JP7126830B2 - Method for regenerating fluorinated liquids and regenerating apparatus using same - Google Patents

Description

FIELD OF THE DISCLOSURE The present disclosure relates to a method of regenerating fluorinated liquids and a regenerating apparatus using the method.

For example, a manufacturing method of an organic EL display (hereinafter sometimes referred to as "OLED") includes a step of forming an organic light-emitting layer by vapor-depositing pigments of three colors of RGB on a substrate such as glass through a metal mask. ing. Since the metal mask is an expensive member, the metal mask is washed with an N-methyl-2-pyrrolidone (hereinafter sometimes referred to as "NMP") solution, followed by a rinsing process with a fluorinated liquid and a drying process. reused.

Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2006-313753) discloses that a metal mask used in a vacuum vapor deposition process in manufacturing a low-molecular-weight organic EL device contains an aprotic polar solvent such as N-methyl-2-pyrrolidinone. A cleaning method is described in which a cleaning solution composition is used for cleaning by immersion or jet water flow, followed by rinsing with a hydrofluoroether.

Patent Document 2 (Japanese Patent Application Laid-Open No. 07-076787) discloses a cleaning device using NMP as a metal cleaning agent, and a regeneration device that removes contaminants from the NMP cleaning liquid after cleaning and circulates it to the cleaning device. A regenerating apparatus for a metal cleaning agent is described in which the filter medium provided in the apparatus is a granular filter medium that contains at least polypropylene and has floating properties with respect to NMP.

Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2008-163400) contains a cleaning liquid containing as a main component one or more selected from (1a) hydrocarbons, (1b) glycol ethers, and (1c) esters. A cleaning tank in which the object to be cleaned is immersed, and a rinse containing a rinse liquid mainly composed of one or more selected from (2a) hydrofluorocarbons and (2b) hydrofluoroethers, in which the object to be cleaned is immersed. A cleaning system is described comprising a liquid bath, a steam bath containing a rinse liquid and generating vapor of the rinse liquid, and a regeneration unit having a still.

JP-A-2006-313753 JP-A-07-076787 Japanese Patent Application Laid-Open No. 2008-163400

As the number of times of cleaning and rinsing the metal mask increases, the mixing ratio of the cleaning agent in the rinsing bath also increases. As a result, the rinsing tank is contaminated with the cleaning agent, and the rinsing liquid needs to be replaced periodically. However, since the fluorinated liquid used as the rinse liquid is also an expensive solvent, generally distillation means are used to recover the fluorinated liquid from the contaminated rinse liquid for reuse. However, since the amount of fluorinated liquid that can be recovered by such distillation means is extremely small, most of the fluorinated liquid is currently disposed of.

The present disclosure provides a method for regenerating a fluorinated liquid that is highly efficient in regenerating a fluorinated liquid mixed with a cleaning agent, and a regenerating apparatus using the method.

According to one embodiment of the present disclosure, the step of contacting a fluorinated liquid mixed with a detergent with water such that the concentration of the detergent in an overlying aqueous phase is no more than about 80% by weight; After the mixed liquid is separated into two liquids, an upper aqueous phase and a lower fluorinated liquid-containing phase, the upper liquid is removed and the lower liquid is collected. A method of regenerating a fluorinated liquid, wherein the cleaning agent is an aprotic polar solvent that dissolves in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof. A method is provided.

According to another embodiment of the present disclosure, there is provided a method of using the fluorinated liquid regenerated using the method for regenerating the fluorinated liquid described above as a rinse liquid for members used in an organic EL display manufacturing apparatus. be done.

According to yet another embodiment of the present disclosure, means for contacting the fluorinated liquid mixed with the detergent with water such that the concentration of the detergent in the overlying aqueous phase is no more than about 80% by weight; a means for removing the upper layer liquid and collecting the lower layer liquid after the mixed liquid after contact with water is separated into two liquids, an upper aqueous phase and a lower fluorinated liquid-containing phase; wherein the cleaning agent is an aprotic polar solvent that dissolves in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof; A fluorinated liquid regeneration device is provided.

The method and apparatus for regenerating a fluorinated liquid of the present disclosure can improve the efficiency of regenerating a fluorinated liquid mixed with a cleaning agent.

Additionally, in some examples of the present disclosure, additional distillation and heating steps can be eliminated by providing sufficient separation. Since these examples can be completed at ambient temperature, they are more energy efficient and require no additional manipulations.

The above description should not be considered a disclosure of all implementations of the disclosure and all advantages associated with the disclosure.

1 is a graph of detergent concentration in water versus purity and yield for various fluorinated liquids using NMP as the detergent and utilizing a method for regenerating a fluorinated liquid according to one embodiment of the present disclosure; FIG. 3 illustrates the relationship between the amount of fluorinated liquid waste after regeneration based on a method of regenerating a fluorinated liquid using distillation only and a method of regenerating a fluorinated liquid according to one embodiment of the present disclosure.

In the method for regenerating a fluorinated liquid according to the first embodiment of the present disclosure, water is added to a fluorinated liquid mixed with a cleaning agent so that the concentration of the cleaning agent in the upper aqueous phase does not exceed about 80% by mass. After the step of contacting and contacting with water, the mixed liquid is separated into two liquids, an upper aqueous phase and a lower fluorinated liquid-containing phase, after which the upper liquid is removed and the lower liquid is collected. wherein the cleaning agent is an aprotic polar solvent soluble in a fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof. The regeneration method of the present disclosure regenerates a high-purity fluorinated liquid with a high output (yield) only by bringing a predetermined amount of water into contact with a mixed system containing a specific cleaning agent and a specific fluorinated liquid. can be done.

The aprotic polar solvent in the method for regenerating a fluorinated liquid in the first embodiment may be a cyclic amide-based solvent, an amine-based solvent, a glycol ether-based solvent, acetone, dimethylsulfoxide, dimethylformamide, or a mixed solvent thereof. good. A combination with such an aprotic polar solvent can further improve the regeneration efficiency of the fluorinated liquid. Above all, when the aprotic polar solvent in the method for regenerating a fluorinated liquid in the first embodiment is a cyclic amide-based solvent, the regeneration efficiency of the fluorinated liquid can be further improved. Here, the regeneration efficiency is determined from the purity and output of the regenerated fluorinated liquid, and when the fluorinated liquid can be regenerated with high purity and high output, the regeneration efficiency is excellent. .

The method for regenerating a fluorinated liquid in the first embodiment can achieve a purity of about 95% or higher for the fluorinated liquid in the collected underlying liquid.

The method for regenerating a fluorinated liquid in the first embodiment can further comprise a step of distilling the lower layer liquid following the step of collecting the lower layer liquid. Higher purity fluorinated liquids can be regenerated by further applying a distillation step.

In the method for regenerating a fluorinated liquid in the first embodiment, when a distillation process is employed, the purity of the fluorinated liquid in the liquid collected by distillation can be made about 99.0% or higher.

The method of using the rinsing liquid for the members used in the organic EL display manufacturing apparatus according to the second embodiment of the present disclosure is the fluorinated liquid regenerated using the method for regenerating the fluorinated liquid according to the first embodiment. can be used. Examples of the member include a metal mask and an anti-adhesion plate. The method for regenerating a fluorinated liquid in the first embodiment can significantly reduce the amount of fluorinated liquid to be discarded compared to the conventional regeneration method that uses only distillation. The method of the second embodiment using the fluorinated liquid can further reduce the manufacturing cost of the organic EL display.

In the fluorinated liquid regeneration apparatus according to the third embodiment of the present disclosure, the fluorinated liquid mixed with the cleaning agent is brought into contact with water so that the concentration of the cleaning agent in the upper aqueous phase does not exceed about 80% by mass. After the mixed liquid after contact with water is separated into two liquids, an aqueous phase located in the upper layer and a phase containing the fluorinated liquid located in the lower layer, the upper layer liquid is removed and the lower layer liquid is collected. wherein the cleaning agent is an aprotic polar solvent soluble in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof. The regenerator of the present disclosure is capable of regenerating high purity fluorinated liquids with high output (yield) for mixed systems containing specific cleaning agents and specific fluorinated liquids.

The fluorinated liquid regeneration apparatus in the third embodiment of the present disclosure may further comprise means for distilling the underlying liquid subsequent to the means for collecting the underlying liquid. Higher purity fluorinated liquids can be regenerated by further applying a distillation step.

The present disclosure is described in more detail below for the purpose of illustrating representative embodiments of the present disclosure, but the present disclosure is not limited to these embodiments.

《Method for regenerating fluorinated liquid》
A method for regenerating a fluorinated liquid according to an embodiment of the present disclosure includes contacting a fluorinated liquid mixed with a detergent with water such that the concentration of the detergent in the upper aqueous phase does not exceed about 80% by mass. step (hereinafter sometimes referred to as "water contacting step"), and after the mixed liquid after contacting with water is separated into two liquids, an aqueous phase located in the upper layer and a phase containing the fluorinated liquid located in the lower layer, and a step of removing the liquid in the upper layer and collecting the liquid in the lower layer (hereinafter sometimes referred to as a “separation/collection step”). The protic polar solvent and fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or mixtures thereof.

<Washing soap>
The cleaning agent that can be mixed in the method for regenerating a fluorinated liquid of the present disclosure is a cleaning agent that is used when cleaning various members, for example, cleaning various members such as metal masks and anti-adhesion plates in organic EL display manufacturing equipment. cleaning agents that are sometimes used. Such a cleaning agent may be any aprotic polar solvent that dissolves in the fluorinated liquid, and is not limited to the following, for example, cyclic amide solvents, amine solvents, glycol ether solvents, Examples include solvents such as acetone, dimethylsulfoxide, dimethylformamide, and mixed solvents thereof. From the viewpoint of cleaning the metal mask or the anti-adhesion plate, it is preferable to use a cyclic amide solvent. Solvents called -alkyl-pyrrolidone solvents or γ-lactam solvents are more preferably used. Aprotic polar solvents can be used alone or in combination of two or more. With the cleaning agent described above, the fluorinated liquid can be efficiently regenerated by the regeneration method of the present disclosure. In addition to the above cleaning agents, the cleaning agent may contain other cleaning agents as long as they do not hinder the regeneration efficiency of the fluorinated liquid. preferably not.

From the viewpoint of application of the distillation process described below, etc., the boiling point of the cleaning agent is preferably about 55° C. or higher, about 100° C. or higher, about 150° C. or higher, about 200° C. or higher, or about 250° C. or higher.

<Fluorinated liquid>
Examples of fluorinated liquids that can be regenerated by the method for regenerating fluorinated liquids of the present disclosure include hydrofluoroethers (hereinafter sometimes abbreviated as "HFE") and hydrofluoroolefins (hereinafter abbreviated as "HFO"). ), or a mixture thereof. In addition to the above fluorinated liquids, the fluorinated liquid may contain other fluorinated liquids (for example, hydrochlorofluorocarbons, hydrofluorocarbons, etc.) within a range that does not impair the regeneration efficiency. From a point of view, it is preferred that no other fluorinated liquids are included.

From the viewpoint of application of the distillation process described below, etc., the boiling point of the fluorinated liquid is about 30° C. or higher, about 55° C. or higher, about 60° C. or higher, or about 75° C. or higher, about 150° C. or lower, or about 100° C. or lower. , or about 80° C. or less.

(hydrofluoroether)
Among the above fluorinated liquids, hydrofluoroether is preferably used from the viewpoint of regeneration efficiency and the like. A hydrofluoroether is a compound containing an etheric oxygen atom between the carbon atoms of a hydrofluorocarbon. The number of etheric oxygen atoms contained in one molecule of the hydrofluoroether may be one, or two or more. 1 or 2 is preferable, and 1 is more preferable, from the viewpoint of the boiling point that is easy to use as a solvent, the stability, and the like. The molecular structure of the hydrofluoroether may be chain-shaped, and may be linear or branched, but linear is preferred from the viewpoint of regeneration efficiency and the like. _{Hydrofluoroethers include ,} but _{are not limited} to _{, C4F9OCH3 , C4F9OCH2CH3 , C5F11OCH3 , C5F11OCH2CH3 , C6F13 OCH3 , C6F13OCH2CH3 , C7F15OCH3 , C7F15OCH2CH3 , C8F17OCH3 , C8F17OCH2CH3 , C9F19OCH3 _ _ _ _ _ _ _ _ _ , C9F19OCH2CH3 , C10F21OCH3 , C10F21OCH2CH3 ; CF3CH2OCF2CF2H , CF3CHFOCH2CF3 , _ _ _ _ _ _ _ CF3CH2OCF2CFHCF3 , CHF2CF2CH2OCF2CF2H , C3F7OC3F6OCFHCF3 , CF3CF ( CF3 ) CF ( OCH3 ) CF2CF3 , CF _ _ 3CF ( CF3} )CF _{( OC2H5} ) _{CF2CF3 ,} CF2 _{( OCH2CF3} ) _{CF2H , CF2 ( OCH2CF3} ) _{CFHCF3 ,} CF2 _{( OCH2CF2CF2} H) Hydrofluoroethers such as _CF2H , _{CF2 ( OCH2CF2CF2H} ) _{CFHCF3 ,} and the like. Among them, the use of a segregated hydrofluoroether is a particularly preferable fluorinated liquid because it can achieve a high purity of about 97% or more, about 98% or more, or about 99% or more just by contacting it with water. be. Among them _, a particularly _{preferred segregated hydrofluoroether} is _{C4F9OCH3 or C4F9OCH2CH3} . Here, the term “seggregate type” means a structure in which one side is fully fluorinated and the other side is composed of carbon and hydrogen with an ether bond interposed therebetween. These hydrofluoroethers can be used alone or in combination of two or more.

(hydrofluoroolefin)
By hydrofluoroolefin is intended a compound in which one or more hydrogen atoms of an olefin have been replaced with fluorine atoms. The number of fluorine atoms in the hydrofluoroolefin is not particularly limited, but may be 1 or more or 2 or more and 10 or less or 6 or less. Hydrofluoroolefins may be either E-type (trans-type) or Z-type (cis-type). The hydrofluoroolefin may be a hydrochlorofluoroolefin (HCFO). A hydrochlorofluoroolefin is a compound in which one or more hydrogen atoms of an olefin are substituted with fluorine atoms and one or more other hydrogen atoms of the olefin are substituted with chlorine atoms. intended to The number of chlorine atoms in the hydrochlorofluoroolefin is not particularly limited, but can be 1 or more, 5 or less, or 3 or less. Hydrofluoroolefins having no chlorine atom include, for example, CF ₃ -CH=CH ₂ , CF ₃ -CF=CH ₂ , CHF ₂ -CH=CHF, CHF ₂ -CF=CH ₂ , CH ₂ F-CH= CF2, CH2F-CF ₌ CHF, _{CH3 -} CF=CF2, _{CF3 -} CH=CH- _CF3 , _CF3 -CH=CF- _CH3 , _CF3 -CF=CH- _CH3 , CF ₃ -CH=CH _- CH2F, CHF2 _- CF=CF- _CH3 , CHF2 _- CF=CH _- CH2F, CHF2 _- CH=CF _- CH2F, CHF2 _- CH=CH-CHF ₂ , CH2F-CF=CF-CH2F, CH2F-CH=CH _{- CF3} , CH2F _- CF=CH _{- CHF2} , _{CF3 - CH2 -} CF= _CH2 , CF3- CHF-CH= _CH2 , _CF3 - _CH2 -CH=CHF, CHF2-CF2-CH= _CH2 , CHF2 _- CHF _- CF= _CH2 , CHF2 _- CHF _- CH ₌ CHF, CH2F -CF2 _- CF= _CH2 , CH2F _- CF2 _- CH ₌ CHF, CH2F-CHF-CF=CHF, CH2F-CHF-CF=CF2, _{CH2F - CH2 -} CF= CF ₂ , CH ₃ -CF ₂ -CF=CHF, CH ₃ -CF ₂ -CH=CF ₂ and the like. Examples of hydrofluoroolefins having chlorine atoms (that is, 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 , CF ₃ -CCl=CH ₂ and the like. A particularly preferred hydrofluoroolefin having chlorine atoms is CF ₃ —CH═CHCl. Hydrofluoroolefins (here, hydrochlorofluoroolefins are also included) can be used alone or in combination of two or more.

<water>
Any water can be used in the method of regenerating a fluorinated liquid of the present disclosure, including, but not limited to, tap water, distilled water, deionized water, and the like.

<Water contact process>
The method for regenerating a fluorinated liquid of the present disclosure includes a step of contacting a fluorinated liquid mixed with a detergent with water so that the concentration of the detergent in the upper aqueous phase does not exceed about 80% by mass (water contact process). In the water contacting step, the concentration of the cleaning agent in the upper aqueous phase can be set to a range of not more than about 75% by mass, or a range of not more than about 70% by mass, from the viewpoint of regeneration efficiency. The lower limit of the concentration of the cleaning agent is not particularly limited, but may be, for example, a range of about 10% by mass or less, a range of about 15% by mass or less, or a range of about 20% by mass or less. be able to. Here, the concentration of the detergent in the aqueous phase located in the upper layer can be measured, for example, by extracting the detergent component from the mixed liquid in the upper layer and analyzing it with a gas chromatography and a trace moisture analyzer. can.

The method of bringing water into contact with a fluorinated liquid mixed with a detergent is not limited to the following, but for example, the following methods (1) to (7) are employed alone or in combination of two or more. It is also possible to combine some of the methods (1) to (7) as appropriate. For example, for the method (1) or (2), physical stirring methods using vibration, stirrers, etc., stirring methods using air, ultrasonic waves, etc. described in (3), (6) or (7) You may apply the stirring method etc. which use.

(1) A method of dripping a fluorinated liquid mixed with a cleaning agent into a container containing water from above the container.
(2) A method of adding water to a container containing a fluorinated liquid mixed with a cleaning agent from below the container.
(3) A method of physically agitating a container containing a mixture of cleaning agent, fluorinated liquid and water, such as by vibrating or using a stirrer or impeller.
(4) In a container containing a mixture of cleaning agent, fluorinated liquid and water, under the condition that the mixture has already separated into two layers, the upper layer and the lower layer are connected with a pipe or the like, and the upper layer is removed by gravity or by a pump. etc. to move to the lower layer.
(5) In a container containing a mixture of cleaning agent, fluorinated liquid and water, under the condition that the mixture has already separated into two layers, the upper layer and the lower layer are connected with a pipe or the like, and the lower layer liquid is removed by gravity or by a pump. etc. to move to the upper layer.
(6) In a container containing a mixture of a cleaning agent, a fluorinated liquid and water, in a state where the mixture has already separated into two layers, a gas such as air is blown into the container to cause mixing. How to mix liquids
(7) A method of mixing a mixture of a cleaning agent, a fluorinated liquid and water by applying ultrasonic waves to the container in which the mixture has already separated into two layers. .

The temperature and time at which water is brought into contact with the fluorinated liquid mixed with the cleaning agent may vary depending on the required performance such as the purity of the fluorinated liquid to be regenerated, and therefore are not limited to the following, for example: The temperature can range from about 20°C or higher, about 23°C or higher, or about 25°C or higher, to about 40°C or lower, about 35°C or lower, or about 30°C or lower.

<Separation/collection process>
In the method for regenerating a fluorinated liquid of the present disclosure, the mixed liquid after contact with water is separated into two liquids, an upper aqueous phase and a lower fluorinated liquid-containing phase, and then the upper liquid is removed. , and a step of collecting the liquid in the lower layer. Separation into two liquids, the upper layer and the lower layer, can be achieved by passing through the step of allowing the liquid mixture containing the cleaning agent and the fluorinated liquid to stand after the above water contacting step.

The lower layer liquid may be collected, for example, directly from below the container containing the mixed liquid via a pipe or the like, or the upper layer liquid may be collected from above the container, and then the lower layer liquid may be collected. Alternatively, the sample may be collected by extending a tube or the like from the top of the container to near the bottom of the container and sucking.

The purity of the lower layer liquid collected at this stage may vary depending on the combination of detergent and fluorinated liquid, etc., but generally, the purity of the fluorinated liquid of about 90% or less before the water contacting step is reduced to about 95% or more. , about 96% or more, or about 97% or more.

<Optional process>
Optionally, the method for regenerating a fluorinated liquid of the present disclosure can be appropriately applied to a distillation process (e.g., a boiling distillation process, a vacuum distillation process, etc.), a cooling separation process, etc. alone or in combination of two or more. .

Among the optional steps, when the purity of the regenerated fluorinated liquid is desired to be higher, it is preferable to apply a distillation step to the lower layer liquid after collecting the lower layer liquid. The distillation temperature in the distillation step can be, for example, but not limited to, about 70° C. or higher, about 72° C. or higher, or about 75° C. or higher, and about 100° C. or lower, about 95° C. or lower, or about It can be 90° C. or less. The purity of the fluorinated liquid in the liquid collected by distillation may vary depending on the combination of detergent and fluorinated liquid, but is generally about 99.0% or higher, about 99.2% or higher, or about 99%. Purities of 0.4% and above can be achieved.

《Fluorinated liquid regeneration device》
The fluorinated liquid regenerating apparatus of one embodiment of the present disclosure includes a means ( Hereinafter, it may be referred to as "water contacting means"), and after the mixed liquid after contacting with water is separated into two liquids, an aqueous phase located in the upper layer and a phase containing the fluorinated liquid located in the lower layer, the upper layer means for removing the liquid and collecting the liquid in the lower layer (hereinafter sometimes referred to as "separation/collection means"), and the cleaning agent used here is an aprotic Polar solvents and fluorinated liquids are hydrofluoroethers, hydrofluoroolefins, or mixtures thereof. The cleaning agent, fluorinated liquid and water in the regeneration device may be the same as in the regeneration method described above.

<Means for contacting water>
As the water contacting means in the fluorinated liquid regenerating apparatus of the present disclosure, any means can be adopted as long as the water contacting step in the method for regenerating the fluorinated liquid described above can be applied. The material, capacity, shape, quantity, location, etc. of the container (sometimes referred to as a “tank”) that holds the liquid and mixed liquid containing water will depend on the intended use or operating environment of the device. It can be selected as appropriate.

<Separation/collection means>
As the separation/collection means in the fluorinated liquid regeneration apparatus of the present disclosure, any means can be adopted as long as the separation/collection steps in the above-described fluorinated liquid regeneration method can be applied. The material, capacity, shape, quantity, arrangement location, etc. of the container (sometimes referred to as a "tank") can be appropriately selected according to the intended use or use environment of the apparatus.

<Arbitrary means>
The apparatus for regenerating a fluorinated liquid of the present disclosure is any means that can apply any process such as a distillation process (e.g., a boiling distillation process, a vacuum distillation process, etc.), a cooling separation process, etc. in the above-described fluorinated liquid regeneration method. For example, the material, capacity, shape, quantity, location, etc. of the container for storing the lower layer liquid used in the distillation process will depend on the intended use or operating environment of the device. can be selected as appropriate. Various means, such as distillation means, cooling separation means, etc., can be applied to the fluorinated liquid regenerator either singly or in combination of two or more.

Among the optional means, when it is desired to further increase the purity of the regenerated fluorinated liquid, it is preferable to add distillation means for distilling the lower layer liquid after collecting the lower layer liquid. As the distillation means, for example, a conventional apparatus comprising a distillation pot for storing and heating the collected lower layer liquid and a cooler connected to the distillation pot for condensing and liquefying the vapor of the lower layer liquid can be used. can.

<<Usage of Recycled Fluorinated Liquid>>
The method and apparatus for regenerating a fluorinated liquid according to the present disclosure can be used online or offline, for example, in an organic EL display manufacturing process. When the method and apparatus for regenerating a fluorinated liquid of the present disclosure are used on-line, they need only be appropriately configured so that the regenerated fluorinated liquid can be reintroduced into the cleaning process. When using these offline, the regenerated fluorinated liquid can be reused in the cleaning process of the organic EL display manufacturing process, while other uses such as rinsing printed wiring boards can be used. It can also be reused for liquids.

The regenerated fluorinated liquid obtained from the fluorinated liquid regeneration method and apparatus of the present disclosure includes, but is not limited to, metals used in organic EL display manufacturing equipment and exposed to cleaning and rinsing operations. It can be used as a rinse for various members such as a mask and an anti-adhesion plate, as well as a rinse for various electronic parts, precision parts, metal parts, printed wiring boards, and the like. Here, the anti-adhesion plate is, for example, a member arranged inside the vacuum chamber of a vacuum deposition apparatus used in the manufacture of an organic EL display, and the vacuum chamber is contaminated from the three colors of RGB dyes that are evaporation sources. It is a member that can be removed and washed to prevent The use as a rinsing liquid is not limited to direct use as a liquid, for example, rinsing off the cleaning agent adhering to the object to be washed by immersing it, but evaporating the rinsing liquid to the surface of the object to be washed. It also includes indirect use such as rinsing off the cleaning agent or the like by adhering the evaporative gas.

<<Examples 1 to 22 and Comparative Examples 1 to 3>>
The following examples illustrate specific embodiments of the disclosure, but the disclosure is not limited thereto.

The products used in this example are shown in Table 1 below.

<Evaluation method>
The following evaluations were performed on the sampled liquid.

(Purity evaluation)
Purity of the regenerated fluorinated liquid was assessed by gas chromatography using Agilent Technologies 7890A. The measurement conditions for the gas chromatography method are as follows.
Column type: HP-1301
Column length: 60m
Column temperature: 260°C
Carrier gas type: helium gas Carrier gas flow rate: 205 mL/min Sample injection volume: 1 μL

(Evaluation of moisture content)
The amount of water in the lower layer liquid sampled after the water contact step was measured using a micro-moisture measuring device manufactured by Mitsubishi Chemical Corporation.

<Test 1: Purity of various fluorinated liquids after water contact step>
(Example 1)
100 g of NOVEC™ 7100 (fluorinated liquid) and 10 g of NMP (cleaning agent) were each added to the sample bottle and shaken for 30 minutes. 40 g of distilled water was added to this mixed solution, and the mixture was further shaken for 30 minutes. The resulting mixture was then transferred to a separatory funnel and allowed to stand until the mixture separated into two layers, an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of the fluorinated liquid NOVEC (trademark) 7100 in the lower layer liquid was measured. Table 2 shows the results. The aprotic polar solvent cleaning agent is more likely to migrate to the distilled water side than the fluorinated liquid. ) is 20% by mass, the concentration of the cleaning agent in the upper aqueous phase does not exceed 20% by mass.

(Example 2)
Purity was measured in the same manner as in Example 1, except that NOVEC™7200 was used instead of NOVEC™7100.

(Example 3)
Purity was determined in the same manner as in Example 1, except that NOVEC™ 7100 was replaced with 1233Z.

(Example 4)
Purity was measured in the same manner as in Example 1, except that Asahiklin (trademark) AE3000 was used instead of NOVEC (trademark) 7100.

(Example 5)
100 g of NOVEC™ 7100 (fluorinated liquid) and 5 g of NBP (cleaning agent) were each added to the sample bottle and shaken for 30 minutes. 10 g of distilled water was added to this mixed solution, and the mixture was further shaken for 30 minutes. The resulting mixture was then transferred to a separatory funnel and allowed to stand until the mixture separated into two layers, an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of the fluorinated liquid NOVEC (trademark) 7100 in the lower layer liquid was measured. Table 2 shows the results. In addition, since the concentration of the cleaning agent in water in the aspect of this embodiment is 33.3% by mass, the concentration of the cleaning agent in the aqueous phase positioned in the upper layer does not exceed 33.3% by mass.

(Example 6)
Purity was measured in the same manner as in Example 5, except that NOVEC™7200 was used instead of NOVEC™7100.

(Example 7)
Purity was determined in the same manner as in Example 5, except that NOVEC™ 7100 was replaced with 1233Z.

(Example 8)
Purity was measured in the same manner as in Example 5 except that Asahiklin (trademark) AE3000 was used instead of NOVEC (trademark) 7100.

(Example 9)
100 g of NOVEC™ 7100 (fluorinated liquid) and 10 g of TETRAGLYME (cleaner) were each added to the sample bottle and shaken for 30 minutes. 80 g of distilled water was added to this mixed solution, and the mixture was further shaken for 30 minutes. The resulting mixture was then transferred to a separatory funnel and allowed to stand until the mixture separated into two layers, an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of the fluorinated liquid NOVEC (trademark) 7100 in the lower layer liquid was measured. Table 2 shows the results. In addition, since the concentration of the detergent in water in the aspect of this example is 11.1% by mass, the concentration of the detergent in the aqueous phase positioned in the upper layer does not exceed 11.1% by mass.

(Example 10)
Purity was measured in the same manner as in Example 9, except that NOVEC™7200 was used instead of NOVEC™7100.

(Example 11)
Purity was measured in the same manner as in Example 9, except that Asahiklin (trademark) AE3000 was used instead of NOVEC (trademark) 7100.

(Example 12)
To the sample bottle, 100 g of NOVEC™ 7100 (fluorinated liquid) and 10 g of AC (cleaner) were each added and shaken for 30 minutes. 80 g of distilled water was added to this mixed solution, and the mixture was further shaken for 30 minutes. The resulting mixture was then transferred to a separatory funnel and allowed to stand until the mixture separated into two layers, an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of the fluorinated liquid NOVEC (trademark) 7100 in the lower layer liquid was measured. Table 2 shows the results. In addition, since the concentration of the detergent in water in the aspect of this example is 11.1% by mass, the concentration of the detergent in the aqueous phase positioned in the upper layer does not exceed 11.1% by mass.

(Example 13)
Purity was measured in the same manner as in Example 12, except that NOVEC™7200 was used instead of NOVEC™7100.

(Example 14)
100 g of 1233Z (fluorinated liquid) and 10 g of DMSO (detergent) were each added to the sample bottle and shaken for 30 minutes. 10 g of distilled water was added to this mixed solution, and the mixture was further shaken for 30 minutes. The resulting mixture was then transferred to a separatory funnel and allowed to stand until the mixture separated into two layers, an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was sampled, and the purity of 1233Z, which is a fluorinated liquid, in the lower layer liquid was measured. Table 2 shows the results. In addition, since the concentration of the detergent in water in the aspect of the present embodiment is 50% by mass, the concentration of the detergent in the aqueous phase positioned in the upper layer does not exceed 50% by mass.

(Example 15)
Purity was measured in the same manner as in Example 14, except that Asahiklin (trademark) AE3000 was used instead of 1233Z.

(Example 16)
To the sample bottle, 100 g of NOVEC™ 7100 (fluorinated liquid) and 10 g of DMF (detergent) were each added and shaken for 30 minutes. 10 g of distilled water was added to this mixed solution, and the mixture was further shaken for 30 minutes. The resulting mixture was then transferred to a separatory funnel and allowed to stand until the mixture separated into two layers, an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of the fluorinated liquid NOVEC (trademark) 7100 in the lower layer liquid was measured. Table 2 shows the results. In addition, since the concentration of the detergent in water in the aspect of the present embodiment is 50% by mass, the concentration of the detergent in the aqueous phase positioned in the upper layer does not exceed 50% by mass.

(Example 17)
Purity was measured in the same manner as in Example 16, except that NOVEC™7200 was used instead of NOVEC™7100.

(Example 18)
Purity was determined in the same manner as in Example 16, except that NOVEC™ 7100 was replaced with 1233Z.

(Example 19)
100 g of Asahiklin™ AE3000 (fluorinated liquid) and 10 g of DMF (cleaning agent) were each added to the sample bottle and shaken for 30 minutes. 80 g of distilled water was added to this mixed solution, and the mixture was further shaken for 30 minutes. The resulting mixture was then transferred to a separatory funnel and allowed to stand until the mixture separated into two layers, an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, and the purity of Asahiklin (trademark) AE3000, which is a fluorinated liquid in the lower layer liquid, was measured. Table 2 shows the results. In addition, since the concentration of the detergent in water in the aspect of this example is 11.1% by mass, the concentration of the detergent in the aqueous phase positioned in the upper layer does not exceed 11.1% by mass.

<result>
As can be seen from the results in Table 2, it can be confirmed that the fluorinated liquid can be regenerated to a purity of about 95% or more by simply contacting it with water using the method for regenerating the fluorinated liquid of the present disclosure. rice field.

<Test 2: Condition of regeneration of various fluorinated liquids after contact with water>
(Example 20)
The amount of distilled water added was 2.5 g (concentration of detergent in water: 80.0% by mass), 5 g (concentration of detergent in water: 66.7% by mass), 10 g (concentration of detergent in water: 50.0%). % by mass), 20 g (concentration of detergent in water: 33.3% by mass), 40 g (concentration of detergent in water: 20.0% by mass), 60 g (concentration of detergent in water: 14.3% by mass), 80 g Purity (%) was measured in the same manner as in Example 1, except that the water contacting step was performed with (concentration of detergent in water: 11.1% by mass), and the yield of the sampled lower layer liquid. (g) was also measured. FIG. 1 shows a graph based on the value obtained by multiplying the measured purity and production amount (hereinafter sometimes referred to as "regeneration value") and the detergent concentration (% by mass) in water. Now, referring to FIG. 1, it is intended that the higher the regeneration value, the better the regeneration of the fluorinated liquid.

(Example 21)
Purity and yield were measured in the same manner as in Example 20 except that NOVEC™ 7200 was used instead of NOVEC™ 7100, and a graph based on these results is shown in FIG.

(Comparative example 1)
Purity and yield were measured in the same manner as in Example 20, except that VERTREL™ XF was used instead of NOVEC™ 7100, and a graph based on these results is shown in FIG.

(Comparative example 2)
Purity and yield were measured in the same manner as in Example 20 except that Asahiklin (trademark) AK-225 was used instead of NOVEC (trademark) 7100, and a graph based on these results is shown in FIG. .

<result>
As is clear from the results in FIG. 1, the embodiments of Examples 20 and 21, which correspond to the regeneration method of the present disclosure, are better than the embodiments of Comparative Examples 1 and 2 using hydrofluorocarbons and hydrochlorofluorocarbons. The higher regeneration value confirms that the regeneration by the water contact step works significantly for fluorinated liquids other than hydrofluorocarbons and hydrochlorofluorocarbons. In particular, with respect to the embodiments of Examples 20 and 21, it was confirmed that the regeneration value was superior when the detergent concentration in water was about 30.0% by mass to about 60.0% by mass. This corresponds to the case where water is brought into contact so that the concentration of the cleaning agent in the aqueous phase located in the upper layer is generally not less than about 30.0% by mass and not more than about 60.0% by mass. do.

<Test 3: Combination of water contact step and distillation step>
(Example 22)
100 g of Asahiklin™ AE3000 (HFE-347pc-f) and 10 g of NMP were each added to the sample bottle and shaken for 30 minutes. Add 40 g of distilled water to this mixed solution, shake further for 30 minutes, and mix Asahiklin (trademark) AE3000 (HFE-347pc-f), water and NMP in a ratio of 100: 40: 10 A liquid was prepared. The mixture was then transferred to a separatory funnel and allowed to stand until the mixture separated into two layers, an upper layer and a lower layer. The lower layer liquid of the liquid separated into two layers was collected, transferred into a distillation flask of a general distillation apparatus used at the experimental level, and distillation was started at a temperature of about 80°C. When the temperature of the thermometer installed near the entrance of the Liebig cooler dropped, the timing was set to end, and the regenerated fluorinated liquid was separated from the residual liquid to be discarded. A series of flows and their results are shown on the right side of FIG. It should be noted that the fact that the sum of the amount of the regenerated fluorinated liquid and the amount of the fluorinated liquid contained in the residual liquid was less than 100 g is considered to be an experimental error.

(Comparative Example 3)
80 g of Asahiklin™ AE3000 (HFE-347pc-f) and 20 g of NMP were each added to the sample bottle and shaken for 30 minutes. This mixed liquid was distilled using the same distillation apparatus and under the same distillation conditions as in Example 22 to separate the regenerated fluorinated liquid and the residual liquid to be discarded. A series of flows and their results are shown on the left side of FIG.

<result>
A calibration curve shows that when a mixture containing a fluorinated liquid and a detergent is distilled at a temperature of about 80° C., the residue contains about 30% detergent and about 70% fluorinated liquid. etc., can be used to derive In the case of Comparative Example 3, which is a conventional method of regenerating a fluorinated liquid using distillation only, distillation at a temperature of about 80° C. yields 33.3 g of fluorinated liquid ( Only HFE-347pc-f) could be regenerated and the remaining 46.7 g of fluorinated liquid had to be discarded as it could not be separated from the cleaning agent (NMP). That is, the amount of fluorinated liquid that had to be discarded was as much as 58.4% of the fluorinated liquid contained in the mixed liquid before regeneration. On the other hand, in the case of Example 22, which is the method for regenerating a fluorinated liquid of the present disclosure that employs a distillation step, the lower layer liquid collected through the water contacting step and the separation/collecting step contains most of the detergent. Since it has already been removed, distillation at a temperature of about 80° C. can recycle 92.6 g of fluorinated liquid, as shown on the right side of FIG. I was able to keep it to a very small amount. That is, the amount of fluorinated liquid that must be discarded (this amount includes the amount of fluorinated liquid in the residue of 5.8 g plus an error of 1.6 g) is included in the mixed liquid before regeneration. was only 7.4% of the fluorinated liquids used. Therefore, it can be confirmed that the disclosed fluorinated liquid regeneration method employing a distillation process reduces the amount of fluorinated liquid to be disposed of by as much as 87.3% compared to the conventional regeneration method using distillation alone. rice field.

It will be apparent to those skilled in the art that various modifications may be made to the above-described embodiments and examples without departing from the underlying principles of the invention. In addition, it will be apparent to those skilled in the art that various modifications and alterations of this invention can be made without departing from its spirit and scope.
Some of the embodiments of the present disclosure are described in [Item 1]-[Item 9] below.
[Item 1]
a step of contacting the fluorinated liquid mixed with the detergent with water such that the concentration of the detergent in the upper aqueous phase does not exceed 80 mass %;
a step of separating the mixed liquid after contact with water into two liquids, an upper aqueous phase and a lower fluorinated liquid-containing phase, removing the upper liquid and collecting the lower liquid; A method of regenerating a fluorinated liquid comprising:
A regeneration method, wherein the cleaning agent is an aprotic polar solvent that dissolves in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof.
[Item 2]
The regeneration method according to item 1, wherein the aprotic polar solvent is a cyclic amide solvent, an amine solvent, a glycol ether solvent, acetone, dimethylsulfoxide, dimethylformamide, or a mixed solvent thereof.
[Item 3]
3. A regeneration method according to item 1 or 2, wherein the purity of the fluorinated liquid in the collected lower layer liquid is 95% or higher.
[Item 4]
3. The regeneration method according to item 1 or 2, further comprising a step of distilling the lower layer liquid following the step of collecting the lower layer liquid.
[Item 5]
5. A regeneration method according to item 4, wherein the purity of the fluorinated liquid in the liquid collected by distillation is 99.0% or higher.
[Item 6]
A method of using the fluorinated liquid regenerated by the regeneration method according to any one of items 1 to 5 as a rinsing liquid for members used in an organic EL display manufacturing apparatus.
[Item 7]
A method according to item 6, wherein the member is a metal mask or an anti-adhesion plate.
[Item 8]
means for bringing water into contact with the fluorinated liquid mixed with the detergent so that the concentration of the detergent in the upper aqueous phase does not exceed 80 mass %;
a means for removing the upper layer liquid and collecting the lower layer liquid after the mixed liquid after contact with water is separated into two liquids, namely, an upper aqueous phase and a lower fluorinated liquid-containing phase; A fluorinated liquid regeneration device comprising:
A fluorinated liquid regenerator, wherein said cleaning agent is an aprotic polar solvent soluble in said fluorinated liquid, and said fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof.
[Item 9]
9. A fluorinated liquid regeneration apparatus according to item 8, further comprising means for distilling said underlayer liquid subsequent to said means for collecting said underlayer liquid.

Claims (9)

contacting the fluorinated liquid mixed with the detergent with water such that the concentration of the detergent in the upper aqueous phase is not more than 10% by weight and not more than 80% by weight;
a step of separating the mixed liquid after contact with water into two liquids, an upper aqueous phase and a lower fluorinated liquid-containing phase, removing the upper liquid and collecting the lower liquid; A method of regenerating a fluorinated liquid comprising:
A regeneration method, wherein the cleaning agent is an aprotic polar solvent that dissolves in the fluorinated liquid, and the fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof. 2. The regeneration method according to claim 1, wherein the aprotic polar solvent is a cyclic amide solvent, amine solvent, glycol ether solvent, acetone, dimethylsulfoxide, dimethylformamide, or a mixed solvent thereof. 3. The regeneration method according to claim 1 or 2, wherein the purity of the fluorinated liquid in the collected lower layer liquid is 95% or higher. 3. The regeneration method according to claim 1, further comprising a step of distilling the lower layer liquid following the step of collecting the lower layer liquid. 5. The regeneration method according to claim 4, wherein the purity of the fluorinated liquid in the liquid collected by distillation is 99.0% or higher. A method of using the fluorinated liquid regenerated by the regeneration method according to any one of claims 1 to 5 as a rinsing liquid for members used in an organic EL display manufacturing apparatus. 7. The method according to claim 6, wherein the member is a metal mask or an anti-adhesion plate. means for contacting the fluorinated liquid mixed with the cleaning agent with water such that the concentration of the cleaning agent in the upper aqueous phase is not more than 10% by mass and not more than 80% by mass;
a means for removing the upper layer liquid and collecting the lower layer liquid after the mixed liquid after contact with water is separated into two liquids, an upper aqueous phase and a lower fluorinated liquid-containing phase; A fluorinated liquid regeneration device comprising:
A fluorinated liquid regenerator, wherein said cleaning agent is an aprotic polar solvent soluble in said fluorinated liquid, and said fluorinated liquid is a hydrofluoroether, a hydrofluoroolefin, or a mixture thereof. 9. The fluorinated liquid regeneration apparatus of claim 8, further comprising means for distilling said underlayer liquid subsequent to said means for collecting said underlayer liquid.

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