KR101285136B1 - Method for purifying organic solvent - Google Patents

Abstract

According to an embodiment, a method of purifying an organic solvent may include preparing an organic solvent mixture including propylene glycol monomethyl ether acetate and impurities; And adding the amine compound to the organic solvent mixture and reacting to remove the impurities.

Description

Purification method of organic solvent {METHOD FOR PURIFYING ORGANIC SOLVENT}

Example relates to a method for purifying an organic solvent.

In general, TFT-LCD is a combination of two key elements to implement the function, the color filter and the TFT circuit (TFT-Array) substrate is the main component and the driver circuit including a driver IC in the periphery Is formed.

The color display of the TFT-LCD is performed through the operation of the TFT and the cell which control the transmittance of the white light of the back light and the additive mixing of the three primary colors that pass through the red, green, and blue color filters.

According to the material of the organic filter used in the manufacture of the color filter, there are a dye method and a pigment method, and depending on the manufacturing method can be classified into dyeing, spraying, electrodeposition, printing method, etc. A common method is pigment spraying.

After spraying each color, the spray nozzle should be cleaned with organic solvent. PGMEA is used because it has excellent cleaning power and low toxicity to human inhalation.

On the other hand, photolithography, which is used to manufacture a color filter, is used in each step of applying red pigment, green pigment, and blue pigment. A photoresist, which is a photosensitive material, is mixed and applied like a pigment, and a pattern is printed. The process of transferring a circuit pattern of a mask to a board | substrate by irradiating light or a laser through the mask which exists.

Negative Color Photoresist, which remains in areas where no photoresist reaction occurs due to irradiated light, should be cleaned with an organic solvent. Again, PGMEA, which is used for color filters, is used because of its cleanability and low toxicity.

The waste PGMEA used in the color filter manufacturing process has been incinerated because it cannot be reused by a simple reprocessing facility because of pigments, pigment dispersants, photoresists, moisture mixed during cleaning, and metallic materials.

The waste PGMEA typically contains impurity solvents such as Propylene Glycol Monomethyl Ether (PGME), Methyl 3-Methoxypropionate (MMP), 2-Methoxypropyl Acetate (MPA), Cyclohexanone (EEP), and Ethyl 3-Ethoxypropionate (EEP). Doing.

The boiling points of these solvents are shown in Table 1 below.

Solvent Name PGME MMP PGMEA MPA Cyclohexanone EEP Boiling point (℃) 120 143 146 148 155 170

In addition, some regeneration companies are unable to remove impurity solvents such as MMP, MPA, cyclohexanone, and EEP after regeneration, and are not able to produce more than 99.0 wt% of purity.

Meanwhile, in the prior art, the low boiling point component and the high boiling point component are removed by the fractional distillation method of other organic solvent impurities contained in the waste PGMEA.

These impurity organic solvents are solvents such as alcohols, esters, ethers, glycols, glycols, ketones, and the like, which are used to make various materials used in the photoresist in solution.

Among them, as shown in Table 1, MMP, MPA, cyclohexanone, and EEP are the most difficult components to be separated from PGMEA in close proximity to the boiling point.

In order to separate these impurities, a high reflux ratio or an appropriate level of distillation column is required. This affects high capital investment and increased operating costs.

As described above, PGMEA is required to be recycled only when the impurity organic solvent component contained in the waste organic solvent is removed, but technology development is required. However, in order to have a desired purity, high facility investment cost and operation cost are increased, and yield is low. Had a problem.

Referring to Korean Patent No. 101005586 and Korean Patent No. 101038042, a method of recovering 99.0 wt% PGMEA by fractional distillation of a PGMEA mixture by changing the boiling point by a chemical reaction of an impurity having a boiling point similar to that of PGMEA. It is open. However, the present inventors have studied to improve the loss of PGMEA, since PGMEA, which is a useful solvent component, is also partially decomposed in the process of changing the boiling point by chemical reaction with strong alkali.

In particular, the method can be changed by treating a strong alkali in the impurity solvent similar to the boiling point and PGMEA contained in the waste PGMEA, but the loss of PGMEA which is a useful solvent due to the high alkali strength.

The embodiment aims to provide a method for purifying an organic solvent which reduces the loss of PGMEA and provides PGMEA having improved purity.

According to an embodiment, a method of purifying an organic solvent may include preparing an organic solvent mixture including propylene glycol monomethyl ether acetate and impurities; And adding the amine compound to the organic solvent mixture and reacting to remove the impurities.

In the method for purifying the organic solvent according to the embodiment, by using an amine compound, the boiling point of the impurity having a similar boiling point to that of PGMEA can be changed. That is, in the purification method of the organic solvent according to the embodiment, the cyclohexanone among the impurities having a boiling point similar to that of PGMEA may be changed to have a boiling point higher than that of PGMEA using an amine compound.

Accordingly, the method of purifying the organic solvent according to the embodiment first changes the boiling point of the cyclohexanone, separates it by fractional distillation, and removes the remaining impurities using a less alkaline mixture, thus making the PGMEA high purity and high. It can be easily purified in yield.

That is, the reaction of the alkali-based mixture with the PGMEA can be minimized, thereby minimizing the loss of the PGMEA during purification.

In addition, the organic solvent purification method according to the embodiment may further add a small amount of the acid catalyst. When using a small amount of the acid catalyst, there is almost no loss of PGMEA, and since only a small amount of alkali can be used to decompose other impurities such as MMP, the loss of PGMEA can be reduced, and PGMEA can be effectively purified through fractional distillation. .

In particular, the amine does not react with PGMEA in the reaction conditions in which the acid catalyst is present. Therefore, the organic solvent purification method according to the embodiment can minimize the loss of PGMEA can be purified in a high yield.

1 is a process flow chart for explaining the organic solvent purification method according to the embodiment.
2 and 3 are views illustrating a gas chromatography chart of a PGMEA mixture before fractional distillation and a gas chromatography chart after the reaction with an amine compound in the method for purifying the PGMEA mixture according to the embodiment.

Purification method of the organic solvent according to the embodiment comprises the steps of preparing an organic solvent mixture comprising propylene glycol monomethyl ether acetate and impurities; And adding the amine compound to the organic solvent mixture and reacting to remove the impurities.

The amine compound may be a compound containing a group of NH 2 atoms. The amine compound may be classified into various amine compounds according to the number of hydrocarbon atom groups in which a hydrogen atom of ammonia (NH 3) is substituted. The primary amine in the amine compound may be represented by the following formula (1).

[Formula 1]

In Formula 1, R is a hydrocarbon atom group having C ₀ to C ₁₂ , and when C ₀ , _two NH ₂ atom groups are directly connected, n may be 1 ≦ n ≦ 6, and when n is 1, , R may be a hydroxyl group (OH).

More specifically, R is selected from an alkyl group having 1 to 12 carbon atoms, an alkylene group, an aryl group, a heteroaryl group, an alkoxy group, a carboxyl group or a hydroxyl group, and n is an integer from 1 to 6.

In this case, the alkyl group may be selected from methyl, ethyl, propyl, butyl, pentyl, hexyl. The alkylene group can be selected from methylene, ethylene, propylene, pentamethylene or hexamethylene. In addition, at least one of hydrogen of the alkyl group may be substituted by a methyl group or the like.

The aryl group can be selected from phenyl or naphthyl. In more detail, the aryl group may be unsubstituted or substituted by a methyl group or the like.

In particular, n is 2, R may be an alkylene group having 1 to 6 carbon atoms. That is, the amine compound may be a diamine compound.

The amine compound is classified into primary amine, secondary amine and tertiary amine, depending on the number of hydrocarbon groups in which the hydrogen atom of ammonia is substituted. That is, the primary amine may be represented by Formula 2 below, the secondary amine may be represented by Formula 3 below, and the tertiary amine may be represented by Formula 4 below.

[Formula 2]

(3)

[Formula 4]

The amine compound according to the embodiment may include a primary amine, a secondary amine or a tertiary amine. Preferably, the amine compound may be a primary amine.

The primary amine may be added in a ratio of about 0.01 wt% to about 2.0 wt% with respect to the organic solvent, but the embodiment is not limited thereto.

In addition, the reaction temperature of the organic solvent mixture and the amine compound may be about 10 ° C to about 160 ° C, but is not limited thereto.

In more detail, the amine compound may be selected from hydrazine, hydroxylamine, hexamethylenediamine or 2-methylpentamethylenediamine.

The acid solvent may be added to the organic solvent mixture at the same time as the glycol mixture is added. In detail, the acid catalyst may include sulfuric acid, methanesulfonic acid, and para-toluenesulfonic acid, but embodiments are not limited thereto.

The acid catalyst may be added at a ratio of about 0.01 wt% to about 1.0 wt% with respect to the organic solvent mixture.

The impurity may be selected from the group consisting of propionate-based compounds and ketone-based compounds.

In more detail, the impurities may be selected from the group consisting of methyl 3-methoxypropionate, cyclohexanone and ethyl 3-ethoxypropionate.

The impurities may be included in the organic solvent mixture in a ratio of about 0.1 wt% to about 8.0 wt%.

Hereinafter, a method of manufacturing an organic solvent according to an embodiment will be described in more detail with reference to FIGS. 1 to 3.

1 is a process flow chart for explaining the organic solvent purification method according to the embodiment, Figures 2 and 3 in the purification method of the PGMEA mixture according to the embodiment, the gas chromatographic chart (Gas Chromatography Chart of the PGMEA mixture before fractional distillation) ) And gas chromatography charts after reaction with amines.

Referring to Figure 1, the organic solvent purification method according to the embodiment, preparing a PGMEA mixture (ST10); Reacting with an amine compound (ST20); Reacting with the alkaline mixture (ST30); And fractional distillation (ST40).

In preparing the PGMEA mixture (ST10), an organic solvent mixture used in a display manufacturing process or a semiconductor manufacturing process is prepared.

The organic solvent mixture mainly contains PGMEA. That is, the organic solvent mixture is a PGMEA mixture. In particular, the organic solvent mixture may be generated after being used in the process of manufacturing a color filter of a display device such as a liquid crystal display or an organic light emitting display.

Here, the PGMEA mixture may include impurities such as pigments, photoresists, and metal components. In particular, the main component of the photoresist may be composed of a polymeric material such as a photoactive compound (PAC), a copolymer, a photopolymerization initiator and a crosslinking agent and other additives. Such impurities may be dissolved or dispersed in the PGMEA mixture.

In more detail, the PGMEA mixture may include a propionate-based compound such as MMP or EEP or a ketone-based compound such as cyclohexanone as impurities. In particular, since MMP and cyclohexanone have similar boiling points as PGMEA, it can be difficult to separate by distillation process.

Subsequently, in the step of reacting with the amine compound (ST20), the PGMEA mixture is reacted with the amine compound.

In detail, after the amine compound is added to the PGMEA mixture and mixed, the PGMEA mixture and the amine compound may be reacted at a temperature of about 10 ° C. to about 160 ° C. for about 30 seconds to about 48 hours. In more detail, the PGMEA mixture and the amine compound may be reacted at a process temperature of about 10 ° C. to about 140 ° C. for about 1 minute to about 4 hours.

The amine compound may comprise a primary amine, secondary amine or tertiary amine. Preferably, the amine compound may be a primary amine. More preferably, the primary amine is aniline, primary aromatic amine, N-cyclohexylamine, NH ₂ NH ₂ , C ₆ H ₁₁ -NH ₂ , n-hexylamine, hexamethylenediamone or 2-methyl Pentamethylenediamine (2-methylpentamethylenediamone) may be included, but embodiments are not limited thereto.

In detail, the primary amine may have a hydrocarbon atom group having C ₀ to C ₁₂ bonded to NH ₂ . In this case, when C ₀ , two NH 2 atom groups are directly connected, n may be 1 ≦ n ≦ 6, and when n is 1, R may be a hydroxyl group (OH).

The amine compound may be added in a ratio of about 0.01 wt% to about 2.0 wt% with respect to the organic solvent mixture, but embodiments are not limited thereto.

Accordingly, the impurities contained in the PGMEA mixture react with the amine compound and are converted into a substance having a boiling point different from that of the PGMEA. In detail, the cyclohexanone among the impurities included in the PGMEA mixture may be changed by the amine compound to have a boiling point different from that of the PGMEA.

Accordingly, the cyclohexanone can be first purified through fractional distillation using the boiling point difference with the PGMEA.

In addition, a small amount of acid catalyst may be added together with the amine compound to facilitate changing the boiling point of the impurity.

The acid catalyst may include sulfuric acid, methanesulphonic acid, para-toluenesulphonic acid, but embodiments are not limited thereto.

The acid catalyst may be included in an amount of about 0.01 wt% to about 1.0 wt based on the organic solvent mixture, but embodiments are not limited thereto.

Accordingly, the PGMEA mixture can change the boiling point of the cyclohexanone differently from the boiling point of the PGMEA by reaction with the amine compound or the amine compound and the acid catalyst, so that the cyclohexanone can be easily purified. In other words, the cyclohexanone is the difference between the boiling point and the PGMEA becomes large, the cyclohexanone in the PGMEA mixture can be easily purified.

At this time, the reaction between the amine compound and the acid catalyst and the PGMEA may not occur at all or may be minimized. In detail, since the amine compound has very weak alkalinity, the reaction with the PGMEA can be minimized.

Thus, the amine compound may minimize or not react with the PGMEA and may be purified using a small amount of alkali-based material when removing MMP, another impurity having a boiling point similar to that of the PGMEA in the PGMEA mixture. can do.

That is, in the purification method of the organic solvent according to the embodiment, by reacting the PGMEA mixture and the amine compound to change the boiling point of the cyclohexanone to first separate the cyclohexanone by a purification process, and then add an alkali-based mixture Since MMP is removed, an alkali-based mixture can be used in a smaller amount than when cyclohexanone and MMP are purified together. Therefore, it is possible to reduce the reaction of the PGMEA and alkali-based mixture, it is possible to minimize the loss of the PGMEA.

Subsequently, in the step of reacting with the alkaline mixture (ST30) and the fractional distillation (ST40), the PGMEA mixture after the reaction with the amine compound is reacted with the alkali-based mixture and then purified through fractional distillation. . Accordingly, most impurities contained in the PGMEA mixture are removed, and PGMEA having a purity of 99.0 wt% or more can be provided. At this time, relatively high boiling point impurities remain in the reactor.

On the other hand, the fractional distillation method described in more detail as follows.

That is, the fractional distillation comprises a first distillation step, a second distillation step, a third distillation step, and a filtration step. Here, the primary distillation step is a process of distilling the PGMEA mixture to concentrate and remove the pigment, photoresist and metal components contained in the solvent to the bottom of the primary distillation column.

Since the first distillation process remains in a portion of the material contained in the photoresist that is not irradiated with light (plasma or laser light) during the manufacture of the color filter, the non-thermally cured material is washed out with a solvent and discharged. Must be operated to minimize scaling on the tube side. Operation must be carried out continuously in a vacuum condition of 80 ℃ to 100 ℃ temperature conditions.

The PGMEA recovered to the upper part of the first distillation column is supplied to the second distillation column for the second distillation process after condensation to remove moisture and low boiling point material, and the lower material of the second distillation column is supplied to the third distillation column for the third distillation process. Remove high boiling point material.

Therefore, the metal ion component contained in the PGMEA mixture may be removed in the three-stage distillation process because it moves to the bottom of the first to third distillation column. Accordingly, the present invention can simply remove the metal ions contained in the PGMEA mixture by recovering the PGMEA at the top of the distillation column.

Each distillation column is made of stainless steel and subjected to pickling before use, and the gasket of the piping material should be constructed by applying a material that does not elute metal components. In the distillation column, if flooding occurs as an overload condition, the metal ions flow out to the upper part of the distillation column, and thus, the operation must be performed at an appropriate reflux amount and an operating condition.

The atmospheric distillation column operating conditions are the temperature of the secondary distillation column is about 100 ℃ to about 160 ℃, the temperature of the third distillation column is about 140 ℃ to about 180 ℃.

Thereafter, a filtration process is performed. The filtration step is a step of removing fine particles in the PGMEA by filtering the PGMEA recovered through the distillation process. The filtration step is a step of removing particles having a large particle size by using a filter having a pore diameter of 0.1 μm to 0.5 μm in three stages as a final step of removing particulate matter.

The filter medium uses a membrane membrane filter made of Teflon. The PGMEA solvent filtered by the regeneration method may allow the fine particles to remain at 40 or less on a particle size of 0.5 μm per 1 ml of the organic solvent.

As described above, in the method for purifying the PGMEA mixture according to the embodiment, impurities having a similar boiling point as that of PGMEA can be easily removed through the amine compound and the alkaline substance. Accordingly, the purification method of the PGMEA mixture according to the embodiment can easily produce PGMEA having a purity of 99 wt% or more in a yield of 80 wt% or more, using a low energy and simple fractional distillation apparatus.

2 and 3, MMP and cyclohexanone have similar boiling points to PGMEA, while boiling points of reaction products formed by the reaction of the cyclohexanone with the amine compound have a large difference from the boiling point of the PGMEA. It can be seen that.

As described above, in the method for purifying the PGMEA mixture according to the embodiment, the boiling point of the cyclohexanone may be changed by adding the amine compound to the PGMEA mixture including impurities and reacting with the cyclohexanone. Subsequently, by reacting the MMP with an alkali mixture having a strong alkalinity, the boiling point of the MMP can be changed to easily recycle the PGMEA with high purity of 99.0 wt% or more by a fractional distillation method.

Therefore, since the cyclohexanone is purified in advance from the PGMEA mixture and then the MMP is purified, a smaller amount of the alkali mixture is used, so that the loss of PGMEA by the alkali mixture can be minimized. It can be easily purified in high yield.

In addition, when the present invention is applied to production, it is possible to achieve a production yield improvement and a breakthrough throughput improvement compared to the conventional production method.

According to the present invention, by removing the unnecessary organic solvent components contained in the waste PGMEA generated in the color filter manufacturing process, and reused in the color filter manufacturing process, it can be reused in the waste liquid generation, improving the environmental problems and cost reduction Can be achieved at the same time.

Hereinafter, the present invention will be described in more detail through the organic solvent purification method according to the experimental and comparative examples. These experimental examples are only presented by way of example in order to explain the present invention in more detail. Therefore, the present invention is not limited to these experimental examples.

Experimental Example

PGMEA  Provide mixture

A PGMEA mixture was provided comprising about 93.4 wt% PGMEA, about 2.0 wt% PGME, about 2.0 wt% MMP, about 0.6 wt% cyclohexanone, and about 2.0 wt% EEP.

PGMEA  Reaction of mixtures and amine compounds

In a flask equipped with a stirrer and a reflux condenser, while the PGMEA mixture (about 100 g) is being stirred, an acid catalyst such as sulfuric acid, methanesulphonic acid, para-toluenesulphonic acid, etc. % To 1.0 wt% were added and reacted according to the process conditions shown in Table 2 below.

If the process is slow, install a distillation column (Column) and remove the water to the top of the distillation column.

division Primary amine compound Ratio (wt%) ^{1 )} Temperature (℃) Hour Experimental Example 1 H ₂ NNH ₂ 0.20 100 2 Experimental Example 2 H ₂ NNH ₂ 0.30 25 6 Experimental Example 3 HMDA ^{2 )} 1.0 120 6 Experimental Example 4 MPMD ^{3 )} 1.2 120 8 Experimental Example 5 H ₂ NOH 0.4 135 4

Note 1. The content of each component of Table 2 is a value converted into weight with respect to 100 weight of the PGMEA mixture.

Note 2. The HMDA is Hexamethylenediamine.

Note 3. The MPMD is 2-methylpentamethylenediamine.

result

In each experiment, the degradation rates of PGMEA, MMP, cyclohexane and EEP were derived as in Table 3 below. That is, referring to Figures 2, 3 and Table 3, it can be seen that the cyclohexanone of the impurities are completely decomposed.

As a result, the primary amine did not degrade PGMEA, MMP, EEP and the like while effectively reacting with cyclohexane.

division % Degradation of PGMEA % Degradation of MMP % Of decomposition of cyclohexanone % Degradation of EEP Experimental Example 1 0.0 0.0 100 0.0 Experimental Example 2 0.0 0.0 100 0.0 Experimental Example 3 0.0 0.0 98 0.0 Experimental Example 4 0.0 0.0 95 0.0 Experimental Example 5 0.0 0.0 95 0.0

Features, structures, effects, and the like described in the above embodiments are included in at least one embodiment of the present invention, and are not necessarily limited to only one embodiment. Furthermore, the features, structures, effects, and the like illustrated in each embodiment may be combined or modified with respect to other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be understood that various modifications and applications are possible. For example, each component specifically shown in the embodiments can be modified and implemented. It is to be understood that all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (12)

Preparing an organic solvent mixture comprising propylene glycol monomethyl ether acetate and cyclohexanone; And
Reacting the organic solvent mixture by adding an amine compound and an acid catalyst to remove the cyclohexanone,
The amine compound comprises at least one of hydrazine, hydroxylamine, hexamethylene diamine and 2-methylpentamethylene diamine,
The amine compound is included by 0.2 wt% to 1.2 wt% with respect to the organic solvent mixture,
The acid catalyst is a purification method of an organic solvent comprising at least one of sulfuric acid, methane sulfonic acid and para-toluene sulfonic acid. The method of claim 1,
The amine compound is a purification method of the organic solvent represented by the following formula (1).
[Formula 1]

(Wherein R is selected from an alkyl group having 1 to 12 carbon atoms, an alkylene group, an aryl group, an alkoxy group, a carboxyl group or a hydroxyl group, and n is an integer of 1 to 6). 3. The method of claim 2,
N is 2, and R is an alkylene group having 1 to 6 carbon atoms. The method of claim 1,
The amine compound is a primary organic amine purification method. delete delete delete delete The method of claim 1,
Reaction temperature of the organic solvent mixture and the amine compound is 10 ℃ to 160 ℃ purification method of the organic solvent. delete delete delete

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