TW202104140A - Method for purifying fluorinated liquid and purification apparatus using same - Google Patents

Abstract

A method for purifying a fluorinated liquid according to one embodiment of the present disclosure includes performing an extraction step two or more times, the extraction step including a first step of bringing water into contact with a fluorinated liquid in which a cleaning agent is mixed and a second step of separating a mixed solution after water contact into two liquids, an aqueous phase located an upper layer and a phase containing the fluorinated liquid located in a lower layer, and then collecting the liquid in the lower layer, in which a total amount of water bought into contact with the liquid until the final extraction step is about 30.0 mass% or less, the cleaning agent is an aprotic polar solvent that is dissolved in the fluorinated liquid, and the fluorinated liquid is hydrofluoroether, hydrofluoroolefin, or a mixture thereof.

Description

Method for purifying fluorinated liquid and purification equipment using it

This disclosure relates to a method for purifying fluorinated liquid and a purification device using the method.

For example, a method for manufacturing an organic EL display includes a step of evaporating RGB three-color dyes on a substrate (such as glass) through a metal mask to form an organic light-emitting layer. Since the metal mask is an expensive component, after the metal mask is cleaned with a detergent (such as N-methyl-2-pyrrolidone), a fluorinated liquid rinse step and a drying step are followed to reuse the metal mask. cover.

Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2006-313753) describes a cleaning method in which when low-molecular-weight organic EL elements are manufactured, the metal mask used in the vacuum evaporation step is obtained by containing aprotic The cleaning liquid composition of a polar solvent (such as N-methyl-2-pyrrolidone) is immersed or cleaned with a jet stream, and then rinsed with hydrofluoroether.

Patent Document 2 (Japanese Unexamined Patent Application Publication No. H07-076787) describes a metal cleaner purification equipment, which includes a cleaning device that uses NMP as the metal cleaner; and a purification device that is cleaned after cleaning. Remove contaminants from the NMP cleaning liquid, and circulate the resulting liquid to the cleaning equipment, which is provided in The filter material in the purification equipment is a granular filter material that contains at least polypropylene and has floatability to NMP.

Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2008-163400) discloses a cleaning system including a cleaning tank containing one or more selected from (1a) hydrocarbons, (1b) glycol ethers, and (1c) The ester cleaning fluid system is stored in it, and the material to be cleaned is immersed in it; the rinse fluid tank contains one or more rinse fluids selected from (2a) hydrofluorocarbons and (2b) hydrofluoroethers as main components It is stored in it, and the material to be cleaned is immersed in it; a steam tank, which stores the rinsing liquid and generates vapor of the rinsing liquid; and a purification unit, which has a distiller.

Reference list

Patent documents

[Patent Document 1]: JP 2006-313753 A

[Patent Document 2]: JP H07-076787 A

[Patent Document 3]: JP 2008-163400 A

Generally speaking, increasing the number of cleaning and rinsing operations also increases the mixing rate of the cleaning agent into the rinsing tank. Therefore, the rinsing tank becomes contaminated with the cleaning agent, and therefore the rinsing liquid needs to be replaced periodically. However, since the fluorinated liquid used as the washing liquid is also an expensive solvent, what is desired is a technique for efficiently collecting and reusing the fluorinated liquid from the contaminated washing liquid.

In recent years, regulations such as reducing environmental load tend to be implemented in various countries, and, for example, in various manufacturing lines, there has been a demand for measures for strict drainage regulations, such as reducing waste water.

The present disclosure provides a method for purifying fluorinated liquid, which helps to reduce environmental load and has excellent purification efficiency for the fluorinated liquid into which the cleaning agent is mixed; and a purification device using the method.

According to an embodiment of the present disclosure, there is provided a method for purifying a fluorinated liquid. The method includes performing an extraction step two or more times. The extraction step includes a first step of contacting water with a fluorinated liquid in which a cleaning agent is mixed. Step, and the second step of separating the mixed solution after the water has contacted the two liquids. The water phase is located in the upper layer, and the phase containing the fluorinated liquid is located in the lower layer, and then the liquid is collected in the lower layer. The total amount of water contacted in the extraction step is about 30.0% by mass or less, the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or a mixture thereof .

According to another embodiment of the present disclosure, there is provided a method for using a fluorinated liquid purified by using the above-mentioned method for purifying a fluorinated liquid as a rinsing liquid for components in an organic EL display manufacturing device.

According to yet another embodiment of the present disclosure, there is provided a fluorinated liquid purification device, which includes an extraction component for performing an extraction step two or more times. The extraction step includes a fluorinated liquid in which water and a cleaning agent are mixed The first step of contact, and contact with water In the second step of separating the mixed solution into the two liquids, the aqueous phase is located in the upper layer, and the phase containing the fluorinated liquid is located in the lower layer, and then the liquid is collected in the lower layer until the total amount of water contacted in the final extraction step It is about 30.0% by mass or less, the cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or a mixture thereof.

According to the present disclosure, it is possible to provide a method for purifying fluorinated liquid, which helps reduce environmental load and has excellent purification efficiency for the fluorinated liquid into which the cleaning agent is mixed; and a purification device using the method.

The above description should not be interpreted as revealing all aspects of the present disclosure and all advantages of the present disclosure.

In the following, a more detailed description is given for the purpose of illustrating representative embodiments of the present disclosure, but the present disclosure is not limited to these embodiments.

In a method for purifying a fluorinated liquid according to an embodiment of the present disclosure, the extraction step is performed two or more times, and the extraction step includes the first step of contacting water with the fluorinated liquid into which the detergent is mixed , And the second step of separating the mixed solution after the water has contacted the two liquids, the water phase is located in the upper layer, and the phase containing the fluorinated liquid is located in the lower layer, and then the liquid is collected in the lower layer until the final extraction step contacts Total water The amount is about 30.0% by mass or less. The cleaning agent used here is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or a mixture thereof. According to the purification method of the present disclosure, although the total amount of water contacted until the final extraction step is as small as about 30.0% by mass or less, the purification efficiency of the fluorinated liquid is excellent, and the amount of waste water is small, and therefore may be helpful To reduce or suppress environmental load.

The cleaning agent that can be mixed in the method for purifying a fluorinated liquid of the present disclosure is a cleaning agent used during cleaning of various components, and examples thereof include metal masks, anti-deposition plates, or Similar to the cleaning agent used during cleaning. The cleaning agent is not particularly limited, as long as it is an aprotic polar solvent dissolved in the fluorinated liquid. Examples thereof include at least one selected from the group consisting of cyclic amide-based solvents, amine-based solvents, glycol ether-based solvents, acetone, dimethyl sulfoxide, and dimethylformamide. These cleaning agents have excellent cleaning effects and are more soluble in water than in fluorinated liquids, and are therefore suitable cleaning agents in the purification method of the present disclosure, which use water to remove from the fluorinated liquid detergent. Among them, from the viewpoint of the balance between the cleaning properties of various components (such as metal masks and anti-deposition plates) and the solubility in fluorinated liquids and water, the solvent based on cyclic amide is preferred, and the more preferred It is N-alkylpyrrolidone solvent (such as N-methyl-2-pyrrolidone (NMP) and N-butyl-2-pyrrolidone (NBP)) or solvent called γ-lactone amine solvent , And particularly preferred is N-methyl-2-pyrrolidone (NMP). Such aprotic polar solvents can be used alone or in combination of two or more. If the above-mentioned cleaning agent is used, the fluorinated liquid can be efficiently purified by the purification method of the present disclosure. In addition to the above cleaning agents, the cleaning agent may be contained within a range that does not inhibit the purification efficiency of fluorinated liquid However, from the standpoint of purification efficiency and the like, it is preferable not to contain other cleaning agents.

The boiling point of the cleaning agent is not particularly limited, but considering, for example, the application of the following distillation step, it is preferably about 55°C or higher, about 100°C or higher, about 120°C or higher, or about 150°C. Or higher, about 180°C or higher, about 200°C or higher, or about 250°C or higher. The upper limit of the boiling point of the cleaning agent is not particularly limited, and can be set to, for example, about 300°C or lower, about 280°C or lower, or about 260°C or lower.

Examples of fluorinated liquids that can be purified by the method for purifying fluorinated liquids of the present disclosure include hydrofluoroethers, hydrofluoroolefins, or mixtures thereof. In addition to the above-mentioned fluorinated liquid, the fluorinated liquid may contain other fluorinated liquids (such as hydrochlorofluorocarbons, hydrofluorocarbons, and the like) within a range that does not inhibit purification efficiency; however, from the purification efficiency and From a similar point of view, it is preferable not to include other fluorinated liquids.

The solubility of water in the fluorinated liquid is not particularly limited. For example, from the viewpoint of separation performance and purification efficiency between the water phase and the phase containing the fluorinated liquid, the water solubility at 25° C. is favorably about 500 ppm or less, about 300 ppm or less, about 200 ppm or Less, or about 150 ppm or less. The lower limit of the solubility is not particularly limited, and can be set to, for example, about 10 ppm or more, about 30 ppm or more, or about 50 ppm or more. Cleaning agents such as NMP dissolve in water more easily than in the fluorinated liquid. Therefore, when the solubility of water in the fluorinated liquid is within this range, it is difficult for the water to dissolve in the fluorinated liquid, and therefore when in contact with water, the cleaning agent in the fluorinated liquid tends to become easier Incorporated into water, and the percentage of cleaning agent remaining in the fluorinated liquid can be further reduced. Here, "the solubility of water in the fluorinated liquid (the solubility of water in the fluorinated liquid” refers to the mass ratio of water that can be dissolved in the fluorinated liquid to the greatest extent under an atmosphere of 25°C, and is measured by the use of trace moisture measuring equipment (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to the Karl Fischer titration method (coulometric titration method) defined by JIS K 0068:2001 to measure the average value obtained at least five times.

The boiling point of the fluorinated liquid is not particularly limited, but in consideration of, for example, the application of the following distillation step, it is preferably about 30°C or higher, about 55°C or higher, about 60°C or higher, or about 75°C or higher, and preferably about 150°C or lower, about 100°C or lower, or about 80°C or lower.

Among the above-mentioned fluorinated liquids, it is preferable to use hydrofluoroether from the viewpoint of separation performance and purification efficiency of the phase containing the water phase and the fluorinated liquid. Hydrofluoroether is a compound containing oxygen atoms that are ether bondable between the carbon atoms of the hydrofluorocarbon. The number of ether bondable oxygen atoms contained in one hydrofluoroether molecule can be one or two or more. From the viewpoint of ease of use as the boiling point, stability, and the like of the solvent, one or two are preferable, and one is more preferable. The molecular structure of hydrofluoroether only needs to be tethered, and can be linear or branched, but from the viewpoint of purification efficiency and the like, it is preferably linear.

Examples of hydrofluoroethers include isolation type hydrofluoroethers, such as C ₄ F ₉ OCH ₃ , C ₄ F ₉ OCH ₂ CH ₃ , C ₅ F ₁₁ OCH ₃ , C ₅ F ₁₁ OCH ₂ CH ₃ , C ₆ F ₁₃ OCH ₃ , C ₆ F ₁₃ OCH ₂ CH ₃ , C ₇ F ₁₅ OCH ₃ , C ₇ F ₁₅ OCH ₂ CH ₃ , C ₈ F ₁₇ OCH ₃ , C ₈ F ₁₇ OCH ₂ CH ₃ , C ₉ F ₁₉ OCH ₃ , C ₉ F ₁₉ OCH ₂ CH ₃ , C ₁₀ F ₂₁ OCH ₃ , and C ₁₀ F ₂₁ OCH ₂ CH ₃ ; and hydrofluoroethers, such as CF ₃ CH ₂ OCF ₂ CF ₂ H, CF ₃ CHFOCH ₂ CF ₃ , CF ₃ CH ₂ OCF ₂ CFHCF ₃ , CHF ₂ CF ₂ CH ₂ OCF ₂ CF ₂ H, C ₃ F ₇ OC ₃ F ₆ OCFHCF ₃ , CF ₃ CF (CF ₃ ) CF (OCH ₃ ) CF ₂ CF ₃ , CF ₃ CF (CF ₃ )CF (OC ₂ H ₅ )CF ₂ CF ₃ , CF ₂ (OCH ₂ CF ₃ )CF ₂ H, CF ₂ (OCH ₂ CF ₃ )CFHCF ₃ , CF ₂ (OCH ₂ CF ₂ CF ₂ H) CF ₂ H, and CF ₂ (OCH ₂ CF ₂ CF ₂ H)CFHCF ₃ . Such hydrofluoroether can be used alone or in combination of two or more.

Among them, the isolated type of hydrofluoroether has low solubility in water, and when in contact with water, compared to other hydrofluoroethers or hydrofluoroolefins, it can reduce the proportion of being dissolved in the water phase, and therefore it is easy to dissolve the water. The phase is separated from the phase containing the fluorinated liquid. Therefore, the separated water phase is less likely to be contaminated by the fluorinated liquid, and therefore it can cope with relatively strict drainage regulations, for example. Among these isolation types of hydrofluoroethers, C ₄ F ₉ OCH ₃ or C ₄ F ₉ OCH ₂ CH _{3 is more} preferable. Here, "segregate-type" refers to a structure in which one side is fully fluorinated, and the other side is composed of carbon and hydrogen with ether bonds interposed therebetween.

Hydrofluoroolefin (hydrofluoroolefin) means a compound in which one or more of the hydrogen atoms in the olefin are replaced by fluorine atoms. The number of fluorine atoms contained in the hydrofluoroolefin is not particularly limited, and may be one or more, or two or more, and may be ten or less, or six or less. The hydrofluoroolefin may be either E type (trans) or Z type (cis). The hydrofluoroolefin may be a hydrochlorofluoroolefin. Hydrochlorofluoroolefin (hydrochlorofluoroolefin) refers to a compound in which one or two or more hydrogen atoms in an olefin are replaced by fluorine atoms and one or two or more other hydrogen atoms in the olefin are replaced by chlorine atoms. The number of chlorine atoms in the hydrochlorofluoroolefin is not particularly limited, and may be one or more, and may be five or less, or three or less.

Examples of hydrofluoroolefins without chlorine atoms include CF ₃ -CH=CH ₂ , CF ₃ -CF=CH ₂ , CHF ₂ -CH=CHF, CHF ₂ -CF=CH ₂ , CH ₂ F-CH=CF ₂ , CH ₂ F-CF=CHF, CH ₃ -CF=CF ₂ , CF ₃ -CH=CH-CF ₃ , CF ₃ -CH=CF-CH ₃ , CF ₃ -CF=CH-CH ₃ , CF ₃ -CH =CH-CH ₂ F、CHF ₂ -CF=CF-CH ₃ 、CHF ₂ -CF=CH-CH ₂ F、CHF ₂ -CH=CF-CH ₂ F、CHF ₂ -CH=CH-CHF ₂ , CH ₂ F-CF=CF-CH ₂ F, CH ₂ F-CH=CH-CF ₃ , CH ₂ F-CF=CH-CHF ₂ , CF ₃ -CH ₂ -CF=CH ₂ , CF ₃ -CHF-CH =CH ₂ , CF ₃ -CH ₂ -CH=CHF, CHF ₂ -CF ₂ -CH=CH ₂ , CHF ₂ -CHF-CF=CH ₂ , CHF ₂ -CHF-CH=CHF, CH ₂ F-CF ₂ -CF=CH ₂ 、CH ₂ F-CF ₂ -CH=CHF、CH ₂ F-CHF-CF=CHF、CH ₂ F-CHF-CF=CF ₂ 、CH ₂ F-CH ₂ -CF=CF ₂ 、 CH ₃ -CF ₂ -CF=CHF, and CH ₃ -CF ₂ -CH=CF ₂ . Examples of hydrofluoroolefins having chlorine atoms (ie, hydrochlorofluoroolefins) include CF ₃ -CH=CHCl, CHF ₂ -CF=CHCl, CHF ₂ -CH=CFCl, CHF ₂ -CCl=CHF, CH ₂ F- CCl=CF ₂ , CHFCl-CF=CHF, CH ₂ Cl-CF=CF ₂ , and CF ₃ -CCl=CH ₂ . Particularly preferred hydrofluoroolefins having chlorine atoms are CF ₃ -CH=CHCl. Hydrofluoroolefins (including hydrochlorofluoroolefins) can be used alone or in combination of two or more.

The water used in the method for purifying the fluorinated liquid of the present disclosure is not particularly limited, and for example, tap water, distilled water, ion exchange water, and the like can be used.

In the method for purifying the fluorinated liquid of the present disclosure, the extraction step is performed two or more times, and the extraction step includes the first step of contacting water with the fluorinated liquid into which the detergent is mixed, and the step of contacting the water to In the second step of separating the mixed solution in the two liquids, the aqueous phase is located in the upper layer and the phase containing the fluorinated liquid is located in the lower layer, and then the liquid is collected in the lower layer. The upper limit of the number of extraction steps is not particularly limited, but from the simplified From the viewpoint of the purification procedure, it is advantageous to have, for example, 5 times or less, 4 times or less, or 3 times or less.

The method of contacting water with the fluorinated liquid into which the detergent is mixed in the first step is not particularly limited, and for example, the methods (1) to (7) below can be used alone or in combination with two or more of them, and It can be performed by combining some of the methods (1) to (7) as appropriate. For example, the physical stirring method using vibration, stirrer, or the like described in (3), (6), or (7), the stirring method using air, and the stirring method using ultrasonic waves, or the like can be applied In method (1) or (2).

(1) A method for dripping the fluorinated liquid into which the detergent is mixed from the top of the container to the container containing water.

(2) A method for adding water from below the container to a container containing a fluorinated liquid in which a detergent is mixed.

(3) A method for physically stirring a container containing a mixed liquid of detergent, fluorinated liquid, and water by using a stirrer, stirring blade, or the like.

(4) In the case where the upper and lower layers are connected to each other by a tube or the like, and the mixed solution has been separated into two layers in a container containing a mixed solution of detergent, fluorinated liquid, and water, the upper liquid system The method of moving to the lower layer by gravity or a pump.

(5) In the case where the upper and lower layers are connected to each other by a tube or the like, and the mixed solution has been separated into two layers in a container containing a mixed solution of detergent, fluorinated liquid, and water, the lower liquid system The method of moving to the upper layer by gravity or a pump.

(6) Where gas (such as air) is blown into the container and bubbling to mix a mixed solution, and the mixed solution has been mixed with detergent, fluorinated liquid, and water. When the mixed solution container is separated into two layers, the lower layer liquid system is moved to the upper layer by gravity or a pump.

(7) In the case where ultrasonic waves are applied to the container to mix a mixed solution, and the mixed solution has been separated into two layers in the container containing the mixed solution of detergent, fluorinated liquid, and water, the lower liquid system The method of moving to the upper layer by gravity or a pump.

The amount of water contacted in the first step may be the same or different from each other in each extraction step. For example, in the case of performing the extraction step three times, a total of 3.0 g of water may be 1.0 g added to the fluorinated liquid into which the cleaning agent is mixed and contacted with the fluorinated liquid. Alternatively, 1.5 g of water may be added for the first time Water, 1.0g for the second time and 0.5g for the third time.

According to the method for purifying fluorinated liquid of the present disclosure, excellent purification efficiency can be achieved by performing the extraction step two or more times, even if the amount of water contacted in the first step performed first is low and until the final extraction The total amount of water contacted in the step is about 30.0% by mass or less. The amount of water contacted in the first step performed first can be about 20.0% by mass or less, about 19.0% by mass or less, or about 18.0% by mass or less, and can be about 3.0% by mass or more, about 4.0% by mass or more, or about 5.0% by mass or more. Here, "the amount of water brought into contact in the first step firstly performed" means the amount of water brought into contact in the first step firstly performed. The value of the percentage of the mass of the cleaning agent contained in the fluorinated liquid and the mass of the added water. In addition, the quality of the cleaning agent contained in the first fluorinated liquid in the first step can be determined by a quantitative analysis method using a calibration curve that indicates the fluorine produced by the gas chromatography analyzer. Correlation of the concentration of the cleaning agent in the chemical liquid.

The temperature and time when the water is in contact with the fluorinated liquid into which the cleaning agent is mixed is not particularly limited, because it may vary depending on the required properties, size, contact method, and the like of the purified fluorinated liquid. For example, the temperature may be about 20°C or higher, about 23°C or higher, or about 25°C or higher, and may be about 40°C or lower, about 35°C or lower, or about 30°C or higher. Low, and the contact time can be set to about 30 seconds or more, about 1 minute or more, or about 5 minutes or more, and can be about 1 day or less, about 10 hours or less, about 1 Hours or less, or about 30 minutes or less.

The second step in the extraction step includes a step of separating the mixed solution after the water is contacted with the two liquids, the water phase is located in the upper layer and the phase containing the fluorinated liquid is located in the lower layer, and then the liquid is collected in the lower layer. The separation of the two liquids of the upper layer and the lower layer can be achieved, for example, by a step of standing still a mixed solution containing the cleaning agent and the fluorinated liquid.

The lower liquid can be collected directly from below the container containing the upper liquid and the lower liquid through a tube or the like, or the upper liquid can be collected from the top of the container, and then the lower liquid can be collected, or the tube or the like can be stretched and pulled from above the container Grows to near the bottom of the container.

The total amount of water contacted until the final extraction step is about 30.0% by mass or less, and when considering, for example, the reduction in the amount of waste water and the balance of purification efficiency, the total amount is advantageously about 29.0% by mass or less, about 28.0% by mass or Less, or about 27.0% by mass or less, about 25.0% by mass or less, about 23.0% by mass or less, or about 20.0% by mass or less, and advantageously about 5.0% by mass or more, about 7.0% by mass or more, or about 9.0% by mass or more. Here, "the total amount of water contacted until the final extraction step (total Amount of water contacted until the final extraction step)” means a value calculated as a percentage of the total added water amount relative to the mass of the cleaning agent contained in the fluorinated liquid for the first time in the first step and the total added water amount.

The purity of the fluorinated liquid purified by the method for purifying the fluorinated liquid of the present disclosure can reach about 95.0% or higher, about 96.0% or higher, about 97.0% or higher, or about 98.0% or higher. The upper limit of the purity of the fluorinated liquid is not particularly limited, and can be set to, for example, less than about 100%, about 99.9% or less, or about 99.8% or less.

The method for purifying the fluorinated liquid of the present disclosure can be suitably performed by using one or two of a heating step, a distillation step (such as a boiling distillation step, a vacuum distillation step, or the like), a cooling separation step, and the like. Or more to impose.

If it is desired to increase the purity of the fluorinated liquid, the purification method of the present disclosure may further include a distillation step of distilling the lower layer liquid collected through the final extraction step. In the related art, distillation components have been commonly used for the purification of fluorinated liquids, but in the case of fluorinated liquid systems that are purified by distillation components alone, because the amount of recoverable fluorinated liquids is extremely low, most of the fluorinated liquids Essentially it must be disposed of. On the other hand, when the distillation step is combined with the method for purifying fluorinated liquid disclosed in the present disclosure, the recovery amount of fluorinated liquid can be greatly improved compared to the purification method using a distillation component alone.

The distillation temperature in the distillation step is not limited to the following, and for example, it may be about 70°C or higher, about 72°C or higher, or about 75°C or higher, and may be about 100°C or lower, about 95°C Or lower, or about 90°C or lower.

In some embodiments, the purification method of the present disclosure may not apply an additional distillation step or heating step. Purification methods that do not include such steps can complete the purification at room temperature To increase energy efficiency and eliminate the need for additional operations. Therefore, from the viewpoint of reducing environmental load, it is advantageous not to employ a distillation step or a heating step.

The fluorinated liquid purification equipment according to an embodiment of the present disclosure includes an extraction member for performing the extraction step two or more times, and the extraction step includes the first step of contacting water with the fluorinated liquid into which the cleaning agent is mixed , And the second step of separating into two phases, the aqueous phase is located in the upper layer, and the phase containing the fluorinated liquid is located in the lower layer, and then the liquid is collected in the lower layer until the final extraction step is in contact with the liquid. The amount of water is about 30.0% by mass or less. The cleaning agent used here is an aprotic polar solvent dissolved in the fluorinated liquid, and the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or a mixture thereof. Examples of cleaning agents, fluorinated liquids, and water that can be used in such purification equipment may be the same as those used in the above-mentioned purification method. In addition, this type of purification equipment can similarly exhibit the effects described in the above-mentioned purification method.

The extraction component in the fluorinated liquid purification equipment of the present disclosure is not particularly limited, as long as the extraction component can perform the extraction step including the first step and the second step in the method for purifying the fluorinated liquid. For example, the material, capacity, shape, quantity, material, capacity, shape, quantity, and material of a container (in some cases referred to as a "tank", or the like) containing a detergent, a fluorinated liquid, and a mixed solution of water used in the extraction member The location or the like can be appropriately selected depending on the use application or use environment of the device.

The fluorinated liquid purification equipment of the present disclosure can optionally perform any steps (such as the heating step, distillation step (such as boiling distillation step, vacuum distillation step, or the like), cooling in the method for purifying fluorinated liquid described above. Separation steps, and the like) components. For example, a container for storing the lower liquid used in the distillation step The material, capacity, shape, number, location, or the like can be appropriately selected depending on the use application or use environment of the device. Various components (such as a heating component, a distillation component, a cooling separation component, and the like) can be applied to the fluorinated liquid purification equipment alone or in combination of two or more.

If it is desired to increase the purity of the fluorinated liquid, the purification device of the present disclosure may further include a distillation unit for distilling the lower layer liquid collected by the extraction unit. Known equipment can be used for the distillation component, which includes, for example, a distillation pot for storing and heating the collected lower layer liquid, and a cooler connected with the distillation pot to condense and liquefy the lower layer liquid vapor.

In some embodiments, the purification device of the present disclosure may not apply additional distillation components or heating components. Purification equipment that does not contain such components can complete purification at ambient temperature, thus increasing energy efficiency and eliminating the need for additional operations. Therefore, from the viewpoint of reducing environmental load, it is advantageous not to use a distillation member or a heating member.

The method and purification equipment for purifying fluorinated liquid disclosed in the present disclosure can be appropriately used as on-line or off-line in various manufacturing lines. In the online situation, when using the method for purifying fluorinated liquid and the purification equipment of the present disclosure, these can be appropriately configured so that the purified fluorinated liquid can be used in the cleaning step or in the washing step, for example. Reuse. If these are used off-line, the fluorinated liquid system that has been used in the manufacturing line (such as the cleaning step or washing step of the organic EL display) is purified in another line and can be reused in the organic EL display manufacturing line ; On the other hand, the purified fluorinated liquid can be reused for another purpose other than the cleaning liquid or flushing liquid for printed wiring boards, for example.

In addition to the rinsing liquid used for various components (such as metal masks and anti-deposition plates exposed to cleaning and rinsing operations), the fluorinated liquid purified using the method for purifying fluorinated liquid and purification equipment of the present disclosure is not limited to the following, And, for example, it is used in organic EL display manufacturing equipment, and can be used as a cleaning liquid or a rinse liquid for various electronic parts, precision parts, metal parts, printed wiring boards, and the like. Here, "deposition-proof plate" refers to a member installed inside the vacuum chamber of a vacuum evaporation equipment used in the manufacture of organic EL displays, and can be removed and cleaned to prevent evaporation from The three colors red (R), green (G), and blue (B) of the vacuum chamber are contaminated. The use of the rinsing fluid is not limited to the direct use of a liquid, for example, by immersing the material to be rinsed and cleaned in the rinsing fluid to rinse off the cleaning agent or the deposited similar, but also includes the evaporating of the rinsing fluid to vaporize the The gas sticks to the surface to be rinsed and cleaned to rinse off detergent or the like.

Instance

Specific embodiments of the present invention will be illustrated in the following examples, but the present invention is not limited to these embodiments.

The products used in these examples and the like are shown in Table 1 below.

The purity of the fluorinated liquid was evaluated by gas chromatography using 7890 A manufactured by Agilent Technologies. The measurement conditions of gas chromatography are as follows:

String type: HP-1301

Length of pipe string: 60m

Column temperature: 260℃

Carrier gas type: helium

Carrier gas flow rate: 205mL/min

Sample injection volume: 1μL

Example 1

Add 100g of NOVEC(TM) 7100 (fluorinated liquid) and 10g of NMP (cleaning agent) to the plastic bottle. 0.2 g of distilled water was added to the mixed solution and shaken in a mechanical shaker for 15 minutes. Next, the resulting mixed solution was left to separate into two layers, an upper layer (aqueous phase) and a lower layer (phase containing fluorinated liquid), and the upper layer (aqueous phase) floating on the surface was collected with a dropper to remove it from the plastic bottle. Remove the upper layer (first extraction step). A microsyringe was used to collect a sample for purity measurement from the lower liquid, and the purity of the NOVEC(TM) 7100 in the lower liquid was measured. A series of operations from adding distilled water to purity measurement were performed four times in total, and the results are shown in Table 2. Here, add 0.2 after the second time The distilled water of g is performed on the lower layer liquid obtained by removing the upper layer (water phase). In addition, the "amount of water after water contact (mass%)" in Table 2 is calculated as the cleanliness of the total added water relative to the total added water and the initial blending amount (10g) The value of the percentage of NMP.

<Examples 2 to 5 and Comparative Examples 1 to 2>

The purity of the fluorinated liquid was measured in the same manner as in Example 1, except that the amount of distilled water added was changed to the amount shown in Table 2. Note that because the amount of water after the water contact exceeds 30.0% by mass, the extraction step after the fourth time in Example 4 and the third or subsequent extraction step in Example 5 were not performed. In addition, in Comparative Example 1, in the second extraction step, the amount of water after water contact was already greater than 30.0% by mass in the first extraction step in Comparative Example 2, and the subsequent extraction step was not performed.

Those skilled in the art should understand that various modifications can be made to the above-mentioned embodiments and examples without departing from the basic principles of the present invention. In addition, it is obvious to those having ordinary knowledge in the technical field that various improvements and modifications can be made to the present invention without departing from the spirit and scope of the present invention.

Claims (11)

A method for purifying fluorinated liquid, which includes Perform the extraction step two or more times. The extraction step includes the first step of contacting water with the fluorinated liquid into which the detergent is mixed, and the second step of separating the mixed solution after the water has contacted the two liquids. The water phase is located In the upper layer, and the phase containing the fluorinated liquid is located in the lower layer, and then the liquid is collected in the lower layer, The total amount of water contacted until the final extraction step is about 30.0% by mass or less, The cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and Wherein the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or a mixture thereof. The purification method of claim 1, wherein the amount of water contacted in the first step performed first is 3.0 to 20.0% by mass. Such as the purification method of claim 1 or 2, wherein the number of times of performing the extraction step is 5 times or less. The purification method according to any one of claims 1 to 3, wherein the aprotic polar solvent is selected from the group consisting of cyclic amide-based solvents, amine-based solvents, glycol ether-based solvents, acetone, dimethylene At least one of sulfide, and dimethylformamide. The purification method of any one of claims 1 to 4, wherein the solubility of water in the fluorinated liquid is 500 ppm or less. The purification method according to any one of claims 1 to 5, which further comprises a step of collecting the lower layer liquid through the final extraction step by distillation. The purification method of any one of claims 1 to 6, wherein the purity of the fluorinated liquid purified by the purification method is 95.0% or greater. A method of using a fluorinated liquid as a rinsing liquid for components in an organic EL display manufacturing device, the fluorinated liquid system being purified by using the purification method according to any one of claims 1 to 7. The method of claim 8, wherein the member is a metal mask or a deposition prevention plate. A fluorinated liquid purification equipment, which contains Extraction means, which performs two or more extraction steps. The extraction step includes a first step of contacting water with a fluorinated liquid into which the detergent is mixed, and a second step of separating the mixed solution after the water has contacted the two liquids , The water phase is located in the upper layer, and the phase containing the fluorinated liquid is located in the lower layer, and then the liquid is collected in the lower layer, The total amount of water contacted until the final extraction step is about 30.0% by mass or less, The cleaning agent is an aprotic polar solvent dissolved in the fluorinated liquid, and Wherein the fluorinated liquid system is hydrofluoroether, hydrofluoroolefin, or a mixture thereof. The purification device of claim 10, which further includes a member for distilling the liquid in the lower layer collected through the extraction member.