TW201610612A - Process for recycling waste photoresist stripper - Google Patents

Abstract

The present invention relates to a process for recycling a waste photoresist stripper which includes a step of contacting a recycled liquid including 40 to 75% by weight of at least one amine compound, 20 to 55% by weight of an alkylene glycolcompound, and 1 to 10% by weight of an additive with a purified liquid of waste photoresist stripper.

Description

Recycling process for photoresist stripper

The present invention relates to a recycling process for a waste stripper for photoresist.

More specifically, the present invention relates to a recycling process for a photoresist stripper, which can shorten the analysis time of the raw material and the dilution time of the additive, thereby improving productivity and reducing cost, and can also quantitatively introduce raw materials and additives. Thereby, the change in the content between the fresh photoresist release agent before the recovery and the recovered photoresist release agent is reduced.

The manufacturing process of the microcircuit or semiconductor integrated circuit of the liquid crystal display device comprises the following steps: forming a plurality of lower films (such as conductive metal films made of aluminum, aluminum alloy, copper, copper alloy, molybdenum or molybdenum alloy) on the substrate. Or an insulating film (such as a hafnium oxide film, a tantalum nitride film or an acryl insulating film); uniformly coating a photoresist on the lower film; exposing and developing the coated photoresist as the case may be Forming a photoresist pattern; and patterning the lower film with the photoresist pattern as a mask.

After these patterning steps, a process of removing the photoresist remaining on the lower film is performed. For this purpose, a stripper composition for removing photoresist is used.

At the same time, the waste stripper is mainly produced during the manufacturing process of an electronic component such as a semiconductor wafer or a glass substrate of a liquid crystal display device. The waste stripper contains not only a stripper solvent but also a photoresist resin, water, and impurities such as heavy metals.

These waste strippers are primarily incinerated or low-recycled in the form of a fuel for the process. Therefore, it may cause secondary pollution and environmental pollution through inefficient energy consumption, and the company's corporate competitiveness in the IT industry will become weak.

In addition, with the rapid development of IT technology, the 7th generation production line capable of manufacturing commercial 40吋 to 47吋 LCD panels and 82吋 size products has been operated in terms of the LCD manufacturing with the highest waste stripping amount discharged. Based on the development plans of the 8th and 9th generation production lines that have been established, the size of the LCD substrate is rapidly increasing and the types of substrates are also diverse. The amount of stripper solvent associated therewith will also increase significantly proportionally.

In view of this reality, there is an urgent need for a recycling technology for waste strippers which not only provides basic recovery of waste strippers, but also enables high purity recovered stripper solvents to be produced at low cost.

Therefore, a technique for recovering a release agent which is carried out by purifying a waste release agent to recover a corresponding raw material, then analyzing the raw material, and adding an additive diluted in a solvent thereto has been proposed.

However, it takes a lot of time and money to recycle the corresponding raw materials, analyze the recovered materials, and dilute the additives in the solvent, and the process efficiency is lowered. In addition, in the process of diluting the additive in the solvent and adding the additive, a significant change occurs and thus there is a disadvantage that it is difficult to quantitatively introduce the additive.

Therefore, there is a need to develop a new process for recycling waste strippers that reduces the time required for material analysis and dilution in a solvent, and enables the quantitative introduction of additives.

An object of the present invention is to provide a process for recovering a waste stripper for photoresist, which can shorten the analysis time of the raw material and the dilution time of the additive, thereby improving productivity and reducing cost, and also producing quality and recycling. The fresh photoresist is equivalent to a recycled stripper.

In the present invention, there is provided a process for recovering a waste release agent for photoresist, comprising the steps of: containing 40% to 75% by weight of at least one amine compound, by weight of 20% to 55% The recovered alkyl diol compound and the recovered liquid in an amount of from 1% to 10% by weight of the additive are contacted with the purified photoresist stripping stripper liquid.

Hereinafter, the recycling process of the photoresist stripper for photoresist according to a specific embodiment of the present invention will be described in more detail.

According to an embodiment of the present invention, there is provided a process for recovering a waste release agent for photoresist, comprising the steps of: containing 40% to 75% by weight of at least one amine compound by weight, 20% by weight The recovered liquid to 55% of the alkylene glycol compound and 1% to 10% by weight of the additive is contacted with the purified photoresist waste stripper liquid.

The present inventors have found through many experiments that when the process for recovering the photoresist stripper for photoresist is used as described above, the recovered liquid containing a material required for a predetermined amount of the stripper for photoresist is used. It is possible to shorten the analysis time of the raw materials and the dilution time of the additives, thereby increasing the productivity and reducing the cost, and it is also possible to quantitatively introduce the raw materials and additives, thereby producing a quality comparable to that of the fresh photoresist for stripping before recycling. Recycled stripper product. The inventors completed the present invention based on this finding.

Specifically, the process for recovering the photoresist stripper for photoresist may include the steps of: containing 40% to 75% by weight of at least one amine compound, and 20% to 55% by weight. The recovered liquid of the alkyl diol compound and 1% to 10% by weight of the additive is contacted with the purified photoresist release stripper solution.

In the above-mentioned recovered liquid, the additive not contained in the purified photoresist stripper liquid is diluted in the alkylene glycol compound solvent in the state where the analysis and filtration have been completed, and thus the analysis time can be shortened And filter time to reduce costs.

Further, since the amount of the additive to be introduced in a small amount can be accurately introduced, it is possible to produce a recovered release agent product having a quality comparable to that of the fresh photoresist for stripper before recycling.

The recovered liquid may comprise at least one amine compound. The amine compound is a component exhibiting peeling ability, and it can be used to dissolve the photoresist and remove it.

Examples of the amine compound used may include, but are not particularly limited to, a chain amine compound such as (2-aminoethoxy)-1-ethanol (AEE), amine B. Aminoethanolamine (AEEA), monomethanolamine, monoethanolamine, N-methylethylamine (N-MEA), 1-aminoisopropanol (AIP), methyldi Methyl dimethylamine (MDEA), diethylenetriamine (DETA), 2-methylaminoethanol (MMEA), 3-aminopropanol (AP), Diethanolamine (DEA), diethylaminoethanol (DEEA), triethanolamine (TEA) and triethylenetetraamine (TETA); or cyclic amine compounds such as imidazolyl-4 - ethanol (imidazolyl-4-ethanol, IME), aminoethylpiperazine (AEP) and hydroxyethylpiperazine (HEP).

The recovered liquid may comprise from 40% to 75% by weight of at least one amine compound.

If the content of the at least one amine compound is less than 40% by weight based on the total weight of the recovered solution, the peeling ability of the stripper for recovering the photoresist is lowered due to a decrease in the content of the amine compound in the stripper for the photoresist finally recovered. Will decrease.

If the content of the at least one amine compound is more than 75% by weight based on the total weight of the recovered solution, the lower film (for example, copper-containing) may be caused due to an excessive increase in the content of the amine compound in the finally recovered photoresist for the photoresist. Corrosion of the film), so it may be necessary to use a large amount of corrosion inhibitor to suppress corrosion.

In this case, since a large amount of corrosion inhibitor is used, a large amount of corrosion inhibitor is absorbed and remains on the surface of the lower film, thereby lowering the electrical characteristics of the copper-containing lower film and the like.

Since the alkylene glycol compound is contained in the recovered liquid, materials well known to those skilled in the art can be used, but the type thereof is not particularly limited.

For example, the alkylene glycol compound used herein may comprise bis(2-hydroxyethyl)ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether , dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, Tripropylene glycol monopropyl ether or tripropylene glycol monobutyl ether and the like. Two or more than two categories selected from them may be used.

Further, in view of the excellent wetting ability of the release agent composition according to one embodiment and the resulting peeling ability and the improvement of the rinsing ability, it can be suitably used for the alkylene glycol or alkylene glycol herein. The monoalkyl ethers include bis(2-hydroxyethyl)ether (HEE) or diethylene glycol monobutyl ether (BDG), and the like.

When the amount of the alkylene glycol compound contained is 20% by weight to 55% by weight based on the total weight of the recovered solution, the peeling ability of the finally recovered photoresist for the photoresist can be ensured, and as time passes, Peeling ability and rinsing ability can be maintained for a long time.

In addition, the recovered liquid may further contain an additive.

As described above, in the recovered liquid, a trace amount of the additive is diluted in the alkylene glycol compound solvent in the state where the analysis and filtration have been completed, and thus the analysis time and the filtration time can be shortened, thereby reducing the cost.

Further, the amount of the additive to be introduced in a small amount can be accurately introduced, thereby producing a recovered release agent product having a quality comparable to that of the fresh photoresist for stripper before recycling.

Further, the amount of the additive may be from 1% by weight to 10% by weight, from 2% by weight to 9% by weight or from 4% by weight to 8% by weight based on the total weight of the recovered liquid.

The additive may comprise one or more selected from the group consisting of a corrosion inhibitor or an anthrone-based nonionic surfactant.

The weight ratio of the corrosion inhibitor to the hydrazine-based nonionic surfactant is from 5:1 to 15:1, from 7:1 to 12:1, from 8:1 to 10:1, or from 8.5:1 to 9.5:1.

Benzimidazole compounds, triazole compounds, tetrazole compounds, and the like can be used as the corrosion inhibitor.

Examples of the benzimidazole compound may include, but are not particularly limited to, benzimidazole, 2-hydroxybenzimidazole, 2-methylbenzimidazole, 2-(hydroxymethyl)benzimidazole, 2-mercaptobenzene And imidazole and the like. Examples of the tetrazole compound may include 5-aminotetrazole or a hydrate thereof and the like.

Further, the triazole compound may contain a compound represented by Formula 1 or Formula 2. [Formula 1]

Herein, R9 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R10 and R11 are the same or different from each other and are each independently a hydroxyalkyl group having 1 to 4 carbon atoms, and a is 1 to 4 Integer, [Formula 2]

Herein, R12 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and b is an integer of 1 to 4.

More specifically, a compound of the formula 1 wherein R9 is a methyl group, R10 and R11 are each a hydroxyethyl group and a is 1, or a compound of the formula 2 wherein R12 is a methyl group and b is 1 and the like can be used.

By using the above-described corrosion inhibitor, the peeling ability of the recovered release agent can be excellently maintained while the corrosion of the metal-containing lower film is effectively suppressed.

Further, the amount of the corrosion inhibitor contained may be 1% by weight to 10% by weight, 2% by weight to 9% by weight or 4% by weight to 8% by weight based on the total weight of the recovered liquid.

If the content of the corrosion inhibitor is less than 1% by weight based on the total weight of the recovered liquid, it may be difficult to effectively suppress the corrosion of the lower film because the content of the corrosion inhibitor in the finally-removed photoresist for the photoresist is reduced.

If the content of the corrosion inhibitor is more than 10% by weight based on the total weight of the recovered liquid, a large amount of the corrosion inhibitor can be absorbed and retained due to an excessive increase in the content of the corrosion inhibitor in the finally recovered photoresist. On the lower film, the electrical properties of the underlying copper-containing film and the like are thereby reduced.

Meanwhile, the quinone-based nonionic surfactant may include a polyoxyalkylene-based polymer.

More specifically, examples of the polyoxyalkylene type polymer may include a polyether-modified acrylic functional polydimethyloxane, a polyether modified nonoxyl alkane, and a polyether modified polydimethyloxene. Alkane, polyethyl alkyl decane, aralkyl modified polymethyl alkyl decane, polyether modified hydroxy functional polydimethyl siloxane, polyether modified dimethyl poly A siloxane, a modified acrylic functional polydimethyl siloxane or a mixture of two or more thereof and the like.

The amount of the quinone-based nonionic surfactant contained may be from 0.1% by weight to 0.9% by weight, from 0.2% by weight to 0.8% by weight, or from 0.3% by weight to 0.7% by weight based on the total weight of the recovered liquid.

If the content of the ruthenium-based nonionic surfactant is less than 0.1% by weight based on the total weight of the recovered liquid, the content of the ruthenium-based nonionic surfactant in the finally-removed photoresist for the photoresist is reduced, so that the fulcrum cannot be sufficiently achieved. The stripping ability and rinsing ability of the recovered stripper.

In addition, if the content of the quinone nonionic surfactant is more than 0.9% by weight based on the total weight of the recovered liquid, the content of the ruthenium nonionic surfactant in the finally recovered photoresist for the photoresist is excessively increased. During the stripping process of the recovered stripper, bubbles are generated under high pressure, thereby causing stains on the lower film or malfunctioning the device sensor.

Meanwhile, a catalyst comprising 40% to 75% by weight of at least one amine compound, 20% to 55% by weight of an alkylene glycol compound, and 1% to 10% by weight of an additive. In the step of contacting the recovered liquid with the purified photoresist by the waste stripper liquid, the weight ratio of the purified photoresist to the stripper liquid to the recovered liquid may be 5:1 to 20:1, 7:1 to 15:1. Or 8:1 to 12:1.

By adjusting the weight ratio of the purified photoresist stripper liquid to the recovered liquid within the above range, it is possible to ensure that the ratio of the components of the finally produced recovered stripper to the composition ratio of the original stripper product before the recovery is substantially the same.

If the weight ratio of the purified photoresist to the waste stripper liquid to the recovered liquid is less than 5:1, since the ratio of the purified photoresist to the waste stripper liquid becomes small, it is not included in the recovered solution but only contains The content of N-methylformamide in the purified photoresist stripper liquid may become too small.

If the weight ratio of the waste photoresist to waste stripper liquid to the recovered liquid is more than 20:1, since the ratio of the recovered liquid becomes small, it is not included in the purified photoresist stripper liquid but only contains The amount of other additives in the recovered liquid may become too small.

Recycled liquid comprising from 40% to 75% by weight of at least one amine compound, from 20% to 55% by weight of an alkylene glycol compound, and from 1% to 10% by weight of an additive The step of contacting the purified photoresist with the waste stripper liquid may further comprise selecting one or more of the group consisting of the aprotic organic solvent and the protic organic solvent and the purified photoresist stripper liquid and the The step of recovering the liquid contact.

Specifically, it may be 60% to 95% by weight of the purified photoresist stripper liquid, 1% to 10% by weight of the recovered liquid, and 1% to 30% by weight. One or more compounds selected from the group consisting of an aprotic organic solvent and a protic organic solvent are contacted.

The aprotic organic solvent can advantageously dissolve the amine compound and also allows the recovered release agent to be wetted on the lower film leaving the photoresist to be removed, thereby ensuring excellent peeling ability and rinsing ability.

Examples of aprotic organic solvents that may be used herein include, but are not particularly limited to, N-methyl-pyrrolidone (NMP), 1,3-dimethyl-2-imidazole 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc), dimethylformamide (DMF), N-methylformamide (NMF), N,N'-diethyl-carboxamide (DCA), dimethylpropionamide (DMP) and analog.

The aprotic organic solvent can make the recovered release agent more preferably wet on the lower film, thereby helping excellent peeling ability, and it can also effectively remove stains such as those on the underlying film of the copper-containing film, thereby improving Flushing ability.

The protic organic solvent may comprise an alkylene glycol or an alkylene glycol monoalkyl ether.

More specifically, the alkylene glycol or alkylene glycol monoalkyl ether may comprise bis(2-hydroxyethyl)ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol single Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, Tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether or a mixture of two or more thereof.

The purified photoresist stripper liquid may comprise an aprotic organic solvent in a weight ratio of 0.5 to 2:1, 0.6:1 to 1.8:1, 0.7:1 to 1.7:1 or 0.8:1 to 1.65:1 and Protic organic solvent.

In the step of contacting one or more of the group consisting of the aprotic organic solvent and the protic organic solvent with the purified photoresist stripper liquid and the recovered liquid, the purified photoresist is discarded by disposal. The aprotic organic solvent and the protic organic solvent contained in the agent liquid contain the above-mentioned contents.

The purified photoresist stripper liquid may further comprise from 0.1% to 10% by weight of the amine compound.

The purified photoresist stripper liquid contains the aprotic organic solvent and the protic organic solvent as mentioned above, and the aprotic organic solvent can cause a decomposition reaction in the presence of an amine over time, and a small amount of the amine can contain In the purified liquid.

And an additive comprising from 40% to 75% by weight of at least one amine compound, from 20% to 55% by weight of an alkylene glycol compound, and from 1% to 10% by weight of an additive and purified light Before the step of contacting the waste stripper solution, the step of purifying the waste stripper for photoresist may be further included.

By the step of purifying the photoresist with a waste stripper, it is possible to effectively and economically use the stripper liquid after the use of the fresh photoresist stripper liquid in the manufacturing process of a semiconductor, a display device, an LED, or a solar cell. The solid, impurities and water are removed from the agent, thereby recovering the high-purity stripper.

Specifically, the step of purifying the photoresist stripping agent may include maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 torr to 140 Torr, and distilling the photoresist with a waste stripper. .

In the step of purifying the photoresist stripping agent, the step of maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 Torr to 140 Torr and distilling the photoresist stripping agent is used for self-resistance. The stripper removes the solid and at the same time removes the photoresist having a boiling point greater than 235 °C.

In the step of purifying the photoresist stripping release agent, a distillation column and the like which recover the purified liquid according to the difference in boiling point as described above may be used.

Specific examples of the distillation column used herein may include, but are not particularly limited to, a common simple distillation and refillable distillation column or multi-stage distillation column.

A distillation column means an experimental apparatus manufactured using the fractionation principle, which is a process for separating a mixed liquid mixture by using a difference in boiling points.

If the temperature of the distillation column is less than 100 ° C, the photoresist stripper for the photoresist cannot be completely removed. Therefore, there is a problem in that the active component is removed together with the solid and the photoresist, thereby reducing the recovery rate of the photoresist stripper.

Further, if the temperature of the distillation column is more than 200 ° C, it is likely that thermal decomposition and deformation of the active component occur in the photoresist stripper. In addition, it may be impossible to remove a portion of the photoresist and solids, thereby causing problems in subsequent purification processes.

In addition, if the pressure condition is less than 60 Torr, it may be difficult to use in industrial processes due to cost problems. If the pressure condition exceeds 140 Torr, the photoresist stripping agent can not be completely distilled out even if the temperature is sufficiently raised. Therefore, the active component is removed together with the solid and the photoresist and thus reduces the recovery of the photoresist stripper.

After maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 Torr to 140 Torr and distilling the photoresist with a waste stripper, it may further comprise maintaining the lower portion of the distillation column at 100 ° C to 200 ° C. Temperature and a pressure of 70 Torr to 130 Torr, and a step of maintaining the upper portion of the distillation column at a temperature of 50 ° C to 110 ° C and a pressure of 10 Torr to 50 Torr, and distilling the photoresist with a waste stripper; and lowering the lower portion of the distillation column Partially maintained at a temperature of 100 ° C to 200 ° C and a pressure of 70 Torr to 130 Torr, and maintaining the upper portion of the distillation column at a temperature of 120 ° C to 130 ° C and a pressure of 70 Torr to 180 Torr, and the exhaust photoresist is discarded by waste. The steps of the agent.

Specifically, by maintaining the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 Torr to 130 Torr, and maintaining the upper portion of the distillation column at a temperature of 50 ° C to 110 ° C and 10 Torr to 50 Torr. The step of pressure and distilling the photoresist with a waste stripper can remove the low boiling point mixture from the photoresist stripper that has removed the solid photoresist.

The low-boiling mixture means an impurity having a boiling point lower than that of the stripper solvent contained in the photoresist release agent.

The lower portion of the distillation column specifically refers to the lowest layer point in the distillation column which is closest to the ground surface. The lower portion can maintain a high temperature, thereby obtaining a liquid vaporized at a high temperature.

On the other hand, the upper portion of the distillation column specifically refers to the uppermost point in the distillation column which is farthest from the ground surface. The upper portion can maintain a relatively lower temperature than the lower portion of the distillation column, thereby obtaining a liquid vaporized at a low temperature.

By maintaining the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 Torr to 130 Torr, and maintaining the upper portion of the distillation column at a temperature of 120 ° C to 180 ° C and a pressure of 70 Torr to 130 Torr, and distillation The step of using a waste stripper for photoresist can remove the high-boiling mixture from the photoresist stripping remover from the low-boiling mixture.

The high-boiling mixture means an impurity having a boiling point higher than that of the stripper solvent contained in the waste release agent for photoresist.

On the other hand, after maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 Torr to 140 Torr and distilling the photoresist stripping agent, it may further comprise maintaining the lower portion of the distillation column at 100 ° C. a temperature of up to 200 ° C and a pressure of from 70 Torr to 130 Torr, and a step of maintaining the upper portion of the distillation column at a temperature of from 120 ° C to 180 ° C and a pressure of from 70 Torr to 130 Torr, and distilling the photoresist with a waste stripper; Maintaining the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 Torr to 130 Torr, and maintaining the upper portion of the distillation column at a temperature of 50 ° C to 110 ° C and a pressure of 10 Torr to 50 Torr, and distilling light The step of obstructing the waste stripper.

By maintaining the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 Torr to 130 Torr, and maintaining the upper portion of the distillation column at a temperature of 120 ° C to 180 ° C and a pressure of 70 Torr to 130 Torr, and distillation The photoresist is used in the step of removing the high-boiling mixture from the solid photoresist stripping stripper.

Further, by maintaining the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 Torr to 130 Torr, and maintaining the upper portion of the distillation column at a temperature of 50 ° C to 110 ° C and a pressure of 10 Torr to 50 Torr, And the step of distilling the photoresist with a waste stripper can remove the low-boiling mixture from the photoresist stripping remover from the high-boiling mixture.

According to the present invention, it is possible to provide a process for recovering a waste stripper for photoresist, which can shorten the analysis time of the raw material and the dilution time of the additive, thereby improving productivity and reducing cost, and also producing quality and freshness before recycling. Recycled release agent equivalent to the release agent for photoresist.

Hereinafter, the present invention will be explained in detail with reference to the following examples. However, these examples are merely illustrative of the concept of the invention, and the scope of the inventive concept is not limited thereto. < Preparation Example 1 to Preparation Example 20 : Preparation of Purified Release Agent Liquid >

A fresh stripper liquid having the composition shown in Table 1 below was used in the manufacturing process of the electronic component. The solid was removed from the resulting photoresist with a waste stripper using a multi-stage distillation column at a temperature of 150 ° C and a pressure of 100 Torr.

Thereafter, the lower portion of the multi-stage distillation column was maintained at a temperature of 150 ° C and a pressure of 100 Torr, and the upper portion of the multi-stage distillation column was maintained at a temperature of 100 ° C and a pressure of 30 Torr to remove the low-boiling mixture.

Next, the lower portion of the multi-stage distillation column was maintained at a temperature of 150 ° C and a pressure of 100 Torr and the upper portion of the multi-stage distillation column was maintained at a temperature of 130 ° C and a pressure of 100 Torr to remove the high-boiling mixture. The purified stripper liquid having the composition shown in Table 2 below was thus recovered. [Table 1] Composition of fresh stripper liquid before recycling [Table 2] Composition of purified stripper liquid < Preparation Example 21 : Preparation of Recycled Liquid >

A recovered liquid having the composition shown in Table 3 below was prepared. [Table 3] Composition of recovered liquid < Example 1 to Example 20 : Preparation of Recycled Release Agent >

The purified release agent liquid obtained in Preparation Example 1 to Preparation Example 20, the recovered liquid obtained in Preparation Example 21, N-methylformamidine in the weight ratio shown in Table 4 below, were placed in a stirrer. The amine and diethylene glycol monobutyl ether were stirred at room temperature for 45 minutes to obtain a recovered release agent having the composition shown in Table 5 below. [Table 4] Mixing ratio of purified stripper liquid, recovered liquid, N-methylformamide and diethylene glycol monobutyl ether [Table 5] Composition of recovered stripper * IME: imidazolyl-4-ethanol* AEE: (2-amino-ethoxy)-1-ethanol* NMF: N-dimethylformamide* BDG: diethylene glycol monobutyl ether* first Corrosion inhibitor: [[(methyl-1-benzotriazol-1-yl)methyl]imino]diethanol* Second corrosion inhibitor: benzimidazole* surfactant: polyether modified Polyoxane

As shown in Table 5 above, the recovered release agents of Examples 1 to 20 included a uniform content of 3.0% by weight of imidazolyl-4-ethanol, 1.0% by weight of (2-aminoethoxy). )-1-ethanol, 54% to 56% by weight of N-methylformamide, 39% to 42% by weight of diethylene glycol monobutyl ether, 0.3% by weight [ [(Methyl-1H-benzotriazol-1-yl)methyl]imino]diethanol, 0.15% by weight of benzimidazole and 0.05% by weight of polyether modified 矽Oxytomane.

Further, it is considered that the fresh photoresist stripper liquid before the recovery shown in Table 1 already contains 3.0% by weight of imidazolyl-4-ethanol; 1.0% by weight of (2-amino group) Ethoxy)-1-ethanol; 54.5% by weight of N-methylformamide; 41% by weight of diethylene glycol monobutyl ether; 0.3% by weight [[(A) -1H-benzotriazol-1-yl)methyl]imino]diethanol; 0.15% by weight of benzimidazole; and 0.05% by weight of polyether modified oxirane Among the components contained in the recovered release agent of Examples 1 to 20, imidazolyl-4-ethanol, (2-aminoethoxy)-1-ethanol, [[(methyl-1H) can be determined. - benzotriazol-1-yl)methyl]imino]diethanol, benzimidazole and polyether modified oxirane exhibit the same content as the fresh photoresist stripper liquid before recycling, without Variety.

Further, in the case of N-methylformamide and diethylene glycol monobutyl ether, the components contained in the recovered release agents of Examples 1 to 20 include 54% to 56% by weight. N-methylformamide and 39% to 42% by weight of diethylene glycol monobutyl ether. Therefore, it exhibits 54.5% by weight of N-methylformamide and 41% by weight of diethylene glycol alone contained in the fresh photoresist stripper shown in Table 1 above. The equivalent level of butyl ether.

Therefore, the recovered release agent obtained in Examples 1 to 20 can introduce a predetermined amount of raw materials and additives even in the case of repeated recycling processes, thereby uniformly maintaining the quality. Further, regardless of the release resist for the photoresist, it can have a quality comparable to that of the fresh photoresist for the photoresist before the recovery.

Specifically, the additive (0.3% by weight of [[(methyl-1H-benzotriazol-1-yl)methyl]imino]diethanol] is added in a small amount, 0.15% by weight. In the case of benzimidazole and 0.05% by weight of polyether modified alkane, it is possible to determine that it is possible to recover the photoresist for the photoresist at a precise level so that the recovered stripper will contain fresh before recycling The photoresist is the same amount as the stripper liquid, and there is no change.

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Claims (16)

A process for recovering a waste stripper for photoresist, comprising the steps of: containing 40% to 75% by weight of at least one amine compound, and 20% to 55% by weight of alkylene glycol The recovered liquid of the compound and 1% to 10% by weight of the additive is contacted with the purified photoresist by a waste stripper liquid. The process for recovering a waste release agent for photoresist according to claim 1, wherein the method comprises containing 40% to 75% by weight of at least one amine compound by weight, 20% by weight The purified photoresist resist stripper is used in the step of contacting the recovered liquid of 55% of the alkylene glycol compound and 1% to 10% by weight of the additive with the purified photoresist stripper liquid. The weight ratio of liquid to the recovered liquid is from 5:1 to 20:1. The process for recycling a photoresist stripper as described in claim 1, wherein the method comprises containing 40% to 75% by weight of at least one amine compound, by weight of 20% to The step of contacting the recovered liquid of the 55% alkylene glycol compound and the additive of 1% to 10% by weight with the purified photoresist by the waste stripper liquid further comprises aprotic organic solvent and proton One or more selected from the group consisting of organic solvents are in contact with the purified photoresist stripper liquid and the recovered liquid. The process for recovering a waste stripper for photoresist according to claim 3, wherein the one or more selected from the group consisting of an aprotic organic solvent and a protic organic solvent are used. The step of contacting the purified photoresist stripper liquid and the recovered liquid comprises: adding 60% to 95% by weight of the purified photoresist resist stripper liquid by weight, 1% by weight Up to 10% of the recovered liquid, and 1% to 30% by weight of one or more compounds selected from the group consisting of the aprotic organic solvent and the protic organic solvent are contacted. The process for recovering a photoresist stripper for removing photoresist according to claim 1, wherein the purified photoresist stripper liquid comprises the aprotic in a weight ratio of 0.5:1 to 2:1. An organic solvent and the protic organic solvent. The process for recovering a photoresist stripper for use in a photoresist according to claim 5, wherein the purified photoresist stripper liquid further comprises 0.1% to 10% by weight of the amine compound. . The process for recovering a photoresist stripper for removing photoresist according to claim 1, wherein the additive comprises one or more selected from the group consisting of a corrosion inhibitor and an anthrone-based nonionic surfactant. By. The process for recovering a photoresist stripper for use in a photoresist according to claim 7, wherein the weight ratio of the corrosion inhibitor to the nonionic hydrazine surfactant is from 5:1 to 15:1. The process for recovering a photoresist stripper for use in a photoresist according to claim 7, wherein the corrosion inhibitor comprises a benzimidazole compound, a triazole compound or a tetrazole compound. The process for recovering a waste stripper for photoresist according to claim 9, wherein the triazole compound comprises a compound represented by Formula 1 or Formula 2: [Formula 1] Wherein R 9 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R 10 and R 11 are the same or different from each other and are each independently a hydroxyalkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 4; [Formula 2] Wherein R12 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and b is an integer of 1 to 4. The process for recovering a photoresist stripper for use in a photoresist according to claim 7, wherein the anthrone-based nonionic surfactant comprises a polyoxyalkylene-based polymer. The process for recovering a photoresist stripping release agent according to claim 11, wherein the polyoxyalkylene type polymer comprises one or more selected from the group consisting of: poly Ether-modified acrylic functional polydimethyloxane, polyether modified alkane, polyether modified polydimethyloxane, polyethylalkyloxyalkane, aralkyl modified Polymethylalkyl siloxane, polyether modified hydroxy functional polydimethyl siloxane, polyether modified dimethyl polyoxy siloxane, and modified acrylic functional polydimethyl siloxane . The process for recovering a waste release agent for photoresist according to claim 1, wherein the method comprises containing 40% to 75% by weight of at least one amine compound by weight, 20% by weight Before the step of contacting the recovered liquid of the 55% alkylene glycol compound and the additive of 1% to 10% by weight with the purified photoresist by the waste stripper liquid, the method further comprises the step of purifying the photoresist for the photoresist step. The process for recovering a photoresist stripper for use in a photoresist according to claim 13, wherein the step of purifying the photoresist stripper comprises maintaining the entire distillation column at a temperature of from 100 ° C to 200 ° C and 60 The step of charging the waste stripping agent for the photoresist was carried out under a pressure of 140 Torr. The process for recovering a waste stripper for photoresist according to claim 14, wherein the whole distillation column is maintained at a temperature of 100 ° C to 200 ° C and a pressure of 60 Torr to 140 Torr and a distillation station. After the step of using the waste stripper for photoresist, the method further comprises maintaining the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 Torr to 130 Torr and maintaining the upper portion of the distillation column at 50 a step of distilling the photoresist waste stripper at a temperature of from ° C to 110 ° C and a pressure of from 10 Torr to 50 Torr; and maintaining the lower portion of the distillation column at a temperature of from 100 ° C to 200 ° C and from 70 Torr to 130 ° The pressure of the tray and the step of maintaining the upper portion of the distillation column at a temperature of 120 ° C to 180 ° C and a pressure of 70 Torr to 130 Torr and distilling the photoresist stripper. The process for recovering a waste stripper for photoresist according to claim 14, wherein the whole distillation column is maintained at a temperature of 100 ° C to 200 ° C and a pressure of 60 Torr to 140 Torr and a distillation station. After the step of using the waste stripper for photoresist, the method further comprises maintaining the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 Torr to 130 Torr and maintaining the upper portion of the distillation column at 120 a step of distilling the photoresist stripping agent by a temperature of from ° C to 180 ° C and a pressure of from 70 Torr to 130 Torr; and maintaining the lower portion of the distillation column at a temperature of from 100 ° C to 200 ° C and from 70 Torr to 130 ° The pressure of the tray and the step of maintaining the upper portion of the distillation column at a temperature of 50 ° C to 110 ° C and a pressure of 10 Torr to 50 Torr and distilling the photoresist stripper.