in Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 24.036% by mass, including a portion charged as a hydrazine-hydrate.

    (Example 7)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 3.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 72.9% by mass and water: 24.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist stripping solution of Example 7.

Example 7 is a composition that reduces the amount of secondary amine in Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 24.036% by mass, including a portion charged as a hydrazine-hydrate.

    (Example 8)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 4.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 71.9% by mass and water: 24.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist stripping solution of Example 8.

Example 8 is a composition that reduces the amount of secondary amine in Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 24.036% by mass, including a portion charged as a hydrazine-hydrate.

    (Example 9)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 70.9% by mass and water: 24.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist peeling liquid of Example 9.

Example 9 has the same composition as the amount of secondary amine in Example 1. However, the amount of water is different from that in Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 24.036% by mass, including a portion charged as a hydrazine-hydrate.

    (Example 10)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 6.0% by mass) was used. The polar solvent is a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 69.9% by mass and water: 24.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist peeling liquid of Example 10.

Example 10 is a composition in which the amount of secondary amine in Example 1 is increased. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 24.036% by mass, including a portion charged as a hydrazine-hydrate.

    (Example 11)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 7.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 68.9% by mass and water: 24.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form the sample resist peeling liquid of Example 11.

Example 11 is a composition in which the amount of secondary amine in Example 1 is increased. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 24.036% by mass, including a portion charged as a hydrazine-hydrate.

    (Comparative example 1)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was mixed with water and N-methylformamide (N-methylformamide (NMF: CAS No. 123-39-7): 74.9% by mass and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form a sample resist peeling liquid of Comparative Example 1.

Comparative Example 1 changed the composition of 1,3-dimethyl-2-imidazolidinyl group (DMI) of the polar solvent of Example 1 to N-methylformamide (NMF). In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative example 2)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was mixed with water and N, N-dimethylformamide (N, N-dimethylformamide (DMF: CAS No. 68-12-2): 74.9% by mass, and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form a sample resist peeling liquid of Comparative Example 2.

Comparative Example 2 changed the composition of 1,3-dimethyl-2-imidazolidinyl (DMI) in the polar solvent of Example 1 to N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative example 3)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was mixed with water and 2-pyrrolidone (2-pyrrolidone (2P: CAS number 616-45-5): 74.9% by mass and water: 20.0% by mass). Hydrazine was used as a reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form a sample resist peeling liquid of Comparative Example 3.

Comparative Example 3 changed the composition of 1,3-dimethyl-2-imidazolidinyl (DMI) of the polar solvent of Example 1 to 2-pyrrolidone (2P). In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative Example 4)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was mixed with water and 1-methyl-2-pyrrolidone (1-methyl-2-pyrrolidone (NMP: CAS No. 872-50-4): 74.9% by mass and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to obtain a sample resist peeling liquid of Comparative Example 4.

Comparative Example 4 changed the composition of 1,3-dimethyl-2-imidazolidinyl (DMI) of the polar solvent of Example 1 to 1-methyl-2-pyrrolidone (NMP). In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative example 5)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was mixed with water and NEP (1-ethyl-2-pyrrolidone (NEP: CAS No. 2687-91-4): 74.9% by mass and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to make a sample resist peeling liquid of Comparative Example 5.

Comparative Example 5 changed the composition of 1,3-dimethyl-2-imidazolidinyl (DMI) of the polar solvent of Example 1 to 1-ethyl-2-pyrrolidone (NEP). In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative Example 6)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was mixed with water and γ-butyrolactone (γ-butyrolactone (GBL: CAS No. 96-48-0): 74.9% by mass and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to make a sample resist peeling liquid of Comparative Example 6.

Comparative Example 6 changed the composition of 1,3-dimethyl-2-imidazolidinyl (DMI) of the polar solvent of Example 1 to γ-butyrolactone (GBL). In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative Example 7)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was mixed with water and ethylene carbonate (ethylene carbonate (EC: CAS No. 96-49-1): 74.9% by mass, and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to make a sample resist peeling liquid of Comparative Example 7.

Comparative Example 7 changed the composition of 1,3-dimethyl-2-imidazolidinyl (DMI) of the polar solvent of Example 1 to ethylene carbonate (EC). In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative Example 8)    

As the amine, N-methyldiethanolamine (N-methyldiethanolamine (MDEA: CAS No. 105-59-9): 5.0% by mass) of a tertiary amine was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (DMI: 74.9% by mass, water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to form a sample resist peeling liquid of Comparative Example 8.

Comparative Example 8 changed the composition of N-methylethanolamine (MMA) of the secondary amine of Example 1 to N-methyldiethanolamine (MDEA) of the tertiary amine. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass as a part of the hydrazine-hydrate input.

    (Comparative Example 9)    

As the amine, pyrrolidine (pyrrolidine (PRL: CAS No. 123-75-1): 1.5% by mass) of a cyclic amine was used. The polar solvent was mixed with water and DMI (1,3-dimethyl-2-imidazolidinyl (DMI): 78.4% by mass, water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to obtain a sample resist peeling liquid of Comparative Example 9.

Comparative Example 9 changed the composition of pyrrolidine (PRL) of a cyclic amine by changing N-methylethanolamine (MMA) of the secondary amine of Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative Example 10)    

As the amine, hydroxyethylpiperazine (hydroxyethylpiperazine (OH-PIZ: CAS No. 103-76-4): 5.0% by mass) of a cyclic amine was used. The polar solvent was mixed with water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolyl (DMI): 74.9% by mass, and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to make a sample resist peeling liquid of Comparative Example 10.

Comparative Example 10 changed the composition of hydroxyethylpiperazine (OH-PIZ), which is a cyclic amine, from N-methylethanolamine (MMA) of the secondary amine of Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative Example 11)    

As the amine, monoethanolamine (monoethanolamine (MEA: CAS No. 141-43-5): 5.0% by mass) of a primary amine was used. The polar solvent was mixed with water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolyl (DMI): 74.9% by mass, and water: 20.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to obtain a sample resist peeling liquid of Comparative Example 11.

Comparative Example 11 changed the composition of monoethanolamine (MEA) of primary amine into N-methylethanolamine (MMA) of the secondary amine of Example 1. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 20.036% by mass, which is included as a portion of the hydrazine-hydrate.

    (Comparative Example 12)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was mixed with water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolyl (DMI): 75.0% by mass and water: 20.0% by mass). No reducing agent was added. The above was mixed and stirred to form a sample resist peeling liquid of Comparative Example 12. Comparative Example 12 is a composition excluding the hydrazine (HN) of the reducing agent of Comparative Example 1.

    (Comparative Example 13)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 74.5% by mass and water: 20.0% by mass). Sorbitol was used as an additive (Sorbitol (Stol: CAS number 50-70-4): 0.5% by mass). The above was mixed and stirred to obtain a sample resist peeling liquid of Comparative Example 13. In Comparative Example 13, the additive (reducing agent: hydrazine (HN)) of Example 1 was changed to a composition of sorbitol.

    (Comparative Example 14)    

N-methylethanolamine (N-methylethanolamine (MMA): 5, 0% by mass) was used as the secondary amine. The polar solvent was mixed with water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolyl (DMI): 74.5% by mass, and water: 20.0% by mass). Diglycerin was used as an additive (diglycerin (CAS No. 627-82-7): 0.5% by mass). The above was mixed and stirred to obtain a sample resist peeling liquid of Comparative Example 14. In Comparative Example 14, the additive (reducing agent: hydrazine (HN)) of Example 1 was changed to a composition of diglycerin.

    (Comparative Example 15)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 74.5% by mass and water: 20.0% by mass). Saccharin was used as an additive (saccharin (CAS No. 81-07-2): 0.5% by mass). The above was mixed and stirred to make a sample resist peeling liquid of Comparative Example 15. Comparative Example 15 changed the additive (reducing agent: hydrazine (HN)) of Example 1 to a composition of saccharin.

    (Comparative example 16)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 74.5% by mass and water: 20.0% by mass). Polyethylene glycol 400 was used as an additive (PEG400) (polyethylene glycol 400 (PEG400: CAS No. 25322-68-3): 0.5% by mass). The above was mixed and stirred to make a sample resist peeling liquid of Comparative Example 16. Comparative Example 16 changed the composition (reducing agent: hydrazine (HN)) of Example 1 to a composition of polyethylene glycol 400.

    (Comparative Example 17)    

As the secondary amine, N-methylethanolamine (N-methylethanolamine (MMA): 5.0% by mass) was used. The polar solvent was a mixture of water and 1,3-dimethyl-2-imidazolidinyl (1,3-dimethyl-2-imidazolidinyl (DMI): 63.9% by mass and water: 31.0% by mass). Hydrazine was used as the reducing agent (hydrazine-hydrate (HN.H ₂ O): 0.1% by mass). The above was mixed and stirred to obtain a sample resist peeling liquid of Comparative Example 17.

Comparative Example 17 is a composition in which the amount of water in Example 1 increased from 20.0% by mass to 31.0% by mass. In addition, 0.1% by mass of hydrazine-hydrate is equivalent to 0.064% by mass of hydrazine. 0.036% by mass of the residual hydrazine-hydrate is water. Therefore, it can be said that the composition ratio of the water described above is 31.036% by mass, including a portion charged as a hydrazine-hydrate.

Table 1 shows the composition and evaluation results of Example 1 and Comparative Examples 1 to 7. In addition, Table 2 shows the compositions and evaluation results of Examples 1 and 2 and Comparative Examples 8 to 11. In addition, Table 3 shows the composition and evaluation results of Example 1 and Comparative Examples 12 to 16. In addition, Table 4 shows the compositions and evaluation results of Examples 1, 3 to 5, and Comparative Example 17. In addition, Table 5 shows the composition and evaluation results of Examples 6 to 11.

Table 1 shows the composition and evaluation results of Example 1 and Comparative Examples 1 to 7. Reference Example 1. N-methylethanolamine (MMA), which is a secondary amine, can be used as the amine, and 1,3-dimethyl-2-imidazolidinyl (DMI), which is a mixed solution of polar solvent and water, can be used. The resist was baked at 170 ° C for 30 minutes, and peeled off within 4 minutes. In addition, the film damage systems of "Cu / Mo" and "Al" also improved.

In addition, the life of the liquid bath when the peeling liquid is left in the open state of the atmosphere does not change the peeling force even after 12 hours have elapsed. In addition, no decrease in hydrazine was found even after storage for 4 days.

In Comparative Example 1, N-methylformamide (NMF) was used instead of 1,3-dimethyl-2-imidazolidinyl (DMI) as the polar solvent of Example 1.

Comparative Example 2 uses N, N-dimethylformamide (DMF) instead of DMI.

Comparative Example 3 uses 2-pyrrolidone (2P) instead of DMI.

Comparative Example 4 uses 1-methyl-2-pyrrolidone (NMP) instead of DMI.

Comparative Example 5 uses 1-ethyl-2-pyrrolidone (NEP) instead of DMI.

Comparative Example 6 uses γ-butyrolactone (GBL) instead of DMI.

Comparative Example 7 uses ethylene carbonate (EC) instead of DMI.

Comparative Example 1 relates to peelability immediately after the preparation, and can peel well. However, when exposed to the atmosphere, the cross section and surface of "Cu / Mo" were damaged. In addition, a reduction in hydrazine was observed in the airtight storage on the 4th.

Comparative Example 2 also relates to peeling properties immediately after the preparation, and peels well. However, after being left in the atmosphere for 12 hours, the cross section and surface of "Cu / Mo" were damaged. In addition, a reduction in hydrazine was observed in the airtight storage on the 4th.

In Comparative Example 3, there was no problem of damage to the metal film after peeling immediately after the preparation and after being left in the air for 12 hours. However, it was observed that the reduction of hydrazine was observed in the airtight storage for 4 days.

Comparative Example 4 did not cause any damage to the metal film after peeling immediately after the preparation and after being left in the air for 12 hours. However, it was observed that the reduction of hydrazine was observed in the airtight storage for 4 days.

In Comparative Example 5, the peelability immediately after the preparation and the problem of damage to the metal film did not occur after being left in the air for 12 hours. However, it was observed that the reduction of hydrazine was observed in the airtight storage for 4 days.

Comparative Example 6 showed good peelability immediately after preparation. However, the cross section and surface of "Cu / Mo" were damaged. Therefore, no test was performed on the life of the liquid bath.

In Comparative Example 7, the resist film that cannot be peeled off immediately after preparation was cured. Therefore, no test was performed on the life of the liquid bath.

As described above, N-methylethanolamine (MMA) of the secondary amine of Example 1 was used, and only a mixed solution of 1,3-dimethyl-2-imidazolidinyl (DMI) and water as a polar solvent was used and The peeling solution containing hydrazine has good results regarding peeling ability and bath life.

Table 2 shows the compositions and evaluation results of Examples 1 and 2 and Comparative Examples 8 to 11. Example 1 is disclosed again, and therefore, Example 1 is shown by brackets. Example 2 was a state where N-methylethanolamine (MMA) was substituted in place of the secondary amine and N-ethylethanolamine (EEA) was used. In Example 2, the peeling force, the damage to the metal, and the life of the liquid bath were also the same as in Example 1, and they became good.

In Comparative Examples 8 to 11, the state of the amine was changed. Comparative Example 8 is a state in which N-methyldiethanolamine (MDEA) of a tertiary amine was used as the amine. In addition, Comparative Example 9 is a state using pyrrolidine (PRL) of a cyclic amine, and Comparative Example 10 is a state using hydroxyethylpiperazine (OH-PIZ) of a cyclic amine. Comparative Example 11 is an example using monoethanolamine (MEA) of a primary amine.

Comparative Examples 8, 9, and 10 are resists that cannot be peeled and cured. Therefore, no test was performed on the life of the liquid bath. In addition, the monoethanolamine (MEA) of the primary amine can peel off the hardening and baking inhibitor immediately after the preparation, but it causes damage to the surface and section of "Cu / Mo". Therefore, even in the case of Comparative Example 11, no test concerning the life of the liquid bath was performed.

Table 3 shows the composition and evaluation results of Example 1 and Comparative Examples 12 to 16. Example 1 is disclosed again, and therefore, Example 1 is shown by brackets. Comparative Example 12 was a composition without added hydrazine (hydrazine-hydrate (HN.H ₂ O)). Comparative Example 12 is a resist that can be peeled and cured immediately after the preparation. However, "Cu / Mo" film damage occurred.

In Comparative Example 13, sorbitol (Stol) was added as an additive. In addition, Comparative Example 14 added diglycerin as an additive. Comparative Example 13 and Comparative Example 14 are the resists which cannot be peeled off immediately after hardening and baking after being prepared.

In Comparative Example 15, saccharin was added as an additive. In Comparative Example 16, polyethylene glycol 400 (PEG400) was added as an additive. Comparative Example 15 and Comparative Example 16 are peelable resists that can be cured immediately after being prepared. However, both comparative examples were damaged at the cross section of "Cu / Mo".

From the above, it can be said that hydrazine (hydrazine-hydrate (HN.H ₂ O)) is the stripping solution of the present invention, and becomes an essential material.

Table 4 shows the compositions and evaluation results of Examples 1, 3 to 5, and Comparative Example 17. Example 1 is disclosed again, and therefore, Example 1 is shown by brackets. Table 4 reviews the amount of water. The water content of Example 3 is 24.0% by mass, the water content of Example 4 is 26.0% by mass, and the water content of Example 5 is 28.0% by mass. On the other hand, Comparative Example 17 increased the water content to 31.0% by mass.

The other components are the same as those of the first embodiment. Therefore, with regard to the peeling force and the bath life, no problem occurred in any sample system. However, Comparative Example 17 in which the moisture content was increased to 31.0% by mass was corroded on the surface and cross section of "Al". From the above, it is known that the moisture content must be 31.0% by mass or less.

Table 5 shows the composition and evaluation results of Examples 6 to 11. Examples 6 to 11 review the amount of amine. The amount of water was 24.0% by mass. In addition, the table is arranged from a small amount of amine to a large amount of amine. The N-methylethanolamine (MMA) of Example 6 was 2.0% by mass, 3.0% by mass of Example 7 and 4.0% by mass of Example 8. These are compared with the composition ratio (5.0% by mass) of N-methylethanolamine (MMA) in Example 1, and the composition has less amine. In addition, the amount of the amine in Example 9 was the same as the composition ratio of MMA in Example 1, and was 5.0% by mass.

The N-methylethanolamine (MMA) of Example 10 was 6.0% by mass, and the N-methylethanolamine (MMA) of Example 11 was 7.0% by mass. In Example 10 and Example 12, compared with Example 1, the amount of N-methylethanolamine (MMA) was larger.

Any of the samples of Examples 6 to 11 shown in Table 5 was as good as Example 1 in terms of peeling force, damage to the metal surface, and life of the liquid bath. That is, even if N-methylethanolamine (MMA) is prepared to have a high concentration like 7.0% by mass, no problem occurs in performance. That is, in the composition of the present invention, even if the amine deviates from a predetermined blending ratio, no problem occurs in performance.

    [Industrial availability]    

The resist peeling liquid system of the present invention can peel off the hardening and baking resist in a particularly reliable manner, and can be appropriately used in a situation where a photoresist is used.

Claims (3)

    A resist stripping solution, comprising a secondary amine, 1,3-dimethyl-2-imidazolidinyl (DMI) as a polar solvent, and water, and a hydrazine as an additive. 10.0% by mass or more and 31.0% by mass or less.         For example, the resist stripping solution according to item 1 of the patent application scope, wherein the aforementioned secondary amine series includes at least one of N-methylethanolamine (MMA) and N-ethylethanolamine (EEA).         A resist stripping solution, which is a barrier stripping solution of a peeling resist, characterized in that by using a secondary amine of 0.5% by mass to 9.0% by mass, a hydrazine of 0.03% by mass and 0.4% by mass, 10.0 Water not less than 3% by mass and not more than 31.0% by mass, and 1,3-dimethyl-2-imidazolidinyl (DMI) as a residual constitute a resist stripping solution.