Apparatus for producing the target compound, method for producing the target compound, and method for producing ammonium salts

Abstract

This invention provides a manufacturing method that enables the production of a high-purity target compound with high yield. [Solution] A countercurrent multi-stage washing and extraction unit (50) having multiple extraction units (10, 20), wherein in at least one extraction unit (10, 20), the mixing containers (11, 21) are located above the separatory tanks (12, 22), and the first supply pipes (13, 23) are provided at an inclination downward relative to the mixing containers (11, 21), and the mixed liquid that has moved from the mixing containers (11, 21) into the first supply pipes (13, 23) is flowed into the separatory tanks (12, 22) by gravity, thereby providing a manufacturing apparatus for a target compound.

Description

[Technical Field]

[0001] The present invention relates to an apparatus for producing a target compound, a method for producing a target compound, and a method for producing an ammonium salt. [Background technology]

[0002] Many ammonium compounds are known to be used as cation curing catalysts for cation curing components of epoxy resins and the like. A method for producing ammonium salts in high yield is known, which involves mixing a tertiary amine compound, ortho-methylbenzyl chloride, and an alkali metal salt of the anion constituting the ammonium salt in water at room temperature and reacting the mixture. (Patent Document 1) [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2017-52759 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, the method described in Patent Document 1 has several drawbacks, such as a decrease in yield and purity due to decomposition of the reaction product or contamination with impurities, which occurs because many post-reaction steps, such as recrystallization of the reactants, washing of the recovered crystals, washing with water and hexane, and drying, are performed after the reaction.

[0005] Furthermore, not limited to the ammonium salts mentioned above, in the production process of target compounds used in the manufacture of electronic components, for example, washing and extraction equipment may be used when washing and extracting an intermediate product-containing solution containing the intermediate product of the target compound with a solvent that is immiscible with the intermediate product-containing solution. In such washing and extraction equipment, malfunctions may occur due to the ingress of impurities produced as by-products during the formation of intermediate products into the pump. Preventing such malfunctions in washing and extraction equipment is an important issue in producing high-purity target compounds with high yields.

[0006] The object of the present invention is to provide an apparatus for producing a target compound, a method for producing a target compound, and a method for producing an ammonium salt, which can produce a high-purity target compound in high yield. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the inventors of the present invention have found that, in a method for producing ammonium salts, which includes a specific reaction step for obtaining an ammonium halide compound and a salt exchange step for exchanging the halide ions contained in the ammonium halide compound with specific ions in a solvent, high-purity ammonium salts can be produced in high yield by performing the reaction step to the salt exchange step using a continuous production facility. Based on this finding, the inventors have arrived at a method for producing ammonium salts according to one aspect of the present invention.

[0008] That is, a method for producing an ammonium salt according to one aspect of the present invention is a method for producing an ammonium salt represented by general formula (1), comprising a reaction step of reacting a tertiary amine with a (substituted) benzyl halide compound to obtain an ammonium halide compound, and a step of using the halide ions contained in the ammonium halide compound obtained in the reaction step as (C6F5)4B - SbF6 - PF6 - (CF3CF2)3PF3 - , (C6F5)4Ga -It has a salt exchange step of performing salt exchange with at least one ion selected from the group consisting of trifluoromethanesulfonate anion and p-toluenesulfonate anion in a solvent, and is a method for producing an ammonium salt in which from the reaction step to the salt exchange step is carried out using a continuous production facility.

[0009] [Chemical formula]

[0010] [In general formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, R 3 represents an aryl group having 6 to 12 carbon atoms which may have a substituent on the aromatic ring, R 4 represents any one of an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, N represents a nitrogen atom, X - is (C6F5)4B - , SbF6 - , PF6 - , (CF3CF2)3PF3 [[ID=二十九]] - , (C6F5)4Ga - , represents trifluoromethanesulfonate anion, or p-toluenesulfonate anion.] Further, as a result of intensive studies to solve the above problems, the inventor has adopted a countercurrent multi-stage type facility as a washing and extraction facility when washing and extracting an intermediate product of the target compound, and in at least one extraction section, the supply of the mixed solution from the mixing container that generates the mixed solution of the intermediate product-containing solution and the solvent to the separation tank that separates the mixed solution into two layers is carried out with a specific structure, thereby preventing the operation failure of the washing and extraction facility due to impurities by-produced during the production of the intermediate product. And based on this finding, the inventors have reached the production apparatus for the target compound and the production method for the target compound according to another aspect of the present invention.

[0011] That is, another embodiment of the present invention relates to a production apparatus for a target compound used in the manufacture of electronic components, comprising a countercurrent multi-stage washing and extraction unit that washes and extracts a target product containing at least one of the target compound and an intermediate product produced in a reaction for producing the target compound, with a solvent that is immiscible with the target product-containing solution, wherein the washing and extraction unit has a plurality of extraction units arranged continuously from the upstream side to the downstream side, and the plurality of extraction units use the target product-containing solution supplied from the preceding extraction unit and the subsequent The extraction unit includes at least one stage, which comprises a mixing container that generates a mixture of the solvent supplied from the stage extraction unit, a separatory tank that separates the mixture into a liquid phase containing the target product and a liquid phase of the solvent, and a first supply pipe that supplies the mixture in the mixing container to the separatory tank. In the at least one stage extraction unit, the mixing container is located above the separatory tank, and the first supply pipe is inclined downward relative to the mixing container, so that the mixture that has moved from the mixing container into the first supply pipe flows into the separatory tank by gravity.

[0012] Furthermore, a method for producing a target compound according to yet another aspect of the present invention is a method for producing a target compound used in the manufacture of electronic components, comprising a countercurrent multi-stage washing and extraction step in which a target product containing at least one of the target compound and an intermediate product produced in a reaction for producing the target compound is washed and extracted with a solvent that is immiscible with the target product-containing solution, the washing and extraction step having a plurality of extraction steps performed continuously from the upstream side to the downstream side, the plurality of extraction steps in which the target product-containing solution supplied from the previous extraction step is mixed in a mixing container The extraction process includes at least one step, comprising: a mixing step to generate a mixture of a solution and the solvent supplied from a subsequent extraction unit; a separation step to separate the mixture into a liquid phase containing the target product and a liquid phase of the solvent in a separatory tank; and a first supply step to supply the mixture in the mixing container to the separatory tank via a first supply pipe, wherein the mixing container is located above the separatory tank, and in the first supply step, the first supply pipe is inclined downward relative to the mixing container, and the mixture that has moved from the mixing container into the first supply pipe is allowed to flow into the separatory tank by gravity. [Effects of the Invention]

[0013] According to these embodiments of the present invention, a high-purity target compound or ammonium salt can be produced in high yield. [Brief explanation of the drawing]

[0014] [Figure 1] This figure shows a schematic configuration of a washing and extraction section provided in a production apparatus for a target compound according to one embodiment of the present invention. [Figure 2] This diagram shows the schematic configuration of an ammonium salt production apparatus shown in general formula (1). [Modes for carrying out the invention]

[0015] One embodiment of the present invention is described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the claims. Furthermore, embodiments or examples obtained by combining the technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Moreover, new technical features can be formed by combining the technical means disclosed in each embodiment. All academic and patent documents mentioned herein are incorporated herein by reference.

[0016] In this specification, unless otherwise specified, "A~B" representing a numerical range means "greater than or equal to A, and less than or equal to B." Furthermore, each drawing is provided for clarity when viewed in conjunction with the following explanation and is not necessarily drawn to a fixed scale.

[0017] [Equipment for manufacturing the target compound] An apparatus for producing a target compound according to one embodiment of the present invention is an apparatus for producing a target compound used in the manufacture of electronic components. The apparatus includes a countercurrent multi-stage washing and extraction unit that washes and extracts a target product-containing solution containing at least one of the target compound and intermediate products produced in the reaction for producing the target compound, with an immiscible solvent. The following description will use the washing and extraction of a target product-containing solution containing intermediate products as an example, but the apparatus for producing a target compound according to one embodiment of the present invention is not limited to this configuration. For example, the target product-containing solution may be a solution containing the target compound.

[0018] Figure 1 is a diagram showing the schematic configuration of a washing and extraction unit 50 provided in a production apparatus for a target compound according to one embodiment of the present invention.

[0019] The washing and extraction unit 50 has multiple extraction units arranged continuously from the upstream side to the downstream side. The number of extraction units is not particularly limited. As shown in Figure 1, in the multiple extraction units, any one extraction unit is designated as the a-th stage extraction unit 10, and the extraction unit located one stage downstream from the a-th stage is designated as the a+1-th stage extraction unit 20.

[0020] The extraction unit 10 comprises a mixing container 11, a separatory tank 12, a first supply pipe 13, and a recovery tank 14. Similarly, the extraction unit 20 comprises a mixing container 21, a separatory tank 22, a first supply pipe 23, and a recovery tank 24.

[0021] Mixing container 11 is a container that produces a mixture of the intermediate product-containing solution supplied from the preceding extraction unit (not shown) and the solvent supplied from the subsequent (a+1) extraction unit 20. Similarly, mixing container 21 is a container that produces a mixture of the intermediate product-containing solution supplied from the a-stage extraction unit 10 and the solvent supplied from the subsequent extraction unit (not shown). Mixing containers 11 and 21 can employ conventionally known configurations as long as they are capable of mixing the intermediate product-containing solution and the solvent. Mixing containers 11 and 21 can, for example, be configured to include a magnetic stirrer (MS).

[0022] Furthermore, the separatory tanks 12 and 22 are tanks that separate a mixture of the intermediate product-containing solution and the solvent into liquid phases 12a and 22a containing the intermediate product and liquid phases 12b and 22b containing the solvent, respectively.

[0023] The first supply pipe 13 is a pipe that supplies the mixed liquid in the mixing container 11 to the separatory tank 12. Branch pipes connecting to the first supply pipe 13 are provided on the side walls of both the mixing container 11 and the separatory tank 12 (not shown). Similarly, the first supply pipe 23 is a pipe that supplies the mixed liquid in the mixing container 21 to the separatory tank 22.

[0024] The recovery tank 14 is a tank for recovering the liquid phase 12b of the solvent in the separatory tank 12. The separatory tank 12 and the recovery tank 14 are connected by piping with an on / off valve (not shown). For this reason, a branch pipe for connecting to the piping with the on / off valve (not shown) is formed on the side wall of the separatory tank 12. Similarly, the recovery tank 24 is a tank for recovering the liquid phase 22b of the solvent in the separatory tank 22.

[0025] Furthermore, the washing and extraction unit 50 is provided with second supply pipes 31 and 32, and third supply pipes 41 and 42.

[0026] The second supply pipe 31 connects the mixing container 11 of the a-stage extraction unit 10 to the recovery tank 24 of the a+1-stage extraction unit 20. Branch pipes connecting to the second supply pipe 31 are formed on the side walls of both the mixing container 11 and the recovery tank 24. Similarly, the second supply pipe 32 connects the mixing container 21 of the a+1-stage extraction unit 20 to the recovery tank of an extraction unit (not shown) located one stage downstream from the extraction unit 20. Pumps are provided in both the second supply pipes 31 and 32. That is, the solvent in the recovery tank 24 of the a+1-stage extraction unit 20 is supplied to the mixing container 11 of the a-stage extraction unit 10 via the second supply pipe 31, driven by the pump. Similarly, the solvent in the recovery tank of the extraction unit (not shown) located one stage downstream from the extraction unit 20 is supplied to the mixing container 21 of the a+1 stage extraction unit 20 via the second supply pipe 32 by pump drive. With this configuration, the solvent used in the a+1 stage extraction unit 20 (downstream) can be reused in the a stage extraction unit 10, thereby reducing the amount of solvent required for washing and extraction.

[0027] The third supply pipe 41 connects the mixing container 21 of the a+1 stage extraction unit 20 to the separatory tank 12 of the a stage extraction unit 10. Branch pipes connecting to the third supply pipe 41 are formed on the side walls of both the mixing container 21 and the separatory tank 12. The third supply pipe 42 connects the mixing container of an extraction unit (not shown) located one stage downstream from the extraction unit 20 to the separatory tank 22 of the a+1 stage extraction unit 20.

[0028] In the separatory tank 12, the positions of the branch pipes connected to the piping to the recovery tank 14 and the branch pipe connected to the third supply pipe 41 are set so that the interface between the liquid phase 12a and the liquid phase 12b is located between these two branch pipes. In the separatory tank 22, the positions of the branch pipes connected to the piping to the recovery tank 24 and the branch pipe connected to the third supply pipe 42 are set in the same manner as in the separatory tank 12.

[0029] In the washing and extraction section 50 of the manufacturing apparatus according to this embodiment, the mixing container 11 is located above the separatory tank 12 in the extraction section 10. The first supply pipe 13 is provided at a downward inclination relative to the mixing container 11.

[0030] The extraction unit 10 is configured to allow the mixed liquid, which has moved from the mixing container 11 into the first supply pipe 13, to flow into the separatory tank 12 by gravity. The mixing container 11 is supplied with an intermediate product solution and a solvent, and a mixed liquid is continuously produced. When the mixed liquid reaches the position of the branch pipe connected to the first supply pipe 13 within the mixing container 11, the mixed liquid moves from the mixing container 11 to the separatory tank 12 by gravity through the branch pipe and the first supply pipe 13.

[0031] In this case, the extraction unit 10 of the washing and extraction unit 50 allows the mixed liquid that has moved from the mixing container 11 into the first supply pipe 13 to flow into the separatory tank 12 by gravity, thus eliminating the need for a pump to move the mixed liquid from the mixing container 11 to the separatory tank 12.

[0032] In the washing and extraction unit 50, the extraction unit 10 utilizes gravity, rather than a pump, to transfer the mixed liquid from the mixing container 11 to the separatory tank 12. Therefore, the manufacturing apparatus according to one embodiment of the present invention can prevent malfunctions of the manufacturing apparatus caused by deposits formed as by-products in the intermediate product formation reaction accumulating inside the pump. Thus, the manufacturing apparatus according to one embodiment of the present invention can produce a high-purity target compound in high yield.

[0033] Furthermore, the first supply pipe 13 is installed at a downward inclination relative to the mixing container 11. In other words, the first supply pipe 13 connects the mixing container 11 and the separatory tank 12 without bending along the way. As a result, after the mixed liquid reaches the position of the branch pipe connected to the first supply pipe 13 within the mixing container 11, the mixed liquid moves smoothly from the branch pipe through the first supply pipe 13.

[0034] As shown in Figure 1, in the extraction unit 20, the mixing container 21 is located above the separatory tank 22. The first supply pipe 23 is installed at a downward inclination relative to the mixing container 21. In the same mechanism as the extraction unit 10, the extraction unit 20 is configured to allow the mixed liquid that has moved from the mixing container 21 into the first supply pipe 23 to flow into the separatory tank 22 by gravity.

[0035] Furthermore, in the manufacturing apparatus according to one embodiment of the present invention, the separatory tank 12 of the a-stage extraction unit 10 is located above the mixing container 21 of the a+1-stage extraction unit 20. The washing extraction unit 50 is configured to supply the liquid phase 12a containing the intermediate product in the separatory tank 12 of the a-stage extraction unit 10 to the mixing container 21 of the a+1-stage extraction unit 20 by gravity via the third supply pipe 41. The mixed liquid that has moved via the first supply pipe 13 separates into liquid phase 12a and liquid phase 12b in the separatory tank 12. As the mixed liquid is continuously supplied to the separatory tank 12, the liquid level rises in the separatory tank 12 as the mixed liquid separates into liquid phase 12a and liquid phase 12b. Then, in the separatory tank 12, when the liquid level of the mixed liquid reaches the branch pipe connected to the third supply pipe 41, the liquid phase 12a is discharged from the branch pipe and moves to the mixing container 21 via the third supply pipe 41. At this time, if the on / off valve provided in the piping to the recovery tank 14 is closed, the amount of liquid phase 12a discharged is the same as the amount of mixed liquid supplied to the separatory tank 12.

[0036] In the liquid separator tank 12, the amount of liquid phase 12b discharged from the branch pipe connected to the piping to the recovery tank 14 is adjusted so that the liquid level of the mixed liquid becomes constant and liquid phase 12a is continuously discharged from the branch pipe connected to the third supply pipe 41. This adjustment is performed by an on / off valve (not shown) provided in the piping to the recovery tank 14.

[0037] As described above, the washing and extraction unit 50 supplies the liquid phase 12a containing the intermediate product in the separatory tank 12 of the a-stage extraction unit 10 to the mixing container 21 of the a+1-stage extraction unit 20 by gravity via the third supply pipe 41. Therefore, a pump is not required to move the liquid phase 12a from the separatory tank 12 to the mixing container 21. Thus, the number of pump parts can be reduced.

[0038] Although not shown in Figure 1, the separatory tank 22 of the extraction unit 20 is located above the mixing container of the extraction unit, which is located one stage downstream from the extraction unit 20. Then, by the same mechanism as the liquid phase 12a containing the intermediate product in the separatory tank 12, the liquid phase 22a containing the intermediate product in the separatory tank 22 is supplied by gravity to the mixing container of the extraction unit, which is located one stage downstream from the extraction unit 20, via the third supply pipe 42.

[0039] In the washing and extraction section 50, the mixed liquid moves from the upstream side to the downstream side, while the solvent moves from the downstream side to the upstream side. The mixed liquid is supplied to the mixing container of the first extraction section by pump drive. After the mixing container of the first extraction section, the mixed liquid moves alternately between the mixing container and the separatory tank by gravity. Meanwhile, the solvent moves from the downstream side to the upstream side by pump drive. Therefore, in order for the continuous washing and extraction operation in each extraction section to be automated without malfunction, it is essential to manage the remaining amount of mixed liquid in the mixing container and the amount of solvent supplied by the pump in each extraction section.

[0040] Therefore, in the washing and extraction unit 50, it is preferable that the pump P3 provided in the second supply pipe 31 is equipped with a solvent flow meter to monitor the flow rate of the solvent from the pump P3. Similarly, it is preferable that the pump P4 provided in the second supply pipe 32 is equipped with a solvent flow meter to monitor the flow rate of the solvent from the pump P4. Pumps equipped with flow meters are commercially available. In order to control the solvent flow rate more precisely, it is preferable that the solvent flow meter be provided separately from the flow meter provided in the pump.

[0041] Furthermore, it is preferable that each of the mixing containers 11 and 21 be equipped with a liquid level sensor to monitor the liquid level of the mixed liquid. This allows for management of the remaining amount of mixed liquid in the mixing containers 11 and 21.

[0042] In the washing and extraction unit 50, the pumps P3 and P4 are controlled by the control unit based on measurements from a solvent flow meter and a liquid level sensor.

[0043] In the washing and extraction section 50, there only needs to be at least one extraction section equipped with a first supply pipe that is inclined downward, and the number of stages in the extraction section can be appropriately set depending on the type of intermediate product of the target compound and the solvent.

[0044] Furthermore, the target compound for the manufacturing apparatus according to one embodiment of the present invention is not particularly limited, as long as it is a compound used in the manufacture of electronic components and requires liquid-liquid washing and extraction in the compound production process. Preferably, the target compound is a compound used in the manufacture of semiconductor components. Examples of such target compounds include a thermoacid generator consisting of an ammonium salt represented by general formula (1), described later; a triarylsulfonium salt type photoacid generator (PAG); and the like. The thermoacid generator is used in the manufacture of anisotropic conductive films (ACF) for displays and underlayer anti-reflective films (BARC) for semiconductor manufacturing. The photoacid generator (PAG) is used as a photoresist material in semiconductor manufacturing. Among these compounds, it is preferable that the target compound is an ammonium salt represented by general formula (1), and the intermediate product is a compound represented by general formula (1a).

[0045] [ka]

[0046] [In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and R 3 R represents an aryl group having 6 to 12 carbon atoms, which may have substituents on the aromatic ring. 4 represents one of the alkyl groups with 1 to 4 carbon atoms, alkenyl groups with 2 to 3 carbon atoms, or alkoxy groups with 1 to 4 carbon atoms, N represents a nitrogen atom, and X - (C6F5)4B - SbF6 - PF6 - (CF3CF2)3PF3 - , (C6F5)4Ga - This represents the trifluoromethanesulfonate anion or the p-toluenesulfonate anion.

[0047] [ka]

[0048] [In general formula (1a), R 1 ~R 3 This is R in general formula (1). 1 ~R 3 It is the same as, where N represents a nitrogen atom, and Xa - It is a halogen ion. Figure 2 shows a schematic configuration of the ammonium salt production apparatus 100 shown in general formula (1). As shown in Figure 2, the production apparatus 100 comprises a reaction section 60, a neutralization section 70, a washing and extraction section 50, a salt exchange section 80, and a solvent distillation section 90.

[0049] The reaction unit 60 reacts a (substituted) benzyl halide compound (sometimes referred to as substrate A) with a tertiary amine (sometimes referred to as substrate B) to produce an ammonium halide compound. The reaction unit 60 comprises a raw material container 61 for containing substrate A solution, a raw material container 62 for containing a mixed solution of substrate B and dimethyl sulfoxide (DMSO) (referred to as substrate B solution), a T-shaped micromixer 63, a heated water bath 64, and piping 65. Part of the piping 65 is immersed in the heated water bath 64. The (substituted) benzyl halide compound and the tertiary amine will be described in detail in the section on [Method for Producing Ammonium Salts] below.

[0050] In the reaction section 60, the substrate A solution in the raw material container 61 is continuously supplied to the T-shaped micromixer 63 by pump drive. Similarly, the substrate B solution in the raw material container 62 is continuously supplied to the T-shaped micromixer 63 by pump drive. Substrate A and substrate B react in the T-shaped micromixer 63 to produce an ammonium halide compound. The mixed reaction solution of substrate A and substrate B passes through the piping 65. This mixed reaction solution is then transferred to the neutralization section 70 while being heated by passing through the piping 65, which is immersed in a heated water bath 64.

[0051] The neutralization unit 70 neutralizes the solution containing the ammonium halide compound obtained from the reaction in the reaction unit 60 with a basic compound (preferably sodium bicarbonate). The neutralization unit comprises a container 71 for holding sodium bicarbonate solution, a mixing container 72, and piping 73. The solution of the ammonium halide compound produced in the reaction unit 60 flows continuously into the mixing container 72 via piping 65. The sodium bicarbonate solution in container 71 is also continuously supplied to the mixing container 72 by a pump. In the mixing container 72, the ammonium halide compound and the sodium bicarbonate solution are mixed to produce a neutralized solution containing the ammonium halide compound. The neutralized solution containing the ammonium halide compound contains the compound represented by general formula (1a).

[0052] The neutralized solution containing the ammonium halide compound produced in the neutralization section 70 is transferred to the washing and extraction section 50 via piping 73 by pump drive. The washing and extraction section 50 is equipped with a solvent storage tank 58 that contains chloroform (CHCl3) as the solvent for washing and extraction. In the manufacturing apparatus 100, the washing and extraction section 50 is equipped with four extraction sections. Of these four extraction sections, three have the same configuration as the extraction section equipped with the first supply pipe shown in Figure 1. The washing and extraction section 50 is equipped with the extraction section 10 shown in Figure 1 as the first extraction section and the extraction section 20 shown in Figure 1 as the second extraction section. In the washing and extraction section 50, the third extraction section is equipped with a mixing container 16, a separatory tank 17, a recovery tank 19, and an intermediate product recovery tank 25. Furthermore, the fourth stage extraction unit includes piping 51 and 52, a T-shaped micromixer 53, a liquid separator 54, recovery tanks 55 and 56, and a solvent storage tank 58.

[0053] In the washing and extraction section 50, the neutralization solution containing the ammonium halide compound is supplied to the mixing container 11 via the piping 73 by a pump. In the mixing container 11, a mixture of the neutralization solution (intermediate product-containing solution) containing the ammonium halide compound and the solvent is formed. The movement of the mixture and solvent from the mixing container 11 to the separatory tank 22 is the same as the configuration shown in Figure 1, so the explanation is omitted. The separatory tank 22 is located above the mixing container 16. The liquid phase 22a containing the neutralization solution containing the ammonium halide compound in the separatory tank 22 is supplied to the mixing container 16 by gravity. The mixing container 16 is located above the separatory tank 17. The first supply pipe 18 is also provided at a downward inclination relative to the mixing container 16. The mixture then moves from the mixing container 21 into the first supply pipe 23 and flows into the separatory tank 17 by gravity.

[0054] The mixture is separated in the separatory tank 17 into a liquid phase 17a containing a neutralization solution with an ammonium halide compound and a liquid phase 17b containing the solvent. The liquid phase 17a containing the neutralization solution with an ammonium halide compound is recovered in the intermediate product recovery tank 25 via the third supply pipe 43. The liquid phase 17b containing the solvent is recovered in the recovery tank 19. The solvent recovered in the recovery tank 19 is supplied to the mixing container 21 via the second supply pipe 32 by pump drive.

[0055] The neutralization solution containing the ammonium halide compound in the intermediate product recovery tank 25 is pumped through piping 51 and supplied to the T-shaped micromixer 53. The solvent in the solvent containment tank 58 is pumped through piping 52 and supplied to the T-shaped micromixer 53. In the T-shaped micromixer 53, a mixture of the neutralization solution containing the ammonium halide compound and the solvent is produced and supplied to the separatory tank 54. In the separatory tank 54, the mixture is separated into a liquid phase 54a containing the neutralization solution containing the ammonium halide compound and a liquid phase 54b containing the solvent. The liquid phase 54a containing the neutralization solution containing the ammonium halide compound is the final washing extract and is recovered in the recovery tank 56. The liquid phase 54b containing the solvent is recovered in the recovery tank 55. The solvent recovered in the recovery tank 55 is pumped through the second supply pipe 33 and supplied to the mixing container 16.

[0056] The neutralized solution containing ammonium halide compounds recovered in the recovery tank 56 is transferred to the salt exchange section 80 via piping 57 by pump drive. The salt exchange section 80 removes the halide ions contained in the ammonium halide compounds using (C6F5)4B - SbF6 - PF6 - (CF3CF2)3PF3 - , (C6F5)4Ga - The salt is converted to at least one ion selected from the group consisting of trifluoromethanesulfonate anion and p-toluenesulfonate anion. The salt exchange unit 80 comprises a salt conversion compound container 81 for containing the salt conversion compound, a reaction vessel 82, a separatory tank 83, and recovery tanks 84 and 85. The salt conversion compound container 81 contains (C6F5)4B - SbF6 - PF6 - (CF3CF2)3PF3 - , (C6F5)4Ga - The tank contains a solution of an alkali metal salt of at least one ion selected from the group consisting of trifluoromethanesulfonate anion and p-toluenesulfonate anion. The separatory tank 83 and the recovery tank 84 are connected by piping having an on / off valve (not shown).

[0057] The neutralization solution containing the ammonium halide compound is supplied to the reaction vessel 82 via piping 57 by pump drive. The alkali metal salt solution in the salt conversion compound container 81 is also supplied to the reaction vessel 82 by pump drive. In the reaction vessel 82, the salt conversion reaction between the ammonium halide compound and the alkali metal salt takes place. The reaction solution in the reaction vessel 82 is supplied to the separatory tank 83, where it is separated into a liquid phase 83a (aqueous phase) and a liquid phase 83b (organic phase) containing the final product, an ammonium salt represented by general formula (1). Liquid phase 83a is recovered in the recovery tank 85. Liquid phase 83b is recovered in the recovery tank 86.

[0058] The ammonium salt solution shown in general formula (1) in the recovery tank 86 is transferred to the solvent distillation section 90. The solvent distillation section 90 includes an evaporator 91, a crystallization filtration tank 92, and a vacuum dryer 93. In the solvent distillation section 90, the ammonium salt solution is transferred to the evaporator 91 and the solvent is recovered. The ammonium salt solution from which the solvent has been recovered is then transferred to the crystallization filtration tank 92. In the crystallization filtration tank 92, ammonium salt crystals are precipitated and filtered by adding deionized water while stirring the ammonium salt solution. The ammonium salt crystal cake recovered by filtration in the crystallization filtration tank 92 is transferred to the vacuum dryer 93 and dried. Preferably, the manufacturing apparatus 100 includes a control unit in the solvent distillation section 90 that controls the solvent removal operation by the evaporator 91, the transfer operation from the evaporator 91 to the crystallization filtration tank 92, and the transfer operation from the crystallization filtration tank 92 to the vacuum dryer 93. This makes it possible to automate various operations of the solvent removal unit 90.

[0059] When ammonium salts are produced by batch processing, the processing time required increases, and the ammonium salts decompose during the manufacturing process. Furthermore, because the processing solution is exposed to the outside during transfer between processing steps, impurities (especially metallic elements) can be introduced into the solution. Therefore, batch processing of ammonium salts presents problems such as reduced yield and decreased purity.

[0060] In the manufacturing apparatus 100, the reaction section 60, neutralization section 70, washing and extraction section 50, and salt exchange section 80 are connected to each other by piping. The movement of processing liquids such as reaction solution, neutralization solution, and washing and extraction solution in the reaction section 60, neutralization section 70, washing and extraction section 50, and salt exchange section 80 is also via piping. Therefore, the intermediate product generated in the reaction section 60 undergoes a continuous process of neutralization in the neutralization section 70, washing and extraction in the washing and extraction section 50, and salt exchange reaction in the salt exchange section 80. This continuous processing reduces the thermal history of each processing liquid and prevents the decomposition of the ammonium salt, thus enabling the production of high-purity ammonium salt in high yield.

[0061] Furthermore, the manufacturing apparatus 100 eliminates the need for manual transfer of the processing liquid in the reaction section 60, neutralization section 70, washing and extraction section 50, and salt exchange section 80. Therefore, the manufacturing apparatus 100 prevents the processing liquid from being exposed to the outside and prevents impurities from contaminating the processing liquid.

[0062] In the manufacturing apparatus 100, the piping through which the processing liquid passes in the reaction section 60, neutralization section 70, washing and extraction section 50, and salt exchange section 80 is preferably made of resin tubing such as fluororesin and silicone resin in order to prevent the contamination of the processing liquid with metal.

[0063] [Method for producing the target compound] A method for producing a target compound according to one embodiment of the present invention is a method for producing a target compound used in the manufacture of electronic components, and includes a countercurrent multi-stage washing and extraction step in which a target product containing a target product, which includes at least one of the target compound and an intermediate product produced in a reaction for producing the target compound, is washed and extracted with a solvent that is immiscible with the target product-containing solution. The washing and extraction step has a plurality of extraction steps that are performed continuously from the upstream side to the downstream side. The plurality of extraction steps include at least one extraction step which includes a mixing step in which a mixture is produced in a mixing container of the target product-containing solution supplied from the preceding extraction step and the solvent supplied from the subsequent extraction unit, a separation step in which the mixture is separated in a separatory tank into a liquid phase containing the target product and a liquid phase of the solvent, and a first supply step in which the mixture in the mixing container is supplied to the separatory tank via a first supply pipe, and the mixing container is located above the separatory tank. In the first supply step, the first supply pipe is installed at a downward inclination relative to the mixing container, and the mixture that has moved from the mixing container into the first supply pipe is allowed to flow into the separatory tank by gravity. According to the method for producing the target compound according to one embodiment of the present invention, in the extraction step, the mixture that has moved from the mixing container into the first supply pipe is allowed to flow into the separatory tank by gravity, so a pump is not required to move the mixture from the mixing container to the separatory tank. Therefore, according to the method for producing the target compound according to one embodiment of the present invention, it is possible to prevent malfunctions of the production apparatus caused by deposits formed as by-products in the reaction of the target product accumulating inside the pump. Thus, according to the method for producing the target compound according to one embodiment of the present invention, it is possible to produce the target compound in high purity with a high yield.

[0064] Furthermore, in a method for producing a target compound according to one embodiment of the present invention, it is preferable that the target compound is an ammonium salt represented by general formula (1), and the target product is the intermediate product, which is a compound represented by general formula (1a).

[0065] Various features of the method for producing the target compound according to one embodiment of the present invention can be appropriately applied to the contents of the section on [Equipment for producing the target compound].

[0066] [Method for producing ammonium salts] One embodiment of the present invention is a method for producing an ammonium salt represented by the following general formula (1).

[0067] [ka]

[0068] In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, 1-methylethyl group, and n-, iso-, or tert-butyl group).

[0069] R 3 R represents an aryl group having 6 to 12 carbon atoms, which may have substituents on the aromatic ring. Examples of aryl groups having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, and o-, m-, or p-biphenyl groups. 3 Examples of substituents that the aryl group represented by may have on the aromatic ring include halogen groups.

[0070] R 4 R represents one of the following: an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include R. 1 and R 2 This is the same as the example given. Examples of C2-C3 alkenyl groups include the ethenyl group and the propenyl group. Examples of C1-C4 alkoxy groups include monovalent groups (such as the methoxy group and the n-butoxy group) in which an oxygen atom is bonded to a carbon atom having a free valence in the C1-C4 alkyl group mentioned above.

[0071] N represents a nitrogen atom, X - (C6F5)4B -SbF6 - PF6 - (CF3CF2)3PF3 - , (C6F5)4Ga - This represents the trifluoromethanesulfonate anion or the p-toluenesulfonate anion.

[0072] A manufacturing method according to one embodiment of the present invention comprises a reaction step of reacting a tertiary amine with a (substituted) benzyl halide compound to obtain an ammonium halide compound.

[0073] Tertiary amines are amines represented by the following general formula (2).

[0074] [ka]

[0075] R in general formula (2) 1 ~R 3 This is R in general formula (1). 1 ~R 3 It is the same as this.

[0076] Among the amines represented by general formula (2), N,N-dimethylaniline is a preferred example.

[0077] Among the (substituted) benzyl halide compounds, 4-methoxybenzyl chloride is a preferred example.

[0078] The reaction between a tertiary amine and a (substituted) benzyl halide compound in the reaction step can be carried out by a condensation reaction (Menschutkin reaction) between the tertiary amine and the (substituted) benzyl halide compound, which is a quaternizing agent, in a polar solvent, or by a method of mixing and heating the tertiary amine and the (substituted) benzyl halide compound, which is a quaternizing agent, in a specific aprotic solvent, as described in Japanese Patent Application Publication No. 2011-88905, or by a method of mixing and heating the tertiary amine and the (substituted) benzyl halide compound, which is a quaternizing agent, without using a solvent.

[0079] The reaction between a tertiary amine and a (substituted) benzyl halide compound can be carried out using a known reaction vessel equipped with a stirring device capable of heating and cooling. In addition, methods such as simultaneously supplying the tertiary amine and the (substituted) benzyl halide compound from separate containers to an inline mixer and mixing them, or simultaneously supplying the tertiary amine and the (substituted) benzyl halide compound from separate containers to a T-type micromixer and mixing them, can also be used.

[0080] In the reaction step, the ratio of moles of the tertiary amine to the (substituted) benzyl halide compound (moles of tertiary amine / moles of (substituted) benzyl halide compound) to be 1 / 1 is most preferably 1 / 1.

[0081] A manufacturing method according to one embodiment of the present invention involves using (C6F5)4B to remove the halide ions contained in the ammonium halide compound obtained in the above reaction step. - SbF6 - PF6 - (CF3CF2)3PF3 - , (C6F5)4Ga - The process includes a salt exchange step in which the salt is exchanged in a solvent with at least one ion selected from the group consisting of trifluoromethanesulfonate anion and p-toluenesulfonate anion.

[0082] The salt exchange reaction involves the exchange of halide ions contained in the ammonium halide compound with (C6F5)4B - SbF6 - PF6 - (CF3CF2)3PF3 - , (C6F5)4Ga - This can be done by a known method of mixing trifluoromethanesulfonate anion and an alkali metal salt (preferably sodium salt) of p-toluenesulfonate anion.

[0083] The salt exchange reaction between an ammonium halide compound and an alkali metal salt can be carried out using a known reaction vessel equipped with a stirring device capable of heating and cooling.

[0084] In the salt exchange reaction, it is preferable to mix the alkali metal salt with the ammonium halide compound in the container in which the salt exchange reaction is carried out, and it is even more preferable to continuously divide and mix the alkali metal salt in the required amount using a dropping device or the like.

[0085] In a manufacturing method according to one embodiment of the present invention, it is preferable to perform a neutralization step between the reaction step and the salt exchange reaction, in which a neutralization step is performed to neutralize the reactant obtained in the reaction step, and an extraction and washing step is performed in which the reactant that has undergone the neutralization step is mixed and separated with a solvent such as chloroform for extraction.

[0086] The neutralization step can be carried out by mixing the reactants obtained in the reaction step with a basic aqueous solution, such as an aqueous solution of a basic compound (preferably sodium bicarbonate), using a known mixing apparatus. The neutralization step may be carried out under heating or without heating, and it is preferable to carry it out without heating.

[0087] There are no restrictions on the concentration of the basic aqueous solution mixed with the reactants, and the pH of the solution after the neutralization step is 7-9.

[0088] In the neutralization step, it is preferable to mix the basic aqueous solution with the reaction mixture in the container. This can be done by adding it all at once, or by continuously adding the required amount in installments using a dropper or the like.

[0089] The extraction and washing step can be carried out by dissolving the reactants obtained in the reaction step or the neutralized mixture obtained in the neutralization step in water such as deionized water as necessary, mixing it with an organic solvent such as chloroform, and then collecting the separated aqueous layer, repeating this process two or more times as necessary. The extraction and washing step may be carried out under heating or without heating, but it is preferable to carry it out without heating.

[0090] The extraction and washing process can be carried out using specialized equipment such as vertically moving extraction devices, rotary continuous liquid extraction devices, and high-performance liquid-liquid extraction devices like "MCEXT" (manufactured by Shinko Environmental Solutions Co., Ltd.), as well as equipment that combines a mixing container equipped with an agitator capable of mixing the liquid to be treated and the washing solution, with a liquid separator tank that separates the mixed liquid into two liquid phases and drains the lower layer.

[0091] One embodiment of the present invention relates to a manufacturing method for producing ammonium salts, in which the reaction process and the salt exchange process are carried out using a continuous production facility.

[0092] A continuous production system that performs processes from reaction to salt exchange is a system that can transfer contents from one device that has performed a certain process to another device that performs the next process, while keeping it isolated from the outside air. It is a system that can perform the next process continuously without leaving the system. Systems that can perform the next process continuously are preferable because they allow multiple processes to be carried out simultaneously in parallel by simultaneously performing the processing (reaction, extraction and washing, etc.) in each device that performs each process, thereby shortening the overall process time. An example of a continuous production system is the manufacturing apparatus 100 shown in Figure 2.

[0093] Preferably, the apparatuses where each step—the reaction step, the neutralization step (if necessary) to neutralize the reactants obtained in the reaction step, the extraction and washing step (if necessary) in which the reactants are mixed and separated with a solvent such as chloroform for extraction, and the salt exchange reaction step—are connected by stainless steel piping or synthetic resin (fluororesin, silicone resin, etc.) tubes, etc., so that the contents after each step are transferred to the apparatus for the next step without coming into contact with the outside air.

[0094] If there is no contact with the outside air, a container for storing the material obtained in the process may be placed between the device where the next process takes place. Having a storage container makes it possible to process a larger quantity in the next process.

[0095] If each of the apparatuses used in the reaction step, the neutralization step (which may be performed if necessary to neutralize the reactants obtained in the reaction step), the extraction and washing step (which may be performed if necessary to mix and separate the reactants with a solvent such as chloroform and extract the mixture), and the salt exchange reaction step are capable of continuous processing, such as continuous mixing apparatuses, then the ammonium salt may be produced by continuously flowing the reaction solution from the reaction step to the salt exchange step without stopping it in one place.

[0096] For example, by using a continuous manufacturing system manufactured by iFactory Co., Ltd., it is possible to produce ammonium salts by continuously flowing the reaction solution from the reaction process to the salt exchange process without stopping it in one place.

[0097] The manufacturing method of the present invention preferably further includes a solvent removal step after the salt exchange step, in which the solvent is removed by distillation.

[0098] The solvent removal process can be carried out using known solvent recovery equipment (such as distillation columns and rotary evaporators).

[0099] In the manufacturing method according to one embodiment of the present invention, it is preferable to carry out the steps from the reaction step to the solvent removal step using a continuous production facility, and this can be done by connecting the equipment that performs the exchange step and the equipment that performs the solvent removal step so that the contents after the salt exchange step are transferred to the equipment for the solvent removal step without coming into contact with the outside air.

[0100] In a manufacturing method according to one embodiment of the present invention, the method may include a solvent removal step and / or a purification step such as recrystallization after the solvent removal step. When a purification step is performed, it is preferable that the apparatus for the purification step and the apparatus for the steps before and after it are connected by stainless steel piping or resin (fluororesin, silicone resin, etc.) tubes so that the contents to be processed do not come into contact with the outside air.

[0101] 〔summary〕 One embodiment of the present invention may include the following configuration:

[0102] <1> A manufacturing apparatus for a target compound used in the manufacture of electronic components, comprising a countercurrent multi-stage washing and extraction unit that washes and extracts a target product containing at least one of the target compound and an intermediate product produced in a reaction for manufacturing the target compound, using a solvent that is immiscible with the target product-containing solution, wherein the washing and extraction unit has a plurality of extraction units arranged continuously from upstream to downstream, and the plurality of extraction units use the target product-containing solution supplied from the preceding extraction unit and the solvent supplied from the subsequent extraction unit to extract the target product-containing solution. An apparatus for producing a target compound, comprising at least one extraction stage, the extraction stage having an extraction stage comprising a mixing container for generating a mixture with a medium, a separatory tank for separating the mixture into a liquid phase containing the target product and a liquid phase of the solvent, and a first supply pipe for supplying the mixture in the mixing container to the separatory tank, wherein in the at least one extraction stage, the mixing container is located above the separatory tank, the first supply pipe is inclined downward with respect to the mixing container, and the mixture that has moved from the mixing container into the first supply pipe flows into the separatory tank by gravity.

[0103] <2> Each of the multiple extraction units is equipped with a recovery tank for recovering the liquid phase of the solvent in the separatory tank, and in the multiple extraction units, any one extraction unit is designated as the a-stage extraction unit, and the extraction unit located one stage downstream from the a-stage is designated as the a+1-stage extraction unit, and a second supply pipe is provided connecting the mixing container of the a-stage extraction unit and the recovery tank of the a+1-stage extraction unit, and the solvent in the recovery tank of the a+1-stage extraction unit is supplied to the mixing container of the a-stage extraction unit by pump drive via the second supply pipe. <1> A device for producing the target compound.

[0104] <3> In the aforementioned multi-stage extraction unit, any one extraction unit is designated as stage a, and the extraction unit located one stage downstream from stage a is designated as stage a+1. The separatory tank of stage a is located above the mixing container of stage a+1. A third supply pipe is provided connecting the mixing container of stage a+1 and the separatory tank of stage a. The liquid phase containing the target product in the separatory tank of stage a is supplied to the mixing container of stage a+1 by gravity via the third supply pipe. <1> or <2> A device for producing the target compound.

[0105] <4> The target compound is an ammonium salt represented by general formula (1), and the target product is the intermediate product, which is a compound represented by general formula (1a). <1> ~ <3> A manufacturing apparatus for any of the target compounds.

[0106] [ka]

[0107] [In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and R 3 R represents an aryl group having 6 to 12 carbon atoms, which may have substituents on the aromatic ring. 4 represents one of the alkyl groups with 1 to 4 carbon atoms, alkenyl groups with 2 to 3 carbon atoms, or alkoxy groups with 1 to 4 carbon atoms, N represents a nitrogen atom, and X - (C6F5)4B - SbF6 - PF6 - (CF3CF2)3PF3 - , (C6F5)4Ga - This represents the trifluoromethanesulfonate anion or the p-toluenesulfonate anion.

[0108] [ka]

[0109] [In general formula (1a), R 1 ~R 3 This is R in general formula (1). 1 ~R 3 It is the same as, where N represents a nitrogen atom, and Xa - It is a halogen ion. <5> A method for producing a target compound used in the manufacture of electronic components, comprising a countercurrent multi-stage washing and extraction step in which a target product containing at least one of the target compound and an intermediate product produced in a reaction for producing the target compound is washed and extracted with a solvent that is immiscible with the target product-containing solution, the washing and extraction step having a plurality of extraction steps performed continuously from upstream to downstream, the plurality of extraction steps in a mixing container, the target product-containing solution supplied from the preceding extraction step and the solvent supplied from the subsequent extraction step A method for producing a target compound, comprising at least one extraction step including a mixing step of generating a mixture with the solvent; a separation step of separating the mixture into a liquid phase containing the target product and a liquid phase of the solvent in a separatory tank; and a first supply step of supplying the mixture in the mixing container to the separatory tank via a first supply pipe, wherein the mixing container is located above the separatory tank, and in the first supply step, the first supply pipe is provided at an angle downward relative to the mixing container, and the mixture that has moved from the mixing container into the first supply pipe flows into the separatory tank by gravity.

[0110] <6> The target compound is an ammonium salt represented by general formula (1), and the target product is the intermediate product, which is a compound represented by general formula (1a). <5> A method for producing the target compound.

[0111] [ka]

[0112] [In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and R 3represents an aryl group having 6 to 12 carbon atoms which may have a substituent on the aromatic ring, and R 4 represents any one of an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, N represents a nitrogen atom, and X - is (C6F5)4B - , SbF6 - , PF6 - , (CF3CF2)3PF3 - , (C6F5)4Ga - represents a trifluoromethanesulfonate anion or a p-toluenesulfonate anion.]

[0113] [Chemical formula]

[0114] [In general formula (1a), R 1 ~R 3 is the same as R 1 ~R 3 in general formula (1), N represents a nitrogen atom, and Xa - is a halogen ion.] <7>A method for producing an ammonium salt represented by general formula (1), comprising a reaction step of reacting a tertiary amine with a (substituted) benzyl halide compound to obtain an ammonium halide compound, and a salt exchange step of performing salt exchange in a solvent of the halide ion contained in the ammonium halide compound obtained in the reaction step with at least one ion selected from the group consisting of (C6F5)4B - , SbF6 - , PF6 - , (CF3CF2)3PF3 - , (C6F5)4Ga - , a trifluoromethanesulfonate anion, and a p-toluenesulfonate anion, and a method for producing an ammonium salt in which the steps from the reaction step to the salt exchange step are performed using continuous production equipment.

[0115] [Chemical formula]

[0116] [In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and R 3 R represents an aryl group having 6 to 12 carbon atoms, which may have substituents on the aromatic ring. 4 represents one of the alkyl groups with 1 to 4 carbon atoms, alkenyl groups with 2 to 3 carbon atoms, or alkoxy groups with 1 to 4 carbon atoms, N represents a nitrogen atom, and X - (C6F5)4B - SbF6 - PF6 - (CF3CF2)3PF3 - , (C6F5)4Ga - This represents the trifluoromethanesulfonate anion or the p-toluenesulfonate anion. <8> The process includes a solvent removal step after the salt exchange step, and the entire process from the reaction step to the solvent removal step is carried out using a continuous production facility. <7> A method for producing ammonium salts. [Examples]

[0117] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, the experiments were conducted at room temperature (20-25°C).

[0118] <Example 1> (4-methoxybenzyl)(dimethyl)(phenyl)ammonium=tetrakis(pentafluorophenyl)borate [hereinafter referred to as Compound-1] is manufactured using a continuous production facility. A continuous production system was created by sequentially connecting a precision liquid transfer pump (Takumina Q-100), a T-shaped micromixer (MiChS α500T) for the reaction process (reaction section), a container with a stirring device for the neutralization process (neutralization section), a liquid transfer pump, a device for the extraction and washing process (washing and extraction section), a liquid transfer pump, and a device for the salt exchange reaction (salt exchange section) using PFA tubing (inner diameter 1.0~1.6 mm).

[0119] The apparatus for the extraction and washing process consists of three containers (referred to as the 1st to 3rd containers, respectively) each having a raw material inlet, branch pipes on the upper part of the container side wall, and a stirrer (washing containers), and a container (extraction container) having a raw material inlet on the top surface and branch pipes on the upper and lower parts of the container side wall. The apparatus performs the extraction and washing process by repeatedly and alternately connecting the branch pipes on the upper part of the side wall of the washing containers to the raw material inlet of the extraction containers using PFA tubing, and connecting the upper branch pipes of the extraction containers to the raw material inlet of the washing containers using PFA tubing.

[0120] The washing containers and extraction containers were connected and installed alternately so that the container connected later was at a lower position. The liquid that moved from the first washing container moved to the next container by gravity, and a container capable of storing liquid was connected to a branch tube at the bottom of the side wall of the third extraction container, which was the last to be located.

[0121] The apparatus for the salt exchange reaction consists of a container (mixing container) having a raw material inlet, branch pipes on the upper part of the container's side wall, and a stirrer, and a container (recovery container) having a raw material inlet on the top surface of the container and branch pipes on the upper and lower parts of the container's side wall. The branch pipes on the upper part of the side wall of the mixing container and the raw material inlet of the recovery container are connected using PFA tubing. Containers capable of storing liquid are connected to the branch pipes on the upper and lower parts of the side wall of the recovery container, respectively.

[0122] The PFA tube connecting the T-shaped micromixer and the container used for the neutralization process was 20m long and had an inner diameter of 4.35mm.

[0123] In a container having a raw material inlet, a branch pipe at the top of the container's side wall, and a stirrer, the same amount of liquid supplied from the inlet overflows from the upper branch pipe and moves to the next container.

[0124] The container, which has a raw material inlet on its top surface and branch pipes on the upper and lower parts of its side walls, has a volume of 30 mL up to the upper branch pipe. The mixed liquid transferred to the container separates into two phases. If the supply of the mixed liquid from the inlet continues, the liquid level rises while separating, and after the liquid level reaches the upper branch pipe, the same amount of liquid supplied from the inlet overflows from the upper branch pipe and moves continuously to the next extraction container or recovery container.

[0125] Furthermore, to ensure that the liquid level in the container remained constant and that liquid continuously flowed out from the upper branch pipe, the lower layer of liquid separated from the lower branch pipe was also drained away.

[0126] <Reaction Process> A mixed solution of N,N-dimethylaniline (2.0 kg, 16.7 mol) and dimethyl sulfoxide (2.6 kg) was prepared, and the reaction process was carried out by continuously supplying the mixed solution and 4-methoxybenzyl chloride (2.6 kg, 16.7 mol) to a T-shaped micromixer using a precision liquid transfer pump (Takumina Q-100). The supply rate of the N,N-dimethylaniline mixture to the T-shaped micromixer was controlled to 2.0 mL / min, and the supply rate of 4-methoxybenzyl chloride to the T-shaped micromixer was controlled to 1.0 mL / min.

[0127] By immersing a PFA tube in a 50°C water bath between the T-shaped micromixer and the container for the neutralization process, the mixture discharged from the T-shaped micromixer was heated within the PFA tube while being transferred to the container for the neutralization process.

[0128] <Neutralization process> In the container used for the neutralization process, the mixture discharged from the micromixer was received, and at the same time, a 5.1 wt% sodium bicarbonate solution was continuously added at a supply rate of 3.6 mL / min using a dropper pump, and the mixture was mixed to perform the neutralization process.

[0129] <Extraction and Washing Process> After the liquid volume in the neutralization container reached 40 mL, the neutralized solution was transferred at a flow rate of 6.6 mL / min to a container with a stirrer (first washing container), while chloroform was continuously added to the same container (first washing container) with the stirrer running at a supply rate of 6.6 mL / min to mix the liquids. The mixed liquid was transferred to a container with upper and lower branch tubes (first extraction container) through a PFA tube connected to the upper branch tube of the washing container. The upper layer (aqueous phase) of the liquid separated in the first extraction container was transferred from the upper branch tube to the next washing container (second washing container), and the lower layer was drained from the lower branch tube. Chloroform was continuously supplied to the second washing container to mix the liquids in the same way as in the first washing container. The liquid overflowing from the upper branch tube of the second washing container was transferred through a PFA tube to the next extraction container (second extraction container), and then the upper layer was transferred to the third washing container and the lower layer was drained in the same way as in the first extraction container. The same procedure was followed in the third washing vessel and the third extraction vessel. The liquid overflowing from the upper branch tube of the third extraction vessel was transferred to the mixing vessel, which constitutes the apparatus for the salt exchange reaction, using a liquid transfer pump at a transfer rate of 6.0 mL / min. The concentration of (4-methoxybenzyl)(dimethyl)(phenyl)ammonium chloride in the liquid (aqueous phase) transferred to the mixing vessel was 24% by weight, with a yield of 76% and an LC purity of 99.0%.

[0130] <Salt exchange process> An anion exchange reaction was carried out by continuously adding a mixed solution of sodium tetrakis(pentafluorophenyl) borate (8.5 kg, 12.1 mol), acetonitrile (8.5 kg), and chloroform (22.4 kg) at a supply rate of 13.62 mL / min while stirring to a mixing vessel into which the aqueous phase was continuously transferred at a liquid flow rate of 6.0 mL / min from a third extraction vessel, which constitutes the apparatus for the extraction and washing process.

[0131] The liquid after the anion exchange reaction, which overflowed from the upper branch of the mixing vessel, was received in a container (recovery container) having branch tubes at the upper and lower parts of the side wall of the container, and the lower layer (organic phase) containing compound-1 was recovered from the lower branch tube. The transfer of the aqueous phase discharged after the extraction and washing process and the addition of the aforementioned mixed solution were continued until the total volume of the recovered organic phase reached 4 L (5.2 kg).

[0132] <Solvent distillation process> The entire volume (4 L) of compound-1 obtained in the salt exchange step was subjected to a solvent removal step using a rotary evaporator (N-3100, manufactured by Tokyo Rikakikai Co., Ltd.) at a water bath temperature of 50°C and a reduced pressure of 180 hPa until the concentration reached 80%, yielding an oily substance. Subsequently, methanol (7.6 kg) was added to the obtained oily substance to dissolve and dilute it, and then it was transferred to a crystallization filtration tank (reaction filtration device, manufactured by Asahi Seisakusho Co., Ltd.), where crystals were precipitated by adding ion-exchanged water (9 kg) while stirring.

[0133] The crystals were collected by filtration from the contents of the crystallization filter tank and dried in a vacuum dryer at 50°C for 15 hours to obtain compound-1, a white crystalline compound (total weight of crystals obtained from 7 treatments: 10.0 kg).

[0134] <Example 2> (4-methoxybenzyl)(dimethyl)(phenyl)ammonium=tetrakis(pentafluorophenyl)gallate [hereinafter referred to as Compound-2] is manufactured using a continuous production facility. <Reaction process ~ Salt exchange process> A solution containing compound-2 was obtained in the same manner as in Example 1, except that in the salt exchange step of Example 1, "sodium tetrakis(pentafluorophenyl)borate (8.5 kg, 12.1 mol)" was changed to "sodium tetrakis(pentafluorophenyl)gallate (9.2 kg, 12.1 mol)".

[0135] <Solvent distillation process> The solution containing compound-2 obtained in the salt exchange process was concentrated using a thin-film evaporator (MF-1000, manufactured by Tokyo Rikakikai Co., Ltd.). The solution containing compound-2 obtained in the salt exchange process was automatically supplied to the thin-film evaporator directly from the storage container by a liquid transfer pump, and the liquid volume was adjusted to a constant amount by a liquid level sensor. The evaporator jacket water temperature was set to 50°C, the pressure was reduced to 130 hPa, and the impeller rotation speed was set to 1200 rpm, and the concentrated liquid with a concentration of 70% was continuously discharged from the thin-film evaporator. The discharged concentrated liquid was transferred to a container equipped with a stirrer at a flow rate of 5 mL / min and methanol at a flow rate of 22 mL / min and mixed.

[0136] Next, this mixed solution and deionized water were transferred to a crystallization filtration tank (reaction filtration device manufactured by Asahi Seisakusho Co., Ltd.) at a transfer rate of 27 mL / min and 15 mL / min, and crystals were precipitated by stirring and mixing the two liquids.

[0137] When 20 L of this suspension had accumulated, the crystals were filtered and recovered by vacuum filtration, and dried in a vacuum dryer at 50°C for 15 hours to obtain compound-2, a white crystalline compound (total weight of crystals obtained after 7 filtration treatments: 10.6 kg).

[0138] <Example 3> (4-Methoxybenzyl)(dimethyl)(phenyl)ammonium = tris(pentafluoroethyl)trifluorophosphate [hereinafter referred to as Compound-3] is manufactured using a continuous production facility. <Reaction process ~ Salt exchange process> A solution containing compound-3 was obtained in the same manner as in Example 1, except that in the salt exchange step of Example 1, "sodium tetrakis(pentafluorophenyl) borate (8.5 kg, 12.1 mol)" was changed to "potassium tris(pentafluoroethyl) trifluorophosphate (5.9 kg, 12.1 mol)".

[0139] <Solvent distillation process> After obtaining 4 L of a solution containing compound-3 obtained in the salt exchange step, a solvent removal step was performed using a rotary evaporator (N-3100, manufactured by Tokyo Rikakikai Co., Ltd.) at a water bath temperature of 50°C and a reduced pressure of 120 hPa to obtain an oily compound-3 (total weight of the oily substance obtained in 7 solvent removal treatments: 8.0 kg).

[0140] <Example 4> (4-methoxybenzyl)(dimethyl)(phenyl)ammonium trifluoromethanesulfonate [hereinafter referred to as Compound-4] is manufactured using a continuous production facility. <Reaction process ~ Salt exchange process> In the salt exchange step of Example 1, "sodium tetrakis(pentafluorophenyl) borate (8.5 kg, 12.1 mol)" was replaced with "sodium A solution containing compound-4 was obtained in the same manner as in Example 1, except that the compound was changed to "trifluoromethanesulfonate (2.1 kg, 12.1 mol)".

[0141] <Solvent distillation process> The solution containing compound-4 obtained in the salt exchange step was concentrated by the same process as in the solvent removal step in Example 2. The jacket water temperature was set to 60°C, the reduced pressure to 110 hPa, and the impeller rotation speed to 1200 rpm. The continuously discharged concentrate had a concentration of 40%.

[0142] This concentrated solution was transferred to a crystallization filter tank (reaction filtration apparatus manufactured by Asahi Seisakusho Co., Ltd.) at a rate of 4 mL / min and methyl-tert-butyl ether at a rate of 12 mL / min. The two liquids were stirred and mixed to precipitate crystals. When 20 L of this suspension had accumulated, the crystals were separated and recovered by vacuum filtration, and dried in a vacuum dryer at 50°C for 6 hours to obtain compound-4, a white crystalline compound (total weight of crystals obtained from three filtration processes: 4.0 kg).

[0143] <Comparative Example 1> Production of Compound-1 without using continuous production equipment <Reaction Process> N,N-dimethylaniline (2.4 kg, 20.0 mol), acetonitrile (0.8 kg), and 4-methoxybenzyl chloride (3.1 kg, 20.0 mol) were homogeneously mixed in a reaction vessel equipped with a stirrer, and the reaction was carried out by heating to 50°C for 6 hours. Acetone (14.7 kg) was then added while stirring, and the mixture was cooled to 5°C while stirring for 1 hour to precipitate crystals of (4-methoxybenzyl)(dimethyl)(phenyl)ammonium chloride. After filtration, 4.2 kg of crystals were obtained (yield 76%), and the LC purity was 99.0%.

[0144] <Salt exchange process> The entire amount of these crystals was mixed with ion-exchanged water (14.6 kg), chloroform (26.8 kg), acetonitrile (10.1 kg), and sodium tetrakis(pentafluorophenyl) borate (10.1 kg, 14.5 mol) in a container and stirred for 1 hour to carry out a salt exchange reaction. After stirring, the mixture was allowed to stand for 30 minutes, and the two phases were separated and the organic layer (lower layer) was collected.

[0145] <Solvent distillation process> The recovered organic layer was placed in a reaction vessel capable of heating and reduced pressure, and the solvent was removed by heating to 40°C under reduced pressure until the concentration reached 80%, thereby removing chloroform and obtaining a white oily substance.

[0146] The entire amount of the white oily substance was dissolved in methanol (72.2 kg), and then ion-exchanged water (88.9 kg) was slowly added to precipitate crystals. The crystals were then filtered to separate and recover them, and then dried in a vacuum dryer at 50°C for 15 hours to obtain compound-1 (10.0 kg) as white crystals.

[0147] Table 1 shows the purity and yield at each step in Examples 1-4 and Comparative Example 1. Purity was measured using HPLC (Hitachi High-Tech Corporation, Chromaster 5160, 5260, 5310, 5430) and calculated from the peak area ratio.

[0148] [Table 1]

[0149] As shown in Table 1, in the examples carried out using a continuous manufacturing facility, high-purity ammonium salts were obtained in high yield. Although ammonium salts are prone to thermal decomposition when dissolved in a solvent, it is believed that the production method of the present invention suppressed thermal decomposition, thereby preventing a decrease in yield and purity. [Industrial applicability]

[0150] The manufacturing method of the present invention can produce high-purity ammonium salts in high yield, and is particularly useful for producing ammonium salts used as thermal acid generators where high purity is required. [Explanation of symbols]

[0151] 10, 20 Extraction part 11, 21 Mixing container 12, 22 Separating tank 12a, 22a Liquid phase (liquid phase containing intermediate products) 12b, 22b Liquid phase (liquid phase containing solvent) 13, 23 1st supply pipe 14, 24 Recovery tanks 31, 32, 33 2nd supply pipe 41, 42, 43 3rd supply pipe 50 Washing and Extraction Section 100 Manufacturing equipment

Claims

1. A manufacturing apparatus for a target compound used in the manufacturing of electronic components, The apparatus comprises a countercurrent multi-stage washing and extraction unit that washes and extracts a target product containing at least one of the target compound and an intermediate product produced in the reaction for producing the target compound, with a solvent that is immiscible with the target product-containing solution. The washing and extraction unit has multiple extraction units arranged continuously from the upstream side to the downstream side. The aforementioned multi-stage extraction unit is A mixing container that generates a mixture of the target product-containing solution supplied from the preceding extraction unit and the solvent supplied from the subsequent extraction unit, A separatory tank for separating the mixture into a liquid phase containing the target product and a liquid phase of the solvent, A first supply pipe that supplies the mixture in the mixing container to the liquid separatory tank, It includes at least one extraction stage equipped with, In the extraction unit of at least one stage, The mixing container is located above the liquid separator, The first supply pipe is installed at an inclination downward with respect to the mixing container, An apparatus for producing a target compound, wherein the mixed liquid that has moved from the mixing container into the first supply pipe is allowed to flow into the separatory tank by gravity.

2. Each of the aforementioned multi-stage extraction units is equipped with a recovery tank for recovering the liquid phase of the solvent in the separatory tank. In the aforementioned multi-stage extraction unit, any one extraction unit is designated as stage a, and the extraction unit located one stage downstream from stage a is designated as stage a+1. A second supply pipe is provided that connects the mixing container of the extraction section of stage a and the recovery tank of the extraction section of stage a+1. The apparatus for producing the target compound according to claim 1, wherein the solvent in the recovery tank of the a+1 stage extraction unit is supplied to the mixing container of the a stage extraction unit by pump drive via the second supply pipe.

3. In the aforementioned multi-stage extraction unit, any one extraction unit is designated as stage a, and the extraction unit located one stage downstream from stage a is designated as stage a+1. The liquid-liquid separator in the a-stage extraction section is located above the mixing container in the a+1-stage extraction section. A third supply pipe is provided that connects the mixing container of the a+1 stage extraction unit and the liquid separator tank of the a stage extraction unit. The apparatus for producing the target compound according to claim 1, wherein the liquid phase containing the target product in the separatory tank of the extraction section of stage a is supplied to the mixing container of the extraction section of stage a+1 by gravity via the third supply pipe.

4. The aforementioned target compound is an ammonium salt represented by general formula (1), The apparatus for producing the target compound according to any one of claims 1 to 3, wherein the target product is the intermediate product and is a compound represented by general formula (1a). 【Chemistry 1】 [In general formula (1), R １ and R ２ each independently represent an alkyl group having 1 to 4 carbon atoms, R ３ represents an aryl group having 6 to 12 carbon atoms which may have a substituent on the aromatic ring, R ４ represents any one of an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, N represents a nitrogen atom, X － is (C ６ F ５ ), ４ B － , SbF ６ － , PF ６ － , (CF ３ CF ２ ), ３ PF ３ － , (C ６ F ５ ), ４ Ga － , a trifluoromethanesulfonic acid anion, or a p-toluenesulfonic acid anion.] 【Chemistry 2】 [In general formula (1a), R １ ~R ３ R in general formula (1) １ ~R ３ It is the same as, where N represents a nitrogen atom, and Xa － It is a halogen ion.

5. A method for producing a target compound used in the manufacture of electronic components, The process includes a countercurrent multi-stage washing and extraction step in which a target product containing at least one of the target compound and an intermediate product produced in a reaction for producing the target compound is washed and extracted with a solvent that is immiscible with the target product-containing solution. The washing and extraction process comprises multiple extraction steps performed continuously from the upstream side to the downstream side. The aforementioned multi-stage extraction process is A mixing step in which a mixture is produced in a mixing container of the solution containing the target product supplied from the preceding extraction step and the solvent supplied from the subsequent extraction unit, A separation step is performed in which the mixture is separated into a liquid phase containing the target product and a liquid phase of the solvent in a separatory tank. The extraction process includes at least one step, which includes a first supply step of supplying the mixture in the mixing container to the liquid separatory tank via a first supply pipe, The mixing container is located above the liquid separator, In the first supply process described above, The first supply pipe is installed at an inclination downward with respect to the mixing container, A method for producing a target compound, comprising moving the mixed liquid from the mixing container into the first supply pipe into the separatory tank by gravity.

6. The aforementioned target compound is an ammonium salt represented by general formula (1), The method for producing the target compound according to claim 5, wherein the target product is the intermediate product and is a compound represented by general formula (1a). 【Transformation 3】 [In general formula (1), R １ and R ２ Each of these independently represents an alkyl group having 1 to 4 carbon atoms, and R ３ R represents an aryl group having 6 to 12 carbon atoms, which may have substituents on the aromatic ring. ４ represents one of the alkyl groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 3 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms, N represents a nitrogen atom, and X － is (C ６ F ５ ) ４ B － SbF ６ － , PF ６ － (CF ３ CF ２ ) ３ PF ３ － , (C ６ F ５ ) ４ Ga － This represents the trifluoromethanesulfonate anion or the p-toluenesulfonate anion. 【Chemistry 4】 [In general formula (1a), R １ ~R ３ R in general formula (1) １ ~R ３ It is the same as, where N represents a nitrogen atom, and Xa － It is a halogen ion.

7. This is a method for producing an ammonium salt represented by general formula (1), A reaction step to obtain an ammonium halide compound by reacting a tertiary amine with a (substituted) benzyl halide compound, and a step to remove the halide ions contained in the ammonium halide compound obtained in the reaction step from (C ６ F ５ ) ４ B － SbF ６ － , PF ６ － (CF ３ CF ２ ) ３ PF ３ － , (C ６ F ５ ) ４ Ga － The process includes a salt exchange step in which at least one ion selected from the group consisting of trifluoromethanesulfonate anion and p-toluenesulfonate anion is exchanged in a solvent. A method for producing ammonium salts, which involves using a continuous production system to carry out the reaction process and the salt exchange process. 【Transformation 5】 [In general formula (1), R １ and R ２ each independently represent an alkyl group having 1 to 4 carbon atoms, R ３ represents an aryl group having 6 to 12 carbon atoms which may have a substituent on the aromatic ring, R ４ represents any one of an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, N represents a nitrogen atom, X － is (C ６ F ５ ), ４ B － SbF ６ － PF ６ － (CF ３ CF ２ ), ３ PF ３ － (C ６ F ５ ), ４ Ga － a trifluoromethanesulfonate anion, or a p-toluenesulfonate anion.]

8. The method for producing an ammonium salt according to claim 7, further comprising a solvent removal step of removing the solvent after the salt exchange step, wherein the steps from the reaction step to the solvent removal step are carried out using a continuous production facility.

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