Filtering device, purification device, liquid medicine manufacturing device, filtered purified product, liquid medicine, and radiation-sensitive or active light-sensitive resin composition

Abstract

The present invention provides a filter device that can obtain a drug solution having excellent performance and in which the life of a filter material is sufficiently long. The present invention also provides a purification device, a drug solution manufacturing device, a filtered purified substance, a drug solution, and a photoreactive or radioreactive resin composition. The filter device of the present invention includes a first filter unit and a second filter unit that are independently disposed in a pipe through which a purified substance is supplied. The first filter unit includes a first filter that satisfies at least one of requirements 1 to 3 and a housing that accommodates the first filter. The second filter unit includes a second filter that is different from the first filter and a housing that accommodates the second filter.

Description

[0001] This application is a divisional application of application number 201880047759.1, entitled "Filtering device, purification device, pharmaceutical preparation device, filtered purified substance, pharmaceutical preparation and photosensitive or radiosensitive linear resin composition". The parent application was filed on July 26, 2018, and the earliest priority date is July 26, 2017. Technical Field

[0002] This invention relates to a filtration device, a purification device, a pharmaceutical preparation device, a filtered purified substance, a pharmaceutical preparation, and a photosensitive or radiosensitive linear resin composition. Background Technology

[0003] In the manufacture of semiconductor devices, solutions containing solvents (typically organic solvents) are used. In recent years, there has been a growing demand for reducing the impurities contained in these solutions. Furthermore, research into the manufacture of semiconductor devices with nodes smaller than 10nm has further increased these requirements.

[0004] Patent Document 1 describes a filter material comprising a non-sieve membrane layer having a specified pore size distribution, a sieve membrane layer having a specified pore size distribution, and a nylon nanofiber layer having a pore size distribution larger than that of the non-sieve membrane layer and the sieve membrane layer, and having a specified pore size distribution.

[0005] Previous technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Publication No. 2014-514158 Summary of the Invention

[0008] The technical problem to be solved by the invention

[0009] The inventors manufactured a filter with the filter material described in Patent Document 1, and used the filter to purify the purified substance. The results showed that the purified liquid contained less impurities, and therefore the liquid had excellent performance. However, the filter material had a short lifespan.

[0010] Therefore, the objective of this invention is to provide a filtration apparatus that yields a pharmaceutical solution with excellent performance and a sufficiently long filter material lifespan. Furthermore, the objective of this invention is to provide a purification apparatus, a pharmaceutical solution manufacturing apparatus, a filtered purified substance, a pharmaceutical solution, and a photosensitive or radiosensitive linear resin composition.

[0011] means for solving technical problems

[0012] In order to achieve the above-mentioned problems, the inventors conducted in-depth research and discovered that the above-mentioned problems can be achieved through the following configuration.

[0013] (1) A filtration device having a first filter unit and a second filter unit independently disposed in a pipeline for supplying a purified substance, the first filter unit comprising a first filter satisfying at least one of the group consisting of elements 1 to 3 described below and a housing containing the first filter, the second filter unit comprising a second filter different from the first filter and a housing containing the second filter.

[0014] (2) The filtration device as described in (1), wherein the difference between the cumulative 10% pore size and the cumulative 75% pore size in the cumulative pore distribution of the filter material of the first filter is 3 nm or more.

[0015] (3) The filter device as described in (2), wherein the ratio of the cumulative 75% pore size to the cumulative 10% pore size is 2.0 to 20.0.

[0016] (4) The filter device as described in any one of (1) to (3), wherein the filter material of the second filter has a pore size of 200 nm or less.

[0017] (5) The filter device as described in any one of (1) to (4), wherein the filter material of the second filter has a pore size of 100 nm or less.

[0018] (6) The filter device as described in any one of (1) to (5), wherein the pore size of the filter material of the second filter is less than or equal to the pore size of the filter material of the first filter.

[0019] (7) The filter device as described in any one of (1) to (6), wherein the second filter unit is on the secondary side of the first filter unit, and the pore size of the filter material of the second filter is less than or equal to the pore size of the filter material of the first filter.

[0020] (8) The filter device as described in any one of (1) to (5), wherein the second filter unit is disposed on the primary side and the first filter unit is disposed on the secondary side.

[0021] (9) The filtration device as described in (8), wherein the pore size of the filter material of the second filter is greater than or equal to the pore size of the filter material of the first filter.

[0022] (10) The filter device according to any one of (1) to (9), wherein a second filter unit is further disposed on the secondary side of the first filter unit, the filter material of the second filter unit disposed on the secondary side has a pore size that is less than or equal to the pore size of the filter material of the first filter, and the filter material of the first filter includes a layer comprising a surface-treated substrate.

[0023] (11) The filter device as described in any one of (1) to (10), wherein the first filter has a filter material comprising two or more layers each containing different materials.

[0024] (12) The filter device as described in any one of (1) to (11), wherein the filter material of the second filter comprises the same material as any one of the two or more layers.

[0025] (13) The filtration apparatus as described in any one of (1) to (12), wherein, in the relationship between the Hansen solubility parameters δDp, δPp, and δHp of at least one filter material selected from the group consisting of the filter material of the first filter and the filter material of the second filter, and the interaction radius R0 and the Hansen solubility parameters δDs, δPs, and δHs of the purified substance, Ra is expressed by the following formula Ra 2 =4(δDs-δDp) 2 +(δPs-δPp) 2 +(δHs-δHp) 2 In the case indicated, the ratio of Ra to R0 is 1.0 or less.

[0026] (14) The filter device as described in any one of (1) to (13), wherein the first filter has a filter material comprising two or more layers with different pore structures.

[0027] (15) The filter device as described in any one of (1) to (14), wherein the first filter has a filter material comprising layers having different pore structures in the thickness direction.

[0028] (16) The filtration apparatus as described in any one of (1) to (15), wherein the filter material of the first filter comprises a layer containing a substrate having ion exchange groups.

[0029] (17) The filter apparatus as described in any one of (1) to (16), wherein the filter material of the first filter comprises a layer containing a surface-treated substrate and a layer containing an untreated substrate.

[0030] (18) The filter device as described in any one of (1) to (17) is capable of backwashing at least one of the group consisting of the first filter and the second filter.

[0031] (19) The filtration device as described in any one of (1) to (18), wherein the filter material of the first filter and the filter material of the second filter comprise at least one material selected from the group consisting of nylon, polyethylene, polypropylene, polyfluorocarbon, cellulose, diatomaceous earth, polystyrene, glass and polysulfone.

[0032] (20) The filtration device as described in any one of (1) to (19), wherein at least one filter material selected from the group consisting of the filter material of the first filter and the filter material of the second filter comprises at least one layer selected from the group consisting of a nanoporous membrane layer and a nanofiber layer.

[0033] (21) The filtration device as described in (20), wherein the first filter has a filter material comprising at least a nanoporous membrane layer and a nanofiber layer.

[0034] (22) The filtration device as described in any one of (1) to (21), wherein the filter material of the first filter includes a non-sieve membrane layer having a pore size distribution of 10 nm to 50 nm, a sieve membrane layer having a pore size distribution of 2 nm to 50 nm, and a nylon nanofiber layer.

[0035] (23) The filtration device as described in (22), wherein the nylon nanofiber layer is located between the non-sieve membrane layer and the sieve membrane layer.

[0036] (24) The filtration device as described in (22), wherein the non-sieve membrane layer is located between the sieve membrane layer and the nylon nanofiber layer.

[0037] (25) The filtration device as described in (22), wherein the sieve membrane layer is located between the non-sieve membrane layer and the nylon nanofiber layer.

[0038] (26) The filter device as described in any one of (19) to (25), wherein the first filter further comprises one or more porous support layers.

[0039] (27) The filtration apparatus as described in any one of (1) to (26) is capable of backwashing the first filter by allowing the cleaning fluid to flow from the secondary side of the first filter unit to the primary side of the first filter unit.

[0040] (28) A purification apparatus comprising a filtration device as described in any one of (1) to (27) and a tank capable of storing the purified material on the primary side of the filtration device.

[0041] (29) The purification apparatus as described in (28) wherein the secondary side of the first filter unit is connected to the tank via a pipeline, and at least the filtered purified material filtered by the first filter is able to be returned to the tank via the pipeline.

[0042] (30) The purification apparatus as described in (28) or (29), wherein a distillation apparatus is further provided on the primary side of the filtration apparatus.

[0043] (31) The purification apparatus as described in any one of (28) to (30), wherein the filtration apparatus further comprises a recyclable path.

[0044] (32) A pharmaceutical liquid manufacturing apparatus comprising a filtration device as described in any one of (1) to (27) and a mixing device for mixing one or more raw materials to prepare a purified substance.

[0045] (33) A filtered purified substance obtained by filtering the purified substance using any one of the filtering devices (1) to (27).

[0046] (34) A liquid medicine containing an organic solvent and filtered using any one of the filtration devices (1) to (27), wherein the organic solvent is at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, γ-butyrolactone, diisopentanone, butyl acetate, isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, n-methyl-2-pyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone and 2-heptanone.

[0047] (35) A medicinal liquid containing water and filtered using any one of (1) to (27).

[0048] (36) The liquid medicine as described in (34) or (35) is used in semiconductor manufacturing.

[0049] (37) A photosensitive or radiosensitive linear resin composition, which is filtered using any one of (1) to (27).

[0050] Invention Effects

[0051] According to the present invention, a filtration apparatus can be provided that yields a pharmaceutical solution with excellent performance and a sufficiently long filter material lifespan. Furthermore, the present invention can also provide a purification apparatus, a pharmaceutical solution manufacturing apparatus, filtered purified material, a pharmaceutical solution, and a photosensitive or radiosensitive linear resin composition. Attached Figure Description

[0052] Figure 1 This is a stereoscopic image of a portion of the first filter being removed.

[0053] Figure 2 This is a stereoscopic image of a portion of the typical second filter being removed.

[0054] Figure 3 This is a perspective view showing an example of a filter unit.

[0055] Figure 4 This is a partial cross-sectional view of the filter unit in the filtration device.

[0056] Figure 5 This is a schematic diagram of a filtration device according to the first embodiment of the present invention.

[0057] Figure 6 This is a schematic diagram of a filtration device according to a second embodiment of the present invention.

[0058] Figure 7 This is a schematic diagram of a drug purification apparatus according to an embodiment of the present invention.

[0059] Figure 8 This is a schematic diagram of a drug purification apparatus according to the second embodiment of the present invention.

[0060] Figure 9 This is a schematic diagram of a manufacturing apparatus according to an embodiment of the present invention. Detailed Implementation

[0061] The present invention will now be described in detail.

[0062] The following description of the constituent elements is based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.

[0063] In addition, in this specification, the numerical range represented by “~” refers to the range including the values ​​recorded before and after “~” as the lower limit and upper limit.

[0064] Furthermore, when the term "preparation" is mentioned in this invention, it refers to the preparation of specified items through procurement, in addition to the synthesis or preparation of specific materials.

[0065] Furthermore, in this invention, "ppm" represents parts per million (ppm). -6 "ppb" means parts-per-billion (10 -9 "ppt" indicates the mega-scale ratio "parts-per-trillion (10)". -12"ppq" indicates gigabit-per-quadrillion (10 -15 )".

[0066] Furthermore, in this specification, 1 Å (angtze) is equivalent to 0.1 nm.

[0067] Furthermore, in the designation of groups (atoms) in this specification, those not marked with "substituted" or "unsubstituted" include substituent groups along with unsubstituent groups, to the extent that it does not impair the effects of the invention. For example, "hydrocarbon group" means that it includes not only unsubstituent hydrocarbon groups (unsubstituted hydrocarbon groups) but also substituent hydrocarbon groups (substituted hydrocarbon groups). This applies to all compounds as well.

[0068] Furthermore, in this invention, "radiation" refers to, for example, far-ultraviolet light, extreme ultraviolet (EUV) lithography, X-rays, or electron beams. Also, in this invention, "light" refers to activated light or radiation. Unless otherwise specified, "exposure" in this invention includes not only exposure via far-ultraviolet light, X-rays, or EUV, but also depiction via particle beams such as electron beams or ion beams.

[0069] [Filtering device]

[0070] The filtration apparatus according to an embodiment of the present invention has a first filter unit and a second filter unit, each independently disposed in a pipeline supplying the purified material. The first filter unit includes a defined first filter and a housing containing the first filter. The second filter unit has a second filter different from the first filter and a housing containing the second filter. The first filter is housed within the housing of the first filter unit, and the first filter has a filter material that satisfies at least one of the following criteria 1 to 3. Furthermore, in the following description, the filter material of the first filter is also referred to as the "first filter material".

[0071] Requirement 1: The filter has filter material comprising two or more layers, each containing different materials.

[0072] Requirement 2: The filter has a filter material comprising two or more layers with different pore structures.

[0073] Requirement 3: The filter has a filter material comprising a layer of different materials mixed together.

[0074] Furthermore, at least one of the two or more filter units contains a second filter within its housing.

[0075] Furthermore, it is preferable that the first filter material satisfies at least one of conditions 1 and 2.

[0076] [First Implementation Form]

[0077] The structure and materials used in the filtration device according to an embodiment of the present invention will be described below. Furthermore, the filtration device described below is an example of an embodiment of the present invention; the structure and materials used can be arbitrarily replaced with known structures and materials as long as they do not impair the desired effect of the present invention.

[0078] Figure 1 This is a perspective view showing a portion of a typical first filter removed from a filter housed in a filter apparatus according to an embodiment of the present invention. The first filter 10 has a filter material 12, which includes three layers (11a to 11c) (the material and pore size of each layer will be described later).

[0079] like Figure 1 As shown, the filter material 12 is formed in a cylindrical shape, and a cylindrical core 13 is disposed inside the filter material 12. The cylindrical core 13 is formed in a mesh shape to allow liquid to pass through easily. The top (bottom) surfaces of the filter material 12 and the core 13 are concentric circles. Furthermore, a cover 14 is disposed on the upper part of the cylindrical filter material 12 and the core 13 to cover the upper ends of the aforementioned components. And, at the lower end of each component, a liquid inlet 15 is disposed for allowing liquid to flow in from the inside of the core 13.

[0080] Figure 2 This is a perspective view of a filter housed in a filter apparatus according to an embodiment of the present invention, with a portion of a typical second filter removed. The second filter 20 has a cylindrical second filter material 21 and a cylindrical core 22 that supports the second filter material 21 in contact with its inner side. The cylindrical core 22 is formed in a mesh shape to allow liquid to pass through easily. The top (bottom) surfaces of the second filter material 21 and the core 22 are concentric circles. A cover 23 is disposed on the upper part of the cylindrical second filter material 21 and the core 22 to cover the upper ends of each component. Furthermore, a liquid inlet 24 for discharging liquid from the inside of the core 22 is disposed at the lower end of each component. A protector may be disposed on the outer side of the second filter material 21 to allow liquid to pass through easily.

[0081] Figure 3 This is a perspective view showing an example of a filter unit according to an embodiment of the present invention. The filter unit 30 has a housing consisting of a body 31 and a cover 32, a filter (not shown) housed in the housing, and the cover 32 is provided with a liquid inlet 34 for connection to a pipe 33(a) and a liquid outlet 35 for connection to a pipe 33(b).

[0082] in addition, Figure 1 The filter unit 30 shown has a liquid inlet 34 and a liquid outlet 35 on the cover 32. However, the filter unit involved in this embodiment of the invention is not limited to this, as will be described in detail later. The liquid inlet and liquid outlet can be disposed at any position on the cover 32 and / or the body 31. Figure 1 The filter unit 30 shown has a housing with a cover 32 and a body 31, but the housing of the filter unit is not limited to the above, and may also be a housing in which the cover and the body are integrally formed.

[0083] Figure 4 This is a partial cross-sectional view of the filter unit 30 included in the filtration apparatus according to an embodiment of the present invention. The filter unit 30 has a liquid inlet 34 and a liquid outlet 35 in the cover 32. The liquid inlet 34 is connected to an internal conduit 41, and the liquid outlet 35 is connected to an internal conduit 42. The flow direction of the purified material is indicated by F1. The purified material flowing in from the liquid inlet 34 flows into the body 31 through the internal conduit 41 provided inside the cover 32, flows from the core of the filter 43 through the filter material to the outer surface, and is purified through this process.

[0084] The purified material flowing out to the outer surface is discharged to the outside through the internal pipe 42 and the liquid outlet 35 (according to the...). Figure 3 (F2 in the diagram represents the flow direction).

[0085] Figure 2 and Figure 3 In this design, the liquid inlet 34 and liquid outlet 35 are disposed on the cover 32 of the housing. However, the housing of the filter unit is not limited to this, and the liquid inlet 34 and liquid outlet 35 can be disposed at any position on the housing. In this case, the liquid inlet 34 is configured to allow the purified material to flow into the filter 43 from the outside, and the liquid outlet 35 is configured to allow the purified material to be discharged from the inside of the core of the filter 43. Furthermore, the above description is merely an example of a filter unit according to an embodiment of the present invention, and the filter unit of the filtration apparatus of the present invention is not limited to the above structure.

[0086] Figure 5This is a schematic diagram of the filtration apparatus 50 according to the first embodiment of the present invention. Regarding the filtration apparatus 50, in the pipelines (denoted as 51(a) to 51(c)) supplying the purified material, a primary filter unit 52 and a secondary filter unit 56 are sequentially arranged from the direction of supplying the purified material. The primary filter unit 52 (the filter unit disposed on the primary side) is connected to pipelines 51(a) and 51(b) at a liquid inlet 53 and a liquid outlet 54, and the secondary filter unit 56 (the filter unit disposed on the secondary side) is connected to pipelines 51(b) and 51(c) at a liquid inlet 57 and a liquid outlet 58.

[0087] In the filtration device 50 described above, the housing of the primary filter unit 52 houses the second filter 20. Furthermore, in the aforementioned filter unit, the housing of the secondary filter unit 56 (the filter unit disposed on the secondary side) houses the first filter 10. That is, in the aforementioned filtration device 50, the primary side of the first filter unit is provided with the second filter unit.

[0088] The flow direction of the purified material is indicated by F1 to F3. In the F1 direction, the purified material flowing in from the liquid inlet 53 is purified by the second filter of the primary filter unit 52, and then output from the liquid outlet 54. Next, the purified material flows through the pipe 51 in the direction indicated by F2, and flows from the liquid inlet 57 into the first filter in the secondary filter unit 56 for purification, and then is output from the liquid outlet 58 towards the F3 direction to the outside of the filter device (typically a filling device or the like connected to the filter device via a pipe).

[0089] In the above-described filtration device 50, a second filter 20 is housed in the housing of the primary filter unit 52, and a first filter 10 is housed in the housing of the secondary filter unit 56. However, the filtration device according to this embodiment of the invention is not limited to the above description; the first filter may be housed in the housing of the primary filter unit 52, and the second filter may be housed in the housing of the secondary filter unit 56. That is, the first filter unit may be disposed on the primary side of the second filter unit. Furthermore, when the first filter unit is disposed on the primary side of the second filter unit, the pore size of the filter material of the second filter may be smaller than or equal to the pore size of the filter material of the first filter.

[0090] The form of each component in the filtration device involved in the above embodiments will be described in detail below.

[0091] [Filter 1]

[0092] The filtration device according to the above embodiment houses a first filter within the housing of the secondary filter unit 56. The first filter of the filtration device according to the first embodiment of the present invention includes a first filter material 12 which is supplied from the primary side ( Figure 1 In the filter, the purified material flows in from the liquid inlet 15 and flows out to the outside through the first filter material 12, so "primary side" refers to the core side. It sequentially includes a nanoporous membrane layer 11a containing polyamide, a nanofiber layer 11b containing nylon, and a nanoporous membrane layer 11c containing ultra-high molecular weight polyethylene (UPE).

[0093] As explained, in the filtration device according to the embodiments of the present invention, the first filter material only needs to satisfy at least one of the specified requirements 1 to 3, and the above is one embodiment of the first filter material. Therefore, the first filter material can be, for example, a two-layer configuration including a nanoporous membrane layer 11a containing polyamide and a nanoporous membrane layer 11c containing UPE, or a single layer including a mixture of polyamide and UPE. The materials of each layer included in the first filter can be arbitrarily selected according to the properties of the substance being purified, the morphology of the filtered object (particles and colloids, etc.).

[0094] In this specification, "porous membrane" refers to a membrane that retains components (holding liquid) in a purified substance such as gels, particles, colloids, cells, and oligomers, but allows components smaller than the pores to pass through. The retention of components in the purified substance through a porous membrane sometimes depends on operating conditions, such as face velocity, the use of surfactants, pH, and combinations thereof, and can also depend on the pore size and structure of the porous membrane, as well as the size and structure of the particles to be removed (whether they are hard particles or gels, etc.). In a preferred embodiment, the porous membrane is a nanoporous membrane. Furthermore, in this specification, a nanoporous membrane refers to a porous membrane with a pore size of 1.0 to 100 nm.

[0095] Furthermore, in this specification, the pore size of the filter material refers to the pore size and pore size distribution determined by the bubble point of isopropanol (IPA).

[0096] From the viewpoint of achieving better results with the present invention, the difference between the cumulative 10% pore size and the cumulative 75% pore size in the cumulative pore distribution of the filter material of the first filter (cumulative 75% pore size - cumulative 10% pore size) is preferably 3 nm or more. Furthermore, the upper limit of the above difference is not particularly limited, but is preferably 50 nm or less, and more preferably 20 nm or less.

[0097] The aforementioned cumulative pore size distribution can be measured using the "Nanoperm porometer" manufactured by Seika Corporation. Cumulative pore size distribution refers to the dV / dlog of pores from 0 to a specified pore diameter. 10 The integral value of (D) (where V is the volume of the pores and D is the diameter of the pores) means that the cumulative 10% pore diameter refers to the pore diameter (nm) at the cumulative 10% of the cumulative pore distribution curve (representing the pore diameter at 10% of the total pore volume), and the cumulative 75% pore diameter refers to the pore diameter (nm) at the cumulative 75% of the cumulative pore distribution curve (representing the pore diameter at 75% of the total pore volume).

[0098] Furthermore, the ratio of the cumulative 75% pore size to the cumulative 10% pore size (cumulative 75% pore size / cumulative 10% pore size) is not particularly limited, but from the viewpoint of achieving better results in this invention, it is preferably 2.0 to 20.0.

[0099] In the above-mentioned filter material, the surface pore size of the primary side surface is different from that of the secondary side surface, preferably with the primary side surface pore size being larger. Furthermore, in the above-mentioned filter material, it is preferable that the pores gradually decrease in size from one surface side to the other.

[0100] The pore size of the filter material used as the first filter is not particularly limited, but is preferably 1 to 100 nm, more preferably 2 to 50 nm, and even more preferably 2 nm or more and less than 50 nm.

[0101] The pore size distribution of the nanoporous membrane layer, i.e., the polyamide membrane layer, is not particularly limited, but the pore size distribution determined by the bubble point measurement based on the IPA or HFE7200 porosity measurement method is preferably 5 to 100 nm, more preferably 5 to 50 nm, and even more preferably 10 to 50 nm.

[0102] Furthermore, the pore size distribution of the nanoporous membrane layer, i.e., the UPE membrane layer, is not particularly limited, but is preferably 2 to 200 nm, more preferably 2 to 100 nm, and even more preferably 2 to 50 nm. The nanofiber layer preferably has a pore size distribution that is larger than that of the polyamide membrane layer or the UPE membrane layer.

[0103] Polyamide films are typically non-sieve films, which are layers that capture particles via a non-sieve holding mechanism or layers optimized for particle capture.

[0104] When the purified material contains gel as an impurity, the gel is often negatively charged. In the removal of such gel, polyamide (e.g., nylon) membranes function as non-sieve membranes. Typical non-sieve membranes include nylon-6 membranes and nylon-6,6 membranes, but are not limited to these.

[0105] In addition, the term "non-sieve retention mechanism" as used in this specification refers to retention generated by mechanisms such as interference, diffusion, and adsorption that are independent of the pressure drop of the filter or the bubble point of the porous membrane.

[0106] Non-sieve retention includes retention mechanisms such as interference, diffusion, and adsorption of target particles from the purified material, independent of the pressure drop of the filter or the bubble point of the filter material. Adsorption of particles to the membrane surface can be mediated, for example, by intermolecular van der Waals forces and electrostatic forces. Interference occurs when particles moving in a non-sieve membrane layer with a serpentine path cannot change direction quickly enough without contact with the membrane. Particle transport via diffusion is mainly generated by the random motion or Brownian motion of small particles, resulting from the constant probability of collision between the particles and the filter material. Non-sieve retention mechanisms can become active when there is no repulsive force between the particles and the filter material. Therefore, the non-sieve retention rate (%) can be evaluated under neutral conditions (e.g., near the isoelectric point of the membrane).

[0107] UPE membranes are typically sieve membranes. Sieve membranes are primarily layers used to capture particles via a sieve holding mechanism, or layers optimized for particle capture via a sieve holding mechanism.

[0108] Typical examples of sieve membrane layers include polytetrafluoroethylene (PTFE) membranes and UPE membranes, but are not limited to these.

[0109] Furthermore, the "sieve retention mechanism" refers to retention based on the result of particles being larger than the pores of a porous membrane. The sieve retention force can be improved by forming a filter cake (which becomes an aggregation of particles that remove the target on the membrane surface). The filter cake effectively functions as a secondary filter.

[0110] Various surfactants can be used to evaluate sieve retention. Particles larger than the pores of the porous membrane result in sieve retention.

[0111] Sodium dodecyl sulfate (SDS) or Triton X-100 can be used as the surfactant. The amount of surfactant used can be selected to exceed the critical micelle concentration (CMC). The concentration of the surfactant exceeding the CMC can be measured using a surface tension meter that monitors the surface tension of the fluid. The surfactant concentration is preferably in the range of 0.1% (w / w) to 0.3% (w / w), and sieving conditions are provided accordingly. Under sieving conditions, the porous membrane preferably has a retention rate of 90-99.99%, 95-99.99%, 98-99.99%, or 99-99.99%. In several embodiments, the porous membrane preferably has a retention rate of at least 90% (preferably 95% or more, more preferably 98% or more, and even more preferably 99% or more) under sieving conditions.

[0112] By combining a nanofiber layer and a nanoporous membrane layer, a filter material can be obtained that requires less time to filter the purified material than when using the nanoporous membrane layer alone. The particle retention energy of the combination of the nanofiber layer and the nanoporous membrane layer in a liquid is superior to that of the nanoporous membrane layer alone in a liquid. Furthermore, the first filter in the filtration device according to the above embodiment includes a filter material (first filter material) comprising a nanoporous membrane layer containing polyamide, a nanoporous membrane layer containing ultra-high molecular weight polyethylene (UPE), and a nanofiber layer containing nylon. However, the first filter material in the filtration device according to the embodiment of the present invention is not limited to the above; for example, the nanoporous membrane layer may also be formed from other polyolefins and polyfluorocarbons.

[0113] Furthermore, if the nanofiber layer is a nylon nanofiber layer, it can retain particles in the purified material more efficiently, thereby improving particle retention energy without increasing the flow time of the purified material required for filtration. Additionally, the nanofiber layer typically comprises a porous support (e.g., a porous nonwoven fabric) and a fiber layer formed on the porous support, but the nanofiber layer included in the first filter material of the embodiment of the present invention comprises a porous support made of nylon and a nylon fiber layer formed on the aforementioned porous support.

[0114] Examples of nanofiber layers include porous supports (porous nonwoven fabric, manufactured by ASAHI KASEIFIBERS CORPORATION, material: nylon, area weight: 40g / m²). 2 The morphology of “NO0540” and the fiber layer formed on the aforementioned support by electrospinning, but not limited thereto.

[0115] The material of the fiber layer is not particularly limited as long as it is a polymer capable of forming a fiber layer. Examples of polymers include polyamides. Examples of polyamides include nylon 6 and nylon 6,6. Poly(ether sulfone) can be used as the polymer forming the fiber layer. When the nanofiber layer is on the primary side of the porous membrane layer, it is preferable that the surface energy of the nanofiber layer is higher than that of the polymer below, which is the material of the porous membrane layer. Examples of such a combination include, for instance, the nanofiber layer being made of nylon and the porous membrane layer being made of polyethylene (UPE).

[0116] The method for manufacturing the fiber layer is not particularly limited, and well-known methods can be used. Examples of methods for manufacturing nanofiber layers include electrospinning, electroblowing, and meltblowing.

[0117] The nanofiber layer can be self-supporting on its own, but typically it is supported by a porous support. Alternatively, the fiber layer formed on the porous support can be peeled off and used as the nanofiber layer alone.

[0118] Porous supports capable of forming nanofiber layers are permeable to liquids, and the porous supports themselves can possess some filtration functions. When forming a fiber layer on a porous support, if the shape of the porous support is pleated, a pleated nanofiber layer can be obtained. Furthermore, by forming a fiber layer on a porous support, the strength of the nanofiber layer and the filter material containing the aforementioned nanofiber layer can also be improved.

[0119] Furthermore, when the filter material is formed from the porous support itself, it is typically a deep-layer filter material formed from the aforementioned porous support. That is, both the fiber layer and the porous support have filtration functions.

[0120] Materials used as porous supports include, for example, nylon 6, nylon 6,6, aramid, polyethylene terephthalate, and polyethersulfone. Specifically, "NO5040," which contains nylon, is an example manufactured by KASEI FIBERS CORPORATION.

[0121] The structure of nanoporous membranes (e.g., porous membranes containing UPE and PTFE) is not particularly limited, and the shape of the pores can be, for example, lace-like, tassel-like, and nodular.

[0122] The size distribution and location of pores in a nanoporous membrane are not particularly limited. The size distribution can be smaller, and the pores can be symmetrical. Alternatively, the size distribution can be larger, and the pores can be asymmetrical (these membranes are also called "asymmetric porous membranes"). In asymmetric porous membranes, the pore size varies within the membrane, typically increasing from one side of the membrane to the other. The surface with larger pores is called the "open side," and the surface with smaller pores is called the "closed side."

[0123] Furthermore, as an asymmetric porous membrane, for example, the size of the pores becomes minimal at a certain point within the membrane's thickness (also known as the "hourglass shape").

[0124] By using an asymmetric porous membrane, the primary side is made to have larger pores; in other words, if the primary side is made to be open, a pre-filtration effect can be achieved.

[0125] When the porous membrane is an asymmetric porous membrane, the nanofiber layer can be stacked on either the "closed side" or the "open side" of the asymmetric porous membrane. The preferred configuration is that the "open side" is in contact with the nanofiber layer.

[0126] Porous membranes can contain thermoplastic polymers such as PESU (polyethersulfone), PFA (a copolymer of perfluoroalkoxyalkane, tetrafluoroethylene and perfluoroalkoxyalkane), polyamide and polyolefin, or polytetrafluoroethylene.

[0127] Among these, ultra-high molecular weight polyethylene (UHMWPE) is preferred as the material for the porous membrane. UHMWPE refers to thermoplastic polyethylene with extremely long chains and a molecular weight of over one million, typically between 2 million and 6 million.

[0128] When the first filter material includes a nanoporous membrane layer, the nanoporous membrane layer can be a nanoparticle sintered membrane layer. A nanoparticle sintered membrane layer refers to a layer with nanopore size obtained by sintering nanoparticles. Specifically, the layers described in Japanese Patent Application Publication No. 2013-047389 and Japanese Patent Application Publication No. 2016-141756 can be used.

[0129] In this specification, the description of a filter having filter material comprising two or more layers with different pore structures typically includes layers in the following combination, or layers further combined from these. Furthermore, the pore structure of each layer is indicated before and after the " / " in the following examples.

[0130] • Nanoporous membrane / nanofiber layer

[0131] • Asymmetric porous membranes / Symmetric porous membranes

[0132] • The distribution of pore size varies in each layer.

[0133] • The pores in each layer are distributed differently in the membrane.

[0134] The shapes of the holes in each layer are different.

[0135] From the perspective of obtaining a filtration device with superior effects of the present invention, it is preferable that the filtration material comprises a nanoporous membrane layer and a nanofiber layer.

[0136] When the first filter material contains a nylon nanofiber layer, as a combination of layers, for example, [examples can be provided].

[0137] • Case where the non-sieve membrane layer is located between the sieve membrane layer and the nylon nanofiber layer

[0138] • Case where the sieve membrane layer is located between the non-sieve membrane layer and the nylon nanofiber layer

[0139] • The case where the nylon nanofiber layer is between the sieve membrane layer and the non-sieve membrane layer

[0140] The materials comprising each layer of the first filter material included in the first filter can be materials other than those described above. Examples of materials for each layer of the first filter material include inorganic and organic materials. Examples of inorganic materials include metals, glass, and diatomaceous earth. Examples of organic materials include polymers, such as nylons like 6-nylon and 6,6-nylon; polyolefins like polyethylene and polypropylene; polystyrene; polyimide; polyamide-imide; polysulfone; polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-trifluorochloroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc.

[0141] In view of the fact that a filtration device with superior effects of the present invention can be obtained, it is preferably selected from at least one of the group consisting of nylon, polyethylene, polypropylene, polyfluorocarbon, cellulose, diatomaceous earth, polystyrene, glass and polysulfone.

[0142] Furthermore, the filter material may include a layer comprising a surface-treated substrate. The method for surface-treating the filter material is not particularly limited, and known methods can be used. Examples of surface-treating methods include chemical modification, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering, with chemical modification or plasma treatment being preferred.

[0143] Plasma treatment is preferred because the surface of the filter material is hydrophilized. The water contact angle of the surface of the filter material that is hydrophilized by plasma treatment is not particularly limited, but the static contact angle at 25°C, measured by a contact angle meter, is preferably 60° or less, more preferably 50° or less, and even more preferably 30° or less.

[0144] As a chemical modification treatment, the preferred method is to introduce ion exchange groups into the substrate.

[0145] That is, as a filter material, the materials mentioned above are used as the substrate, and it is preferable to introduce ion exchange groups into the substrate. Typically, a filter material having a layer of substrate containing ion exchange groups on the surface of the substrate is preferred. As a surface-modified substrate, there is no particular limitation, but from the perspective of easier manufacturing, it is preferable to introduce ion exchange groups into the polymer.

[0146] Regarding ion exchange groups, examples of cation exchange groups include sulfonic acid groups, carboxyl groups, and phosphate groups, while examples of anion exchange groups include secondary, tertiary, and quaternary ammonium groups. The method for introducing ion exchange groups into polymers is not particularly limited; examples include reacting compounds possessing ion exchange groups and polymerizable groups with the polymer, typically through grafting.

[0147] For example, when using polyolefin fibers (such as polyethylene and polypropylene) as a substrate, these fibers are irradiated with ionizing radiation (alpha rays, beta rays, gamma rays, X-rays, and electron beams, etc.) to generate active components (free radicals) in the polymer substrate. The irradiated substrate is then immersed in a monomer-containing solution, allowing the monomer to graft polymerize onto the substrate. As a result, the monomer is generated as a graft polymerized side chain bonded to the polyolefin fiber. The polyolefin fiber, with this generated monomer as a side chain, is then contacted with a compound containing anion exchange groups or cation exchange groups, thereby introducing ion exchange groups into the monomer of the grafted side chain to obtain the final product. This product does not introduce ion exchange groups into the polyolefin fiber as the main chain, but rather into the monomer of the side chain grafted to the main chain.

[0148] Furthermore, the filter material can be a structure that combines woven or nonwoven fabrics with ion exchange groups formed by radiation graft polymerization and conventional glass wool, woven or nonwoven filter materials.

[0149] Furthermore, the first filter material can comprise layers with different pore structures in the thickness direction. Examples of different pore structures in the thickness direction include structures where the surface pore size of the primary side of the first filter material differs from the surface pore size of the secondary side of the filter material.

[0150] The first filter has a first filter material with the aforementioned characteristics, thus enabling it to remove impurities from the purified material more efficiently. This tendency is particularly pronounced when the first filter material comprises two or more layers, each containing a different material.

[0151] [Second Filter]

[0152] The filtration device according to the above embodiment houses a second filter within the housing of the primary filter unit 52. The second filter material 21 of the second filter in the filtration device according to the first embodiment of the present invention comprises polytetrafluoroethylene.

[0153] The pore size of the second filter material is not particularly limited, but from the viewpoint of obtaining a filter device with better effects than those of the present invention, it is preferably 200 nm or less, more preferably 100 nm or less, further preferably 50 nm or less, particularly preferably 10 nm or less, and most preferably 5 nm or less. As a lower limit, it is preferably 1 nm or more, more preferably 2 nm or more.

[0154] The pore size of the second filter material is not particularly limited. However, considering the possibility of obtaining a filtration device with superior effects of the present invention, the pore size of the filter material in the second filter is preferably less than or equal to the pore size of the first filter material. Furthermore, "less than or equal to the pore size of the first filter material" means that when two or more second filters are housed in multiple housings of the filtration device, the pore size of the second filter material in each second filter is less than or equal to the pore size of the first filter material.

[0155] In addition, the pore size of the second filter material in the second filter can be greater than or equal to the pore size of the first filter material in the first filter.

[0156] The ratio of the pore size of the second filter material to the pore size of the first filter material (pore size of the second filter material / pore size of the first filter material) is not particularly limited, but is preferably 0.1 to 10, more preferably 0.1 to 1.0, even more preferably less than 0.1, and particularly preferably 1, 0.1 to 0.9.

[0157] The material used as the second filter material is not particularly limited, and the material already described as the first filter material can be used. However, from the viewpoint of obtaining a filter device with better effects of the present invention, it is preferable to include at least one material selected from the group consisting of nylon, polyethylene, polypropylene, polyfluorocarbon, cellulose, diatomaceous earth, polystyrene, glass, and polysulfone.

[0158] In addition, the second filter material may be different from at least one of the groups consisting of filter media, layer structure, micropore structure and pore size selected as the first filter material.

[0159] From the viewpoint that a filtration device with superior effects of the present invention can be obtained, it is preferable that the second filter material comprises the same material as any one of the two or more layers of the first filter material.

[0160] Apart from the above, the preferred form of the second filter material is not specifically described, and the preferred form of the first filter material has already been described.

[0161] The operating temperature of the filtration device described in the above embodiments is not particularly limited, but it is generally preferred to operate it at a temperature below room temperature. In this case, it is preferable to remove impurities from the filter material that have not been washed out of the purified material.

[0162] To prevent impurities originating from the filter material from being washed into the purified material, it is only necessary to adjust the value of the distance (Ra) between the purified material and the filter material in the Hansen space, and the radius of the interaction sphere of the filter material, i.e., the value of the interaction radius (R0).

[0163] That is, considering the possibility of obtaining a filtration device with superior effects of the present invention, in the relationship between the Hansen solubility parameters δDp, δPp, and δHp, and the interaction radius R0 of at least one filter material selected from the group consisting of the filter material of the first filter and the filter material of the second filter, and the Hansen solubility parameters δDs, δPs, and δHs of the purified substance, Ra is determined by the following formula:

[0164] Ra 2 =4(δDs-δDp) 2 +(δPs-δPp) 2 +(δHs-δHp) 2

[0165] In the case of Ra, the ratio of Ra to R0 is preferably 1.0 or less.

[0166] Furthermore, it is even more preferable that the above-mentioned content is satisfied in the relationship between the second filter material (the filter material included in the second filter) and the purified material, and it is particularly preferable that the above-mentioned content is satisfied in the respective relationships between the first filter material and the second filter material and the purified material.

[0167] Furthermore, when the first filter material is a filter material comprising two or more layers each containing different materials, the first filter material satisfying the above relationship means that the above relationship is satisfied in at least one layer, and more preferably, the above relationship is satisfied in all layers.

[0168] The ratio (Ra / R0) of the distance (Ra) in the Hansen space between the purified material and the filter material to the interaction radius (R0) of the filter material is not particularly limited. However, considering that impurities are less likely to be washed from the filter material into the purified material, it is preferably 1.0 or less, more preferably 0.98 or less, even more preferably 0.95 or less, and particularly preferably 0.93 or less. As a lower limit, it is not particularly limited, but it is preferably 0.5 or more, more preferably 0.6 or more, and even more preferably 0.7 or more.

[0169] If Ra / R0 is within the above range, the filter material is not easily dissolved in the purified substance. That is, impurities originating from the filter material are not easily washed into the purified substance.

[0170] In addition, in this specification, the Hansen solubility parameters, etc., can be the values ​​described in Charles M. Hansen's "Hansen Solubility Parameters: A User's Handbook", CRC Press (2007) and Allan FM Barton's "The CRC Handbook and Solubility Parameters and Cohesion Parameters" (1999).

[0171] Hansen solubility parameters, etc., can also be calculated using "Molecular Modeling Pro" software, version 5.1.9 (ChemSW, Fairfield CA, www.chemsw.com) or HansenSolubility from Dynacomp Software.

[0172] In addition, the value of R0 can be obtained experimentally or by using the value recorded in literature.

[0173] Ra can be calculated from the three components of the Hansen solubility parameter: the dispersive force component (δD), the polar or dipole interaction component (δP), and the hydrogen bonding component (δH). Furthermore, the unit of the Hansen solubility parameter is (MPa). 1 / 2 .

[0174] The above three components can be considered as coordinates in a three-dimensional space (Hansen space). When plotting the filter material and the purified substance in Hansen space, the closer they are, the easier they are to dissolve in each other, which means that impurities originating from the filter material are easily washed into the purified substance.

[0175] At this point, the distance Ra between the Hansen solubility parameter of the filter material and the Hansen solubility parameter of the purified substance is expressed by the following formula.

[0176] (Formula) Ra 2 =4(δDs-δDp) 2 +(δPs-δPp) 2 +(δHs-δHp) 2

[0177] Furthermore, in the above formula, δDp, δPp, and δHp represent the components of the Hansen solubility parameter of the filter material, and δDs, δPs, and δHs represent the components of the Hansen solubility parameter of the purified substance. This is compared with the radius (R0) of the interaction sphere centered on the Hansen solubility parameter of the filter material.

[0178] The following table illustrates the values ​​of each component of the Hansen solubility parameter for the organic solvent used as the purified substance, and Ra / R0 when the filter material is polyethylene.

[0179] [Table 1]

[0180]

[0181] [Second Implementation Form]

[0182] The second embodiment of the present invention relates to a filtration device having a second filter unit on both the primary and secondary sides of a first filter unit.

[0183] Figure 6 This is a schematic diagram of the filtration device 60 according to the second embodiment of the present invention. Regarding the filtration device 60, in the pipeline (including 51(a) to 51(d)) for supplying the purified material, a primary filter unit 52, a secondary filter unit 56 and a tertiary filter unit 61 are arranged sequentially from the direction of supplying the purified material.

[0184] The tertiary filter unit 61 is connected to pipes 51(c) and 51(d) at the liquid inlet 62 and liquid outlet 63.

[0185] In the filtration device 60 described above, a second filter is housed in the housing of the primary filter unit 52, a first filter is housed in the housing of the secondary filter unit 56, and a second filter is housed in the housing of the tertiary filter unit 61. That is, a second filter unit is disposed on the primary side of the first filter unit, and another second filter unit is disposed on the secondary side of the first filter unit.

[0186] The flow direction of the purified material is indicated by F1 to F4. In the F1 direction, the purified material flowing into the primary filter unit 52 from pipe 51(a) via liquid inlet 53 is purified by the second filter contained within the primary filter unit 52, and then output from liquid outlet 54. Next, the purified material flows in the F2 direction through pipe 51(b) via liquid inlet 57 into the secondary filter unit 56. The purified material is purified by the first filter contained within the secondary filter unit 56, and then output from liquid outlet 58. Next, the purified material flows in the F3 direction through pipe 51(c) via liquid inlet 62 into the tertiary filter unit 61. The purified material is purified by the second filter contained within the tertiary filter unit 61, and then output from liquid outlet 63, flowing in the F4 direction through pipe 51(d).

[0187] The filter material of the filter included in the filter device according to this embodiment will be described in detail below.

[0188] <First Filter Material>

[0189] The material used as the first filter material is not particularly limited, but from the viewpoint of obtaining a filter device with superior effects of the present invention, it is preferable to include a layer comprising a surface-treated substrate. The form of the surface-treated substrate is as already described.

[0190] Furthermore, the first filter material meets the specified requirements, but as the first filter material of this embodiment, examples include a layer comprising a surface-treated substrate and a layer comprising an untreated substrate (preferably the same substrate).

[0191] <Second Filter Material>

[0192] The materials and pore sizes of the two second filter materials are not particularly limited, and the materials and pore sizes described in the first embodiment can be used. However, considering the possibility of obtaining a filtration device with superior effects of the present invention, the pore size of the second filter material housed in the housing of the third filter unit 61 is preferably less than or equal to the pore size of the first filter material. The pore size of the second filter on the secondary side is generally preferably 1.0 to 50 nm, more preferably 1.0 to 10 nm, and even more preferably 1.0 to 2.0 nm.

[0193] <Variations of the second embodiment>

[0194] A variation of the filtration device described in the second embodiment is as follows: a second filter unit is disposed on the primary side of the first filter unit, and the second filter unit is also disposed on the secondary side of the first filter unit. The filter material of the second filter unit disposed on the secondary side has a pore size that is less than or equal to the pore size of the filter material of the first filter unit. The filter material of the first filter includes a layer comprising a substrate that has undergone surface treatment.

[0195] The configurations of the various parts of the filtration device involved in this embodiment are as described above.

[0196] [Other Implementation Forms]

[0197] Other embodiments of the present invention involve a filtration device in which the first filter is configured as a backwashable filtration device by allowing cleaning fluid to flow from the secondary side of the first filter unit to the primary side of the filter unit.

[0198] Regarding the configuration of the first filter as backwashable, an example is the inclusion of a cleaning fluid supply device on the secondary side of the filter unit. The cleaning fluid supply device typically includes a reservoir for cleaning fluid connected to the secondary side of the filter unit via a pipeline, and a pump and valve disposed within the pipeline. During backwashing, cleaning fluid is supplied from the reservoir to the pipeline, and transferred from the secondary side of the filter unit to the primary side under pressure or without pressure, thereby cleaning the first filter.

[0199] The cleaning solution that can be used in the above description is not particularly limited, and examples include the medicine itself, the liquid used to dilute the medicine, the solvent (organic solvent and / or water) contained in the medicine, and mixtures of the above solvents.

[0200] Furthermore, the filtration device according to this embodiment is configured to backwash the first filter. However, the filtration device according to the embodiment of the present invention is not limited to the above, and may also be configured to backwash one or more second filters.

[0201] [Purification Device]

[0202] Figure 7 This is a schematic diagram illustrating a pharmaceutical purification apparatus according to an embodiment of the present invention. The pharmaceutical purification apparatus 70 according to an embodiment of the present invention includes a filter device 60, as already described, in the pipeline.

[0203] The filter device 60 is connected to the manufacturing tank 71 via pipe 51(a) and to the filling device 72 via pipe 51(d). Pipe 51(d) then branches off via valve 74(d) and connects to the manufacturing tank 71 via circulation pipe 73(a).

[0204] In addition, the above-mentioned circulation pipe 73(a) conforms to a circulatory path.

[0205] In the purification apparatus 70, the purified material is supplied from the pipeline 73(b) described later to the manufacturing tank 71 for storage. The stored purified material flows into the filtration apparatus 60 via the pipeline 51(a) for purification (in the figure, according to the flow direction indicated by F5).

[0206] The purified substance (medicinal solution) obtained in the filtration device 60 is transferred to the filling device 72 via the pipeline 51(a) and filled into the container to produce the medicinal solution container described later (in the figure, according to the flow direction indicated by F6).

[0207] Here, when the purified material that has been purified in the filtration device 60 is purified again in the filtration device, the purified material that has been purified by the third filter unit 61 is sent back to the manufacturing tank 71 from the pipeline 51 (d) through the valve 74 (d) via the circulation pipeline 73 (a), so that the above process can be repeated again (in the figure, according to the flow direction indicated by F7).

[0208] The purified material, which has been purified in the three-stage filter unit 61, can be returned to the manufacturing tank 71. This allows the purified material to be circulated and filtered in the purification device, thereby enabling the production of a drug solution with superior defect suppression performance.

[0209] in addition, Figure 7 In the purification apparatus, valve 74(d) is disposed in pipeline 51(d). However, the purification apparatus according to the embodiment of the present invention is not limited to the above description and may be disposed in pipeline 51(c), and may not have valve 74(d). In the purification apparatus without valve 74(d), the purified material is not sent back to the manufacturing tank.

[0210] Furthermore, in the aforementioned purification apparatus, the first filter is configured to be backwashable by allowing the cleaning solution to flow from the secondary side to the primary side. When backwashing the first filter, valves 74(e) and 74(f) are opened, and cleaning solution is supplied from line 75(b) (at this time, valves 74(b) and 74(d) are preferably closed). Line 75(b) is connected to a cleaning solution supply device (not shown). The supplied cleaning solution then flows from the secondary side to the secondary filter unit 56, cleaning the first filter housed within the housing of the filter unit 56, and is recovered from line 75(a). Line 75(a) is connected to a cleaning solution recovery device (not shown).

[0211] In the purification apparatus, the first filter is configured to be backwashable as described above, thereby extending the lifespan of the first filter.

[0212] Furthermore, in the filtration apparatus described in the above embodiments, the first filter (secondary filter unit 56) is configured to be backwashable. However, the purification apparatus of the present invention is not limited to the above, and the primary filter unit 52 and the tertiary filter unit 61 may also be configured to be backwashable.

[0213] [Second Embodiment of the Purification Device]

[0214] The second embodiment of the present invention is a purification apparatus for a drug solution that further includes a distillation apparatus on the primary side of the above-mentioned filtration apparatus. Figure 8 A schematic diagram showing the purification apparatus for the pharmaceutical solution involved in the above-described embodiment.

[0215] The purification apparatus 80 for the pharmaceutical solution described in this embodiment has the same structure in the pipeline as the purification apparatus 70 already described.

[0216] Furthermore, in the purification apparatus 80, the manufacturing tank 71 is connected to the distillation column 81 via pipe 83(b). The purified material is supplied to the distillation column 81 from pipe 73(c), where it is distilled. The distilled purified material is then introduced into the manufacturing tank 71 via pipe 73(b) (flow direction of F8 in the figure). After the purified material is introduced into the manufacturing tank 71, the solution is purified using the method described above.

[0217] Furthermore, while the purification apparatus 80 includes a manufacturing tank in its piping, the purification apparatus for the pharmaceutical solution described in this embodiment may not include such a manufacturing tank. That is, it may be configured such that the primary side of the filtration apparatus 60 is connected to the distillation column via piping.

[0218] [Manufacturing equipment]

[0219] Figure 9 This diagram illustrates the manufacturing apparatus according to an embodiment of the present invention. The pharmaceutical solution manufacturing apparatus 90 of this embodiment has the same structure in its piping as the purification apparatus 80 described previously, and the distillation column 81 is connected to the mixing apparatus 91 via pipe 73(b). The mixing apparatus 91 consists of multiple water storage tanks (92(a), 92(b), and 92(c)) and pipes 73(d) and 73(c) connecting them. Water storage tanks 92(b) and 92(c) are connected to water storage tank 92(a) via pipes 73(d) and 73(e), respectively.

[0220] Furthermore, water storage tanks 92(b) and 92(c) are connected to reaction tanks 93(a) and 93(b) respectively via pipes 73(f) and 73(g).

[0221] The method for manufacturing a pharmaceutical solution using the above-described manufacturing apparatus 90 will be described. First, the raw materials are reacted in reaction tanks 93(a) and 93(b) to generate reactants.

[0222] The reactants are not particularly limited; for example, the various components described above as being contained in the pharmaceutical solution can be cited. For example, the organic solvents contained in the pharmaceutical solution can be cited.

[0223] The method for obtaining reactants is not particularly limited, and well-known methods can be used. For example, a method can be given in which one or more raw materials are reacted in the presence of a catalyst to obtain reactants.

[0224] More specifically, examples include processes for producing butyl acetate by reacting acetic acid with n-butanol in the presence of sulfuric acid; processes for producing 1-hexanol by reacting ethylene, oxygen, and water in the presence of Al(C2H5)3; processes for producing 4-methyl-2-pentene by reacting cis-4-methyl-2-pentene in the presence of Ipc2BH ((+)-diisopinocampheylborane); processes for producing PGMEA (propylene glycol 1-monomethyl ether 2-acetic acid) by reacting propylene oxide, methanol, and acetic acid in the presence of sulfuric acid; processes for producing IPA (isopropyl alcohol) by reacting acetone and hydrogen in the presence of copper oxide-zinc oxide-aluminum oxide; and processes for producing ethyl lactate by reacting lactic acid and ethanol.

[0225] Next, the obtained reactants are mixed in a specified amount using mixing device 91 to prepare the desired pharmaceutical solution composition. Specifically, the reactants generated in reaction tanks 93(a) and 93(b) are transferred to water storage tanks 92(b) and 92(c) according to their type via pipelines 73(f) and 73(g). The transferred reactants are then transferred to water storage tank 92(a) via pipelines 73(d) and 73(e), where they are mixed in specified amounts to prepare the purified product.

[0226] Next, the obtained purified substance is purified using distillation column 81. That is, the purified substance is transferred to distillation column 81 via line 73(c) for distillation. The distilled purified substance is transferred to manufacturing tank 71 via line 73(b), and then the same method as described for purifying the drug solution using purification device 70 is performed.

[0227] In the pharmaceutical liquid manufacturing apparatus 90 described in the above embodiment, a mixing device 91 is provided on the primary side of the filtration device 60. However, the pharmaceutical liquid manufacturing apparatus according to the embodiment of the present invention is not limited to the above, and the mixing device 91 may also be provided on the secondary side of the filtration device 60.

[0228] In addition, the filtration device, purification device and manufacturing device described above are equipped with valves and pumps for transferring the purified material in each pipeline, but these are omitted in the above drawings and are not shown.

[0229] [Corrosion-resistant materials]

[0230] The materials used for the wetted portions of each unit (manufacturing tank, pipeline, and filling device, etc.) in the aforementioned filtration, purification, and manufacturing apparatus are not particularly limited. From the viewpoint of obtaining a pharmaceutical solution with superior defect suppression performance, the materials are formed from at least one material (corrosion-resistant material) selected from the group consisting of fluorinated resin and electropolished metal material. The metal material is preferably composed of at least one material selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is more than 25% by mass relative to the total mass of the metal material. Furthermore, regarding the wetted portions being formed from the aforementioned material, examples can be given of the aforementioned components being constructed from the aforementioned material or of forming a coating layer by covering the wetted portions of the aforementioned components with the aforementioned material.

[0231] <Metal materials that have undergone electropolishing>

[0232] The metal material used in the manufacture of the aforementioned electropolished metal material is not particularly limited as long as it contains at least one of the components selected from chromium and nickel, and the total content of chromium and nickel is more than 25% by mass relative to the total mass of the metal material. Examples include stainless steel and nickel-chromium alloys.

[0233] The total content of chromium and nickel in the metallic material is preferably 25% by mass or more, and more preferably 30% by mass or more, relative to the total mass of the metallic material.

[0234] Furthermore, the upper limit of the total content of chromium and nickel in metallic materials is not particularly limited, but is generally preferred to be 90% by mass or less.

[0235] The type of stainless steel is not particularly limited, and any known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferred, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferred. Examples of austenitic stainless steels include SUS (Stainless Steel for Steel) 304 (8% by mass of Ni and 18% by mass of Cr), SUS304L (9% by mass of Ni and 18% by mass of Cr), SUS316 (10% by mass of Ni and 16% by mass of Cr), and SUS316L (12% by mass of Ni and 16% by mass of Cr).

[0236] In addition, the Ni and Cr contents in parentheses above are the proportions relative to the total mass of the metallic material.

[0237] The nickel-chromium alloy is not particularly limited, and any known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy with a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferred relative to the total mass of the metal material.

[0238] Examples of nickel-chromium alloys include HASTELLOY (trade name, hereinafter the same), Monel (trade name, hereinafter the same), and Inconel (trade name, hereinafter the same). More specifically, examples include HASTELLOY C-276 (Ni content 63% by mass, Cr content 16% by mass), HASTELLOY-C (Ni content 60% by mass, Cr content 17% by mass), and HASTELLOY C-22 (Ni content 61% by mass, Cr content 22% by mass).

[0239] Furthermore, nickel-chromium alloys may contain boron, silicon, tungsten, molybdenum, copper, and cobalt, in addition to the alloys mentioned above, depending on the requirements.

[0240] The method for electropolishing metallic materials is not particularly limited, and known methods can be used. For example, the methods described in paragraphs

[0011] -

[0014] of Japanese Patent Application Publication No. 2015-227501 and paragraphs

[0036] -

[0042] of Japanese Patent Application Publication No. 2008-264929 can be used.

[0241] It is speculated that the passivation layer on the surface of the metallic material is electropolished to make the chromium content in it higher than that in the parent phase. Therefore, the metallic components are less likely to flow from the inner wall covered by the electropolished metallic material, or from the units having inner walls formed by the electropolished metallic material, into the purified material.

[0242] Additionally, the metal material can be polished. The polishing method is not particularly limited, and known methods can be used. The size of the polishing abrasive used in fine polishing is not particularly limited, but considering that the surface roughness of the metal material is more easily reduced, a size of #400 or less is preferred. Furthermore, polishing is preferably performed before electropolishing.

[0243] Fluororesin

[0244] As for the aforementioned fluoropolymer, there are no particular limitations as long as it is a resin (polymer) containing fluorine atoms, and known fluoropolymers can be used. Examples of fluoropolymers include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer, and cyclized polymers of perfluoro(butenyl vinyl ether) (CYTOP (registered trademark)).

[0245] The manufacturing method for each of the above-mentioned components is not particularly limited, and can be manufactured by known methods. For example, by attaching a fluoropolymer lining to the wetted portion of each component containing metal or resin, or by forming a film by coating the wetted portion of each component containing metal or resin with a composition containing fluoropolymer, the inner walls of each component covered with the above-mentioned material (corrosion-resistant material) can be manufactured.

[0246] Furthermore, for example, by electropolishing the wetted parts of each component of a metal material whose total content of chromium and nickel exceeds 25% by mass relative to the total mass of the metal material, it is possible to manufacture components whose inner walls are formed of a material (corrosion-resistant material).

[0247] <Medicinal Solution>

[0248] The pharmaceutical solution that can be produced using the purification apparatus described above is not particularly limited, and known pharmaceutical solutions can be cited as examples. Among them, a pharmaceutical solution for semiconductor manufacturing is preferred.

[0249] (The first form of the liquid medicine)

[0250] The pharmaceutical solution according to one embodiment of the present invention contains a solvent. The solvent is not particularly limited and can include water or organic solvents.

[0251] The content of solvent in the pharmaceutical solution is not particularly limited, but it is generally preferred to be 97.0% to 99.999% by mass relative to the total mass of the pharmaceutical solution, and more preferably 99.9% to 99.9% by mass. Solvent 1 can be used alone or in combination with two or more organic solvents. When two or more organic solvents are used, the total content is preferably within the above range.

[0252] Furthermore, in this specification, "solvent" refers to water and / or liquid organic compounds contained in the total mass of the above-mentioned pharmaceutical solution at a concentration exceeding 10,000 ppm by mass per component. That is, in this specification, water and / or liquid organic compounds containing more than 10,000 ppm by mass relative to the total mass of the above-mentioned pharmaceutical solution are referred to as conforming solvents.

[0253] In addition, the term "liquid" in this specification refers to a liquid at atmospheric pressure and a temperature of 25°C.

[0254] The type of organic solvent is not particularly limited, and known organic solvents can be used. Examples of organic solvents include alkylene glycol monoalkyl ether carboxylic esters, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionic acid esters, cyclic lactones (preferably with 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably with 4 to 10 carbon atoms), alkylene carbonate esters (e.g., diethyl carbonate), alkyl alkoxyacetic acid esters, and alkyl pyruvate esters.

[0255] Furthermore, as an organic solvent, solvents described in, for example, Japanese Patent Application Publication No. 2016-057614, Japanese Patent Application Publication No. 2014-219664, Japanese Patent Application Publication No. 2016-138219 and Japanese Patent Application Publication No. 2015-135379 can be used.

[0256] The organic solvent is preferably selected from at least one of the following groups: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, γ-butyrolactone, diisopentanone, butyl acetate, isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, n-methyl-2-pyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone, and 2-heptanone.

[0257] The solution may contain components other than organic solvents. Examples of such components include metallic impurities, organic impurities, and fluoride ions.

[0258] The solution may contain metallic impurities (metal particles and metal ions). The definition and determination method of metal ions have been explained.

[0259] The content of metal particles in the medicinal solution is not particularly limited, but generally, it is preferably 100 ppt by mass or less relative to the total mass of the medicinal solution, more preferably 50 ppt by mass or less, and even more preferably 30 ppt by mass or less. The lower limit is not particularly limited, but is generally preferably 0.001 ppt by mass or more. The medicinal solution may contain only one type of metal particle or two or more types. When the medicinal solution contains two or more types of metal particles, the total content is preferably within the above-mentioned range.

[0260] The content of metal ions in the medicinal solution is not particularly limited, but generally, it is preferably 100 ppt by mass or less relative to the total mass of the medicinal solution, more preferably 50 ppt by mass or less, and even more preferably 30 ppt by mass or less. The lower limit is not particularly limited, but is generally preferably 0.001 ppt by mass or more. The medicinal solution may contain only one type of metal ion or two or more types. When the medicinal solution contains two or more types of metal ions, the total content is preferably within the above-mentioned range.

[0261] The pharmaceutical solution may contain organic impurities. The definition and determination methods for organic impurities have been explained.

[0262] The content of organic impurities in the medicinal solution is not particularly limited. From the viewpoint of obtaining better effects of the present invention, it is preferably 10 ppb or less by mass relative to the total mass of the medicinal solution, more preferably 5 ppb or less by mass, and even more preferably 3 ppb or less by mass. The lower limit is not particularly limited, but it is preferable that the solution does not contain organic impurities.

[0263] When the chemical solution contains organic impurities, these impurities act as ligands relative to the metal, forming complexes with it. These complexes are highly hydrophobic and easily remain on the surface of semiconductor substrates treated with the chemical solution, resulting in defects.

[0264] The solution may contain fluoride ions. The definition and determination method of fluoride ions have been explained.

[0265] The content of fluoride ions in the solution is not particularly limited. From the viewpoint of obtaining better effects of the present invention, it is preferably 1 ppm or less relative to the total mass of the solution, more preferably 0.5 ppm or less, and even more preferably 0.3 ppm or less. The lower limit is not particularly limited, but it is preferable that the solution does not contain fluoride ions.

[0266] (Second implementation of the liquid medicine)

[0267] The pharmaceutical solution involved in the second embodiment of the present invention can be a photosensitive or radiosensitive linear resin composition. The photosensitive or radiosensitive linear resin composition is not particularly limited, but is preferably the photosensitive or radiosensitive linear resin composition described below.

[0268] (Photosensitive or radiosensitive linear resin composition)

[0269] (A) Resin

[0270] Photosensitive or radiosensitive linear resin compositions typically contain a resin whose polarity increases through the action of an acid, thereby reducing its solubility relative to a developer containing an organic solvent.

[0271] The resin (hereinafter also referred to as "resin (A)") whose polarity increases due to the action of acid and whose solubility relative to the developer containing organic solvent decreases is preferably a resin (hereinafter also referred to as "acid-decomposing resin" or "acid-decomposing resin (A)") having a group (hereinafter also referred to as "acid-decomposing group") in the main chain or side chain of the resin, or in both the main chain and side chain, that decomposes and generates an alkali-soluble group by the action of acid.

[0272] Furthermore, resin (A) is more preferably a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure (hereinafter also referred to as "alicyclic hydrocarbon acid-degradable resin"). Resins having a monocyclic or polycyclic alicyclic hydrocarbon structure have higher hydrophobicity, which is believed to improve the developability when developing areas of photosensitive or radiosensitive linear films with weak light irradiation intensity using organic developing solutions.

[0273] The photosensitive or radiosensitive linear resin composition containing resin (A) is preferably used in cases of irradiation with ArF excimer laser light.

[0274] Examples of alkali-soluble groups contained in resin (A) include groups having phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl)methylene groups, (alkylsulfonyl) (alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tri(alkylcarbonyl)methylene groups, and tri(alkylsulfonyl)methylene groups.

[0275] Preferred alkali-soluble groups include carboxylic acid groups, fluorinated alcohol groups (preferably hexafluoroisopropanol) or sulfonic acid groups.

[0276] The preferred group as a group that can be decomposed by acid (acid-decomposable group) is a group in which the hydrogen atoms of these base-soluble groups are replaced by a group that can be decomposed by acid.

[0277] Examples of groups that can be removed by acid include -C(R) 36 (R) 37 (R) 38 ), -C(R) 36 (R) 37 (OR) 39 ) and C(R) 01 (R) 02 (OR) 39 )wait.

[0278] In the formula, R 36 ~R 39 Each can be independently represented as alkyl, cycloalkyl, aryl, aralkyl, or alkenyl. R 36 With R 37They can bond together to form a ring.

[0279] Among them, R 01 ~R 02 Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkyl group, or alkenyl group.

[0280] As an acid-degrading group, walnut ester group, enol ester group, acetal ester group, third-order alkyl ester group, etc. are preferred. Third-order alkyl ester group is even more preferred.

[0281] As resin (A), it is preferred to have a resin containing repeating units having a partial structure represented by the following formula (pI) to general formula (pV).

[0282] [Chemical Formula 1]

[0283]

[0284] In the general formulas (pI) to (pV),

[0285] R 11 The radical represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or dibutyl, and Z represents the atomic group required to form a cycloalkyl group with a carbon atom.

[0286] R 12 ~R 16 Each of these groups independently represents a straight-chain or branched alkyl or cycloalkyl group having 1 to 4 carbon atoms. R 12 ~R 14 At least one of them or R 15 and R 16 Any one of them represents a cycloalkyl group.

[0287] R 17 ~R 21 Each of these groups independently represents a straight-chain or branched alkyl or cycloalkyl group having 1 to 4 hydrogen atoms and carbon atoms. R 17 ~R 21 At least one of them represents a cycloalkyl group. And, R 19 R 21 Any one of them represents a straight-chain or branched alkyl or cycloalkyl group with 1 to 4 carbon atoms.

[0288] R 22 ~R 25 Each of these groups independently represents a straight-chain or branched alkyl or cycloalkyl group having 1 to 4 hydrogen atoms and carbon atoms. R 22 ~R 25 At least one of them represents a cycloalkyl group. And, R 23 With R 24 They can bond together to form a ring.

[0289] In equations (pI) to (pV), R is... 12 ~R 25 The alkyl group in the text refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms.

[0290] R 11 ~R 25 The cycloalkyl group or the cycloalkyl group formed by Z and carbon atoms can be monocyclic or polycyclic. Specifically, examples include groups having a monocyclic, bicyclic, tricyclic, or tetracyclic structure with 5 or more carbon atoms. The number of carbon atoms is preferably 6 to 30, more preferably 7 to 25. These cycloalkyl groups may also have substituents.

[0291] Preferred cycloalkyl groups include adamantyl, noradamantyl, decahydronaphthalene residue, tricyclodecyl, tetracyclododecyl, norcamphenyl, cedrolyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl. More preferably, adamantyl, norcamphenyl, cyclohexyl, cyclopentyl, tetracyclododecyl, or tricyclodecyl are also preferred.

[0292] Examples of further substituents for these alkyl or cycloalkyl groups include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). Examples of further substituents that may be present in the aforementioned alkyl, alkoxy, or alkoxycarbonyl groups include hydroxyl groups, halogen atoms, and alkoxy groups.

[0293] The structures represented by formulas (pI) to (pV) in the aforementioned resin can be used to protect alkali-soluble groups. Various groups known in the art can be cited as alkali-soluble groups.

[0294] Specifically, examples include structures in which the hydrogen atoms of the carboxylic acid group, sulfonic acid group, phenolic group, and thiol group are replaced by structures represented by general formulas (pI) to (pV), with the preferred example being structures in which the hydrogen atoms of the carboxylic acid group or sulfonic acid group are replaced by structures represented by general formulas (pI) to (pV).

[0295] The repeating unit having an alkali-soluble group protected by the structure represented by formulas (pI) to (pV) is preferably the repeating unit represented by the following formula (pA).

[0296] [Chemical Formula 2]

[0297]

[0298] In this context, R represents a hydrogen atom, a halogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. Multiple Rs may be the same or different.

[0299] A represents a single or combination of two or more groups selected from the group consisting of single bonds, alkylene groups, ether groups, thioether groups, carbonyl groups, ester groups, amide groups, sulfonamide groups, carbamate groups, and urea groups. A single bond is preferred.

[0300] Rp1 represents any one of the groups in the above formulas (pI) to (pV).

[0301] The repeating unit represented by formula (pA) is preferably based on 2-alkyl-2-adamantyl (meth)acrylate or dialkyl (1-adamantyl)methyl (meth)acrylate.

[0302] The following shows specific examples of repeating units represented by formula (pA), but the present invention is not limited thereto.

[0303] [Chemical Formula 3]

[0304]

[0305] In one embodiment, the repeating unit having an acid-decomposable group is preferably an acid-decomposable repeating unit having an acid-dissociating group a having 4 to 7 carbon atoms, and satisfies any one of the following conditions (i-1) to (iv-1).

[0306] (i-1): The maximum number of carbon atoms in the acid-free radical a above is 4, and the protection rate is less than 70 mol%.

[0307] (ii-1): Resins with a maximum carbon number of 5 for the acid-free radical a and a protection rate of 60 mol% or less.

[0308] (iii-1): The maximum number of carbon atoms in the acid-free radical a above is 6, and the protection rate is less than 47 mol%.

[0309] (iv-1): Resins with a maximum carbon number of 7 for the acid-free radical a and a protection rate of 45 mol% or less.

[0310] The protection rate represents the proportion of the total number of acid-degradable repeating units contained in the resin to all repeating units.

[0311] Furthermore, the number of carbon atoms in the aforementioned acid detachment group a refers to the number of carbon atoms contained in the detachment group.

[0312] This enables a reduction in the shrinkage of the resist film, an increase in the depth of focus (DOF), and a reduction in line edge roughness (LER).

[0313] When the resist film is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light (EUV, etc.) with a wavelength of less than 50 nm, the resin (A) preferably contains repeating units having aromatic hydrocarbon groups, and more preferably contains repeating units having phenolic hydroxyl groups. As repeating units having phenolic hydroxyl groups, repeating units shown below are particularly preferred.

[0314] [Chemical Formula 4]

[0315]

[0316] [Chemical Formula 5]

[0317]

[0318] The resin (A) may contain one type of repeating unit with an acid-decomposable group, or two or more types may be used together.

[0319] The resin (A) is preferably a repeating unit containing a lactone structure or a sulcinolone (cyclic sulfonate) structure.

[0320] As the lactone group or sulfonolactone group, any lactone or sulfonolactone structure can be used, preferably a 5- to 7-membered ring lactone or sulfonolactone structure. It is more preferable to have other ring structures formed by condensing the 5- to 7-membered ring lactone or sulfonolactone structure into a bicyclic or spirocyclic structure. More preferably, it has repeating units having a lactone or sulfonolactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17), (SL1-1), and (SL1-2). Furthermore, the lactone or sulfonolactone structure can be directly bonded to the main chain. As the lactone or sulfonolactone structure, general formulas (LC1-1), (LC1-4), (LC1-5), and (LC1-8) are preferred, with general formula (LC1-4) being more preferred. By using specific lactone or sulfonolactone structures, LWR and development defects are improved.

[0321] [Chemical Formula 6]

[0322]

[0323] [Chemical Formula 7]

[0324]

[0325] The lactone or sulopentalide moiety may or may not have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 2 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-degradable groups. More preferably, they are alkyl groups with 1 to 4 carbon atoms, cyano groups, or acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple substituents (Rb2) may be the same or different, and the multiple substituents (Rb2) may bond with each other to form a ring.

[0326] Optical isomers are typically present in repeating units having lactone or sulcinolone groups, and any optical isomer can be used. Furthermore, a single optical isomer can be used alone, or multiple optical isomers can be used in combination. When primarily using one optical isomer, its optical purity (ee) is preferably 90% or higher, more preferably 95% or higher.

[0327] Regarding the content of repeating units having lactone or sulfonyl lactone structures, when multiple types are included, their total content relative to all repeating units in the resin is preferably 15 to 60 mol%, more preferably 20 to 50 mol%, and even more preferably 30 to 50 mol%.

[0328] To improve the effect, two or more repeating units with lactone or sulfonyl lactone structures can be used together.

[0329] When the photosensitive or radiosensitive linear resin composition is used for ArF exposure, from the viewpoint of transparency to ArF light, the resin (A) is preferably free of aromatic groups.

[0330] As resin (A), it is preferable that all repeating units are composed of (meth)acrylate repeating units. In this case, it is possible to use any one of the following: all repeating units are methyl acrylate repeating units, all repeating units are acrylate repeating units, or all repeating units are a mixture of methyl acrylate repeating units and acrylate repeating units, wherein the acrylate repeating units are preferably 50 mol% or less of all repeating units.

[0331] As a preferred resin (A), for example, the resin described in paragraphs

[0152] to

[0158] of Japanese Patent Application Publication No. 2008-309878 can be cited, but the present invention is not limited thereto.

[0332] Resin (A) can be synthesized using conventional methods (e.g., free radical polymerization). Examples of common synthesis methods include uniform polymerization, where the monomer and initiator are dissolved in a solvent and polymerized by heating, and dropwise polymerization, where a solution of the monomer and initiator is added dropwise to a heated solvent over 1 to 10 hours. Dropwise polymerization is preferred. Examples of reaction solvents include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; and solvents for dissolving photosensitive or radiosensitive linear resin compositions, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone (described later). It is preferable to use the same solvent as that used for the photosensitive or radiosensitive linear resin composition for polymerization. This helps suppress particle formation during storage.

[0333] The polymerization reaction is preferably carried out in an inert gas environment such as nitrogen and / or argon. Commercially available free radical initiators (azo initiators, peroxides, etc.) are used as polymerization initiators. Azo initiators are preferred, especially those with ester, cyano, or carboxyl groups. Examples of preferred initiators include azobisisobutyronitrile, azobis(dimethyl)valerate, and dimethyl 2,2'-azobis(2-methylpropionate). The initiator is added in addition or in batches as needed. After the reaction is complete, the polymer is recovered by adding it to a solvent and recovering it as a powder or solid. The reaction concentration is 5–50% by mass, preferably 10–30% by mass. The reaction temperature is typically 10°C–150°C, preferably 30°C–120°C, and more preferably 60–100°C.

[0334] Purification can be achieved using the following common methods: liquid-liquid extraction to remove residual monomers or oligomers by washing with water or combining with appropriate solvents; purification methods in solution states, such as ultrafiltration, to extract only molecules below a certain molecular weight; reprecipitation methods to remove residual monomers by adding a resin solution dropwise to a poor solvent to coagulate the resin in the poor solvent; and purification methods in solid states, such as washing the resin slurry obtained by filtration with a poor solvent.

[0335] Regarding the weight-average molecular weight (Mw) of resin (A), as the polystyrene conversion value obtained by GPC (gel permeation chromatography), it is preferably 1,000 to 200,000, more preferably 1,000 to 20,000, and even more preferably 1,000 to 15,000. By setting the weight-average molecular weight to 1,000 to 200,000, it is possible to prevent the deterioration of heat resistance and dry etching resistance, as well as the deterioration of developability and film-forming properties due to increased viscosity.

[0336] The dispersion (molecular weight distribution) of the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) in resin (A) (Mw / Mn) is typically 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably in the range of 1.2 to 2.0. The smaller the dispersion, the better the resolution and pattern shape, and the smoother the sidewalls of the pattern, and the better the roughness.

[0337] The content of resin (A) in the total solids of the photosensitive or radiosensitive linear resin composition is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass.

[0338] Furthermore, resin (A) can be used in combination with one type or multiple types.

[0339] From the viewpoint of compatibility with the composition for forming a protective film, resin (A) is preferably free of fluorine atoms and silicon atoms.

[0340] (B) Compounds that produce acids upon exposure to activating light or radiation.

[0341] Photosensitive or radiosensitive linear resin compositions typically contain compounds that produce acid upon exposure to activating light or radiation (also known as "photoacid generators").

[0342] As such photoacid-generating agents, known compounds and mixtures thereof that generate acid by irradiation with activating light or radiation, such as photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, pigment-based photodecolorizing agents, photochromic agents, or microresists, can be appropriately selected.

[0343] Examples include diazonium salts, phosphonium salts, sulfonium salts, monazine salts, imide sulfonates, oxime sulfonates, diazonium disulfones, disulfones, and o-nitrobenzyl sulfonates.

[0344] Furthermore, compounds obtained by introducing groups or compounds that generate acids through irradiation with activating light or radiation into the main chain or side chain of a polymer can be used, such as those described in U.S. Patent No. 3,849,137, German Patent No. 3,914,407, Japanese Patent Application Publication No. 63-026653, Japanese Patent Application Publication No. 55-164824, Japanese Patent Application Publication No. 62-069263, Japanese Patent Application Publication No. 63-146038, Japanese Patent Application Publication No. 63-163452, Japanese Patent Application Publication No. 62-153853, and Japanese Patent Application Publication No. 63-146029.

[0345] Furthermore, it is also possible to use compounds that generate acids through light, as described in U.S. Patent No. 3,779,778 and European Patent No. 126,712.

[0346] As a photoacid-generating agent contained in a photosensitive or radiosensitive linear resin composition, it is preferably a compound that generates an acid with a cyclic structure by irradiation with activating light or radiation. As the cyclic structure, a monocyclic or polycyclic alicyclic group is preferred, more preferably a polycyclic alicyclic group. As the carbon atom constituting the cyclic skeleton of the alicyclic group, it is preferably free of carbonyl carbon.

[0347] As a photoacid generator contained in a photosensitive or radiosensitive linear resin composition, examples that are preferred include, for example, compounds that generate acid by irradiation with activating light or radiation as represented by the following formula (3) (specific acid generator).

[0348] [Chemical Formula 8]

[0349]

[0350] (Anions)

[0351] In equation (3),

[0352] Xf represent either a fluorine atom or an alkyl group substituted with at least one fluorine atom.

[0353] R4 and R5 represent hydrogen atoms, fluorine atoms, alkyl groups, or alkyl groups substituted with at least one fluorine atom, respectively. When multiple R4 and R5 are present, they can be the same or different.

[0354] L represents a binary linkage base. When multiple bases exist, L can be the same or different.

[0355] W represents an organic group containing a cyclic structure.

[0356] o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0357] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0358] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is more preferably a fluorine atom or CF3. Particularly preferred are two Xf atoms that are fluorine atoms.

[0359] R4 and R5 represent hydrogen atoms, fluorine atoms, alkyl groups, or alkyl groups substituted with at least one fluorine atom, respectively. When multiple R4 and R5 are present, they can be the same or different.

[0360] The alkyl group used as R4 and R5 is preferably an alkyl group that can have substituents and has 1 to 4 carbon atoms. R4 and R5 are preferably hydrogen atoms.

[0361] Specific examples and preferred methods of alkyl groups substituted with at least one fluorine atom are the same as those of Xf in general formula (3).

[0362] L represents a binary linkage base. When multiple bases exist, L can be the same or different.

[0363] Examples of divalent linkers include -COO- (-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene (preferably with 1 to 6 carbon atoms), cycloalkylene (preferably with 3 to 10 carbon atoms), alkenyl (preferably with 2 to 6 carbon atoms), or combinations thereof. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene- are preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene-, or -OCO-alkylene- are more preferred.

[0364] W represents an organic group containing a cyclic structure. Preferably, the organic group is cyclic.

[0365] Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

[0366] Alicyclic groups can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl, cyclohexyl, and cyclooctyl monocyclic cycloalkyl groups. Examples of polycyclic alicyclic groups include norcamphenyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. From the viewpoint of suppressing diffusion in the film and improving MEEF (Mask Error Enhancement Factor) in the PEB (post-exposure heating) process, alicyclic groups with a large volume structure having 7 or more carbon atoms, such as norcamphenyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, didamantylgroup, and adamantyl, are preferred.

[0367] The aryl group can be monocyclic or polycyclic. Examples of such aryl groups include phenyl, naphthyl, phenanthryl, and anthracene. Among them, naphthyl is preferred because it has a relatively low absorbance at 193 nm.

[0368] The heterocyclic group can be monocyclic or polycyclic, but polycyclic groups are better at suppressing acid diffusion. Furthermore, the heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocycles include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. Furan rings, thiophene rings, pyridine rings, or decahydroisoquinoline rings are particularly preferred as heterocycles in the heterocyclic group. Furthermore, examples of lactone and sulfonyl lactone rings include the lactone and sulfonyl lactone structures illustrated in the aforementioned resins.

[0369] The aforementioned cyclic organic groups may also have substituents. Examples of such substituents include alkyl groups (which can be straight-chain or branched, preferably with 1 to 12 carbon atoms), cycloalkyl groups (which can be monocyclic, polycyclic, or spirocyclic, preferably with 3 to 20 carbon atoms), aryl groups (preferably with 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atoms constituting the cyclic organic groups (the carbon atoms that contribute to ring formation) can be carbonyl carbons.

[0370] o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0371] In one embodiment, o in formula (3) is an integer from 1 to 3, p is an integer from 1 to 10, and q is preferably 0. Xf is preferably a fluorine atom, R4 and R5 are both preferably hydrogen atoms, and W is preferably a polycyclic hydrocarbon group. o is more preferably 1 or 2, and even more preferably 1. p is more preferably an integer from 1 to 3, even more preferably 1 or 2, and particularly preferably 1. W is more preferably a polycyclic cycloalkyl group, and even more preferably adamantyl or didamantyl.

[0372] Among the anions represented by the above general formula (3), SO3 is preferably an example of a combination of partial structures other than W. - -CF2-CH2-OCO-, SO3 - -CF2-CHF-CH2-OCO-, SO3 - -CF2-COO-, SO3 - -CF2-CF2-CH2-、SO3 - -CF2-CH(CF3)-OCO-.

[0373] (cation)

[0374] In general formula (3), X + It represents a cation.

[0375] X+ There is no particular limitation as long as it is a cation, but as a preferred embodiment, for example, the cation (Z) in formula (ZI) or (ZII) described later can be cited. - (The part other than)

[0376] (Preferred method)

[0377] Preferred agents for a particular acid generator include, for example, compounds represented by the following general formulas (ZI) or (ZII).

[0378] [Chemical Formula 9]

[0379]

[0380] In the above general formula (ZI),

[0381] R 201 R 202 and R 203 Each organic group can be represented independently.

[0382] As R 201 R 202 and R 203 The number of carbon atoms in the organic groups is usually 1 to 30, preferably 1 to 20.

[0383] Furthermore, R 201 ~R 203 Two of the atoms can bond to form a ring structure, which can contain oxygen atoms, sulfur atoms, ester bonds, amide bonds, and carbonyl groups. As R 201 ~R 203 The group formed by the two bonds in the group can be alkylene (e.g., butylene, pentylene).

[0384] Z - The anions in formula (3) specifically refer to the following anions.

[0385] [Chemical Formula 10]

[0386]

[0387] As a result of R 201 R 202 and R 203 The organic groups represented can be exemplified by the corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3), and (ZI-4) described later.

[0388] Alternatively, it can be a compound having multiple structures represented by the general formula (ZI). For example, it can also be a compound having R represented by the formula (ZI). 201 ~R 203At least one of the compounds in the formula (ZI) is linked to the R group of another compound via a single bond or linker. 201 ~R 203 Compounds with at least one bond in the structure.

[0389] As further preferred (ZI) components, compounds (ZI-1), (ZI-2), (ZI-3), and (ZI-4) described below can be cited.

[0390] First, the compound (ZI-1) will be described.

[0391] Compound (ZI-1) is R of the above general formula (ZI). 201 ~R 203 arylsulfonium compounds in which at least one aryl group is an aryl group, i.e., compounds with arylsulfonium as a cation.

[0392] In arylsulfonium compounds, R can be 201 ~R 203 All are aryl, or can be R 201 ~R 203 One part is aryl and the remainder is alkyl or cycloalkyl.

[0393] Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0394] The aryl group in the arylsulfonium compound is preferably phenyl or naphthyl, more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, nitrogen atom, or sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups can be the same or different.

[0395] The alkyl or cycloalkyl groups in the arylsulfonium compound are preferably straight-chain or branched alkyl groups with 1 to 15 carbon atoms and cycloalkyl groups with 3 to 15 carbon atoms, such as methyl, ethyl, propyl, n-butyl, dibutyl, tributyl, cyclopropyl, cyclobutyl and cyclohexyl.

[0396] R 201 ~R 203 The aryl, alkyl, and cycloalkyl groups may also have alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 14 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups as substituents.

[0397] Next, the compound (ZI-2) will be described.

[0398] Compound (ZI-2) is represented by R in formula (ZI). 201 ~R 203 Each of these refers to a compound that does not have an aromatic ring. The aromatic ring is an aromatic ring that also contains heteroatoms.

[0399] As R 201 ~R 203 The organic groups that do not contain aromatic rings typically have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0400] R 201 ~R 203 Each of the following is preferably alkyl, cycloalkyl, allyl or vinyl, more preferably straight-chain or branched 2-oxoalkyl, 2-oxocycloalkyl or alkoxycarbonylmethyl, and even more preferably straight-chain or branched 2-oxoalkyl.

[0401] As R 201 ~R 203 Alkyl and cycloalkyl groups, preferably including straight-chain or branched alkyl groups having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl) and cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl, cyclohexyl and norbenzene).

[0402] R 201 ~R 203 It can be further substituted with halogen atoms, alkoxy groups (e.g., 1 to 5 carbon atoms), hydroxyl groups, cyano groups, or nitro groups.

[0403] Next, the compound (ZI-3) will be described.

[0404] The compound (ZI-3) refers to the compound represented by the following formula (ZI-3), which is a compound having a benzoylmethylsulfonium salt structure.

[0405] [Chemical Formula 11]

[0406]

[0407] In formula (ZI-3),

[0408] R 1c ~R 5c Each of these can be independently represented as a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group, or arylthio group.

[0409] R 6c and R 7cEach can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or aryl group.

[0410] R x and R y Each can be independently represented as alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl, or vinyl.

[0411] R 1c ~R 5c Any two or more of them and R 5c With R 6c R 6c With R 7c R 5c With R x and R x With R y They can be bonded separately to form a ring structure, which may contain oxygen atoms, sulfur atoms, ketone groups, ester bonds or amide bonds.

[0412] Examples of the aforementioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, or polycyclic fused rings composed of two or more of these rings. Examples of ring structures include 3 to 10-membered rings, preferably 4 to 8-membered rings, and more preferably 5 or 6-membered rings.

[0413] As R 1c ~R 5c Any two or more of them and R 6c With R 7c and R x With R y Examples of groups formed by bonding include butenyl and pentylene.

[0414] As R 5c With R 6c and R 5c With R x The bonded group is preferably a single bond or an alkylene group. Examples of alkylene groups include methylene and ethylene.

[0415] Zc - The anions in equation (3) are specifically as described above.

[0416] As R 1c ~R 5c Specific examples of the alkoxy group in the alkoxycarbonyl group and the above-mentioned R 1c ~R 5c The specific examples are the same as those for alkoxy groups.

[0417] As R 1c ~R 5cSpecific examples of alkyl groups in alkyl carbonyl groups and alkyl thio groups are the same as those of alkyl groups in the above-mentioned R1c to R5c groups.

[0418] As R 1c ~R 5c Specific examples of cycloalkyl groups in cycloalkyl carbonyl groups and R as described above 1c ~R 5c The specific examples are the same for cycloalkyl groups.

[0419] As R 1c ~R 5c Specific examples of aryl groups in aryloxy and arylthio groups and as described above R 1c ~R 5c The specific examples are the same as those of aryl groups.

[0420] As cations in compounds (ZI-2) or (ZI-3) of the present invention, examples can be found in paragraph

[0036] of the specification of U.S. Patent Application Publication No. 2012 / 0076996.

[0421] Next, compound (ZI-4) will be described.

[0422] The compound (ZI-4) is represented by the formula (ZI-4).

[0423] [Chemical Formula 12]

[0424]

[0425] In formula (ZI-4),

[0426] R 13 This refers to a hydrogen atom, fluorine atom, hydroxyl group, alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, or a group containing a cycloalkyl group. These groups may have substituents.

[0427] R 14 When multiple groups are present, each independently represents a hydroxyl, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkanecarbonyl, alkylsulfonyl, cycloalkylsulfonyl, or a group having a cycloalkyl group. These groups may have substituents.

[0428] R 15 Each R15 group can independently represent an alkyl, cycloalkyl, or naphthyl group. These groups may have substituents. Two R15 groups can bond together to form a ring. 15 When atoms bond together to form a ring, the ring framework can also contain heteroatoms such as oxygen and nitrogen atoms. In one mode, two R atoms... 15 Preferably, they are alkylene groups bonded together to form a ring structure.

[0429] l represents an integer from 0 to 2.

[0430] r represents an integer from 0 to 8.

[0431] Z - The anions in equation (3) are specifically as described above.

[0432] In equation (ZI-4), R is... 13 R 14 and R 15 The alkyl group is preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms, and is preferably methyl, ethyl, n-butyl, tributyl, etc.

[0433] Examples of cations that can be used as compounds represented by formula (ZI-4) in this invention include those described in paragraphs

[0121] ,

[0123] ,

[0124] of Japanese Patent Application Publication No. 2010-256842 and paragraphs

[0127] ,

[0129] ,

[0130] of Japanese Patent Application Publication No. 2011-076056.

[0434] Next, equation (ZII) will be explained.

[0435] In formula (ZII), R 204 and R 205 Each can be represented independently as aryl, alkyl, or cycloalkyl.

[0436] As R 204 and R 205 The aryl group is preferably phenyl or naphthyl, more preferably phenyl. 204 and R 205 The aryl group can be an aryl group having a heterocyclic structure including oxygen atoms, nitrogen atoms, or sulfur atoms. Examples of aryl groups with heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0437] As R 204 and R 205 Alkyl and cycloalkyl groups are preferably straight-chain or branched alkyl groups with 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl) and cycloalkyl groups with 3 to 10 carbon atoms (cyclopentyl, cyclohexyl, norbenzene).

[0438] R 204 and R 205 Aryl, alkyl, and cycloalkyl groups can have substituents. As R 204 and R 205 The aryl, alkyl, and cycloalkyl groups may have substituents, such as alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 15 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.

[0439] Z - The anions in equation (3) are specifically as described above.

[0440] In one embodiment, the molecular weight of the acid-generating agent is preferably 870 or less, more preferably 800 or less, even more preferably 700 or less, and particularly preferably 600 or less. This improves DOF ​​and LER.

[0441] Furthermore, in this invention, when a compound that produces acid by irradiation with activating light or radiation has a molecular weight distribution, the weight-average molecular weight is used as a reference for the molecular weight.

[0442] Acid-generating agents can be used alone or in combination of two or more.

[0443] The content of the acid generating agent in the composition (the total of multiple components) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, further preferably 3 to 20% by mass, and particularly preferably 3 to 15% by mass, based on the total solid content of the composition.

[0444] As an acid generating agent, when a compound represented by formula (ZI-3) or (ZI-4) is included, the content of the acid generating agent included in the composition (the total of multiple acid generating agents if they exist) is based on the total solid content of the composition, preferably 5 to 35% by mass, more preferably 8 to 30% by mass, further preferably 9 to 30% by mass, and particularly preferably 9 to 25% by mass.

[0445] (C) Solvent

[0446] Examples of organic solvents that can be used to dissolve the above-mentioned components to prepare photosensitive or radiosensitive linear resin compositions include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionic acid esters, cyclic lactones with 4 to 10 carbon atoms, monoketone compounds with 4 to 10 carbon atoms that may contain rings, alkylene carbonates, alkyl alkoxyacetic acid esters, and alkyl pyruvate esters.

[0447] Examples of alkylene glycol monoalkyl ether carboxylic esters include, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

[0448] Examples of alkylene glycol monoalkyl ethers include, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

[0449] Examples of alkyl lactate esters include, for example, methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

[0450] Alkyl alkoxypropionate esters, such as ethyl 3-ethoxypropionate, 3-methoxypropionate, 3-ethoxymethylpropionate and ethyl 3-methoxypropionate, are preferred examples.

[0451] Examples of cyclic lactones having 4 to 10 carbon atoms include, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanoic acid lactone, and α-hydroxy-γ-butyrolactone.

[0452] Examples of preferred monoketone compounds containing rings and having 4 to 10 carbon atoms include 2-butanone, 3-methylbutanone, tributyl ethyl ketone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6- Dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, and 3-methylcycloheptanone.

[0453] Examples of alkylene carbonates include, for example, propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

[0454] Examples of alkyl alkoxyacetic acid esters include, for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-2-propyl acetate.

[0455] Alkyl esters of pyruvate are preferably methyl pyruvate, ethyl pyruvate and propyl pyruvate.

[0456] Solvents with a boiling point of 130°C or higher at room temperature and pressure are examples of solvents that can be used optimally. Specifically, examples include cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, propylene carbonate, butyl butyrate, isoamyl acetate, and methyl 2-hydroxyisobutyrate.

[0457] The above solvents can be used alone or in combination with two or more.

[0458] As an organic solvent, a mixed solvent can be used, which is a mixture of solvents containing hydroxyl groups in the mixed structure and solvents that do not contain hydroxyl groups in the mixed structure.

[0459] Examples of solvents containing hydroxyl groups include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate, among which propylene glycol monomethyl ether and ethyl lactate are particularly preferred.

[0460] Examples of solvents that do not contain hydroxyl groups include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N,N-dimethylacetamide, and dimethyl sulfoxide. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, or butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, or 2-heptanone are most preferred.

[0461] The mixing ratio (mass ratio) of the solvent containing hydroxyl groups to the solvent without hydroxyl groups is 1 / 99 to 99 / 1, preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 60 / 40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of the solvent without hydroxyl groups is particularly preferred.

[0462] The solvent is preferably a mixture of two or more solvents containing propylene glycol monomethyl ether acetate.

[0463] (D) Basic compounds

[0464] To reduce the time-dependent performance changes from exposure to heating, the photosensitive or radiosensitive linear resin composition preferably contains an alkaline compound.

[0465] Furthermore, from the viewpoint of DOF and EL performance, the photosensitive or radiosensitive linear resin composition preferably contains an alkaline compound. That is, the alkaline compound contained in the photosensitive or radiosensitive linear resin composition migrates to the protective film during pre-baking after the protective film is formed, and a portion of it returns to the unexposed areas of the photosensitive or radiosensitive linear film during PEB. At this time, the exposed areas become more susceptible to acid diffusion due to the reduced alkaline compound content, while the unexposed areas become less susceptible to acid diffusion due to the increased alkaline compound content. Thus, the contrast in acid diffusion between the exposed and unexposed areas of the photosensitive or radiosensitive linear film becomes stronger, resulting in further improvement in DOF and EL performance.

[0466] As basic compounds, compounds having the structures represented by the following formulas (A) to (E) are preferred examples.

[0467] [Chemical Formula 13]

[0468]

[0469] In equations (A) to (E),

[0470] R 200 R 201 and R 202 They can be the same or different, and represent hydrogen atoms, alkyl groups (preferably with 1 to 20 carbon atoms), cycloalkyl groups (preferably with 3 to 20 carbon atoms), or aryl groups (with 6 to 20 carbon atoms), wherein R 201 With R 202 They can bond together to form a ring.

[0471] Regarding the aforementioned alkyl group, the preferred alkyl group having a substituent is an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

[0472] R 203 R 204 R 20 5 and R 206 They can be the same or different, representing alkyl groups with 1 to 20 carbon atoms.

[0473] The alkyl groups in these formulas (A) to (E) are more preferably unsubstituted.

[0474] Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc. Further preferred compounds include compounds having imidazole structure, diazabicyclic structure, onium hydroxide structure, carboxylic onium salt structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having hydroxyl and / or ether bonds, aniline derivatives having hydroxyl and / or ether bonds, etc.

[0475] Examples of compounds with an imidazole structure include imidazole, 2,4,5-triphenylimidazolium, and benzimidazole. Examples of compounds with a diazabicyclic structure include 1,4-diazabicyclic [2,2,2]octane, 1,5-diazabicyclic [4,3,0]non-5-ene, and 1,8-diazabicyclic [5,4,0]undec-7-ene. Examples of compounds with a onium hydroxide structure include triarylsulfonium hydroxide, benzoylmethylsulfonium hydroxide, and sulfonium hydroxides containing a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)sulfonium hydroxide, benzoylmethylthiophenonium hydroxide, and 2-oxopropylthiophenonium hydroxide. Compounds having a carboxylic acid onium salt structure are compounds whose anionic portion is a carboxylic acid salt, such as acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Compounds having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Aniline compounds include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris(methoxyethoxyethyl)amine. Aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0476] Furthermore, as an alkaline compound, the compound described herein as an alkaline compound (XC) contained in the above-mentioned protective film forming composition (also known as an upper film forming composition or a top coating composition) can be used more preferably.

[0477] These basic compounds can be used alone or in combination of two or more.

[0478] The amount of alkaline compound used is based on the solid content of the photosensitive or radiosensitive linear resin composition, preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

[0479] The preferred molar ratio of photoacid generator to basic compound in the photosensitive or radiosensitive linear resin composition is 2.5 to 300. That is, from the viewpoint of sensitivity and resolution, a molar ratio of 2.5 or higher is preferred, and from the viewpoint of suppressing the decrease in resolution caused by pattern coarsening over time from exposure to heat treatment, a molar ratio of 300 or lower is preferred. A molar ratio of photoacid generator to basic compound is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0480] (E) Hydrophobic resin

[0481] The photosensitive or radiosensitive linear resin composition may contain a hydrophobic resin (E). As a hydrophobic resin, the above-mentioned resin (XB) contained in the protective film forming composition is preferably used, for example. Furthermore, examples such as "[4] hydrophobic resin (D)" described in paragraphs

[0389] to

[0474] of Japanese Patent Application Publication No. 2014-149409 are also preferred.

[0482] The weight-average molecular weight of the hydrophobic resin (E) converted from standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 15,000.

[0483] Furthermore, one type of hydrophobic resin (E) may be used, or multiple types may be used in combination.

[0484] The content of the aqueous resin (E) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and even more preferably 0.1 to 7% by mass, relative to the total solid content in the photosensitive or radiosensitive linear resin composition.

[0485] (F) Surfactants

[0486] The photosensitive or radiosensitive linear resin composition preferably further contains (F) a surfactant, more preferably contains one or more of fluorine-based and / or silicone-based surfactants (fluorine-based surfactants, silicone-based surfactants, surfactants having both fluorine and silicon atoms).

[0487] When the photosensitive or radiosensitive linear resin composition contains the above-mentioned (F) surfactant, it can provide patterns with good sensitivity and resolution and few development defects when using an exposure light source of 250 nm or less, especially 220 nm or less.

[0488] Examples of fluorinated and / or silicone surfactants include Japanese Patent Application Publication Nos. 62-036663, 61-226746, 61-226745, 62-170950, 63-34540, 7-230165, 8-062834, 9-054432, and 9-005988. The surfactants described in U.S. Patent No. 2002-277862, U.S. Patent No. 5405720, U.S. Patent No. 5360692, U.S. Patent No. 5529881, U.S. Patent No. 5296330, U.S. Patent No. 5436098, U.S. Patent No. 5576143, U.S. Patent No. 5294511, and U.S. Patent No. 5824451 can also be used directly with commercially available surfactants.

[0489] Examples of commercially available surfactants that can be used include: Ftop EF301, EF303 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Fluorad FC430, 431, 4430 (manufactured by Sumitomo 3M Limited), MEGAFACE F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by ASAHIGLASS CO.,LTD.), Troy Sol S-366 (manufactured by Troy Chemical Industries Inc.), GF-300, GF-150 (manufactured by TOAGOSEI CO.,LTD.), Surflon S-393 (manufactured by SEIMI CHEMICAL CO.,LTD.), and Eftop. Fluoropolymer surfactants and silicone surfactants include EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, 352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA Solutions Inc.), FTX-204D, 208G, 218G, 230G, 204D, 208D, 212D, 218, 222D (manufactured by Neos Corporation). Furthermore, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

[0490] Furthermore, in addition to the known surfactants described above, surfactants utilizing copolymers having fluoroaliphatic groups can also be used as surfactants. These fluoroaliphatic groups are derived from fluoroaliphatic compounds produced by telomerization (also known as telomerization) or oligomerization (also known as oligomerization). Fluoroaliphatic compounds can be synthesized using the method described in Japanese Patent Application Publication No. 2002-90991.

[0491] As copolymers containing fluorinated aliphatic groups, copolymers of monomers containing fluorinated aliphatic groups with (poly(oxyalkylene)) acrylates and / or (poly(oxyalkylene)) methyl acrylate are preferred. These copolymers can be irregularly distributed or block copolymers. Furthermore, examples of poly(oxyalkylene) groups include poly(ethylene oxide) groups, poly(propylene oxide) groups, and poly(butylene oxide) groups. These can be alkylene units with different chain lengths within the same chain length, such as poly(block copolymers of ethylene oxide and propylene oxide) or poly(block copolymers of ethylene oxide and propylene oxide). Moreover, copolymers of monomers containing fluorinated aliphatic groups with (poly(oxyalkylene)) acrylates (or methyl acrylate) are not only binary copolymers but can also be ternary or higher copolymers that simultaneously copolymerize monomers with two or more different fluorinated aliphatic groups, or two or more different (poly(oxyalkylene)) acrylates (or methyl acrylate).

[0492] For example, commercially available surfactants include MEGAFACE F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC Corporation). Furthermore, surfactants containing C6F... 13 Copolymers of acrylate (or methyl acrylate) with (poly(oxyalkylene)) acrylate (or methyl acrylate), copolymers of acrylate (or methyl acrylate) with C3F7 group with (poly(oxyethylene)) acrylate (or methyl acrylate) and (poly(oxypropylene)) acrylate (or methyl acrylate), etc.

[0493] Furthermore, it is possible to use surfactants other than fluorinated and / or silicone surfactants. Specifically, examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitol fatty acid esters such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and nonionic surfactants such as polyoxyethylene sorbitol fatty acid esters.

[0494] These surfactants can be used individually or in combination.

[0495] (F) The amount of surfactant used relative to the total amount of the photosensitive or radiosensitive linear resin composition (excluding solvent) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.

[0496] (G) Carboxylic acid salts

[0497] The photosensitive or radiosensitive linear resin composition may contain a (G) carboxylate salt. Examples of carboxylate salts include sulfonium carboxylate salts, ferrophosphate carboxylate salts, and ammonium carboxylate salts. Ferrophosphate salts and sulfonium salts are particularly preferred as (G) carboxylate salts. More preferably, the carboxylic acid ester residues of the (G) carboxylate salt do not contain aromatic groups or carbon-carbon double bonds. As a particularly preferred anionic portion, it is an alkyl carboxylic acid anion with 1 to 30 carbon atoms and a straight chain, branched structure, or cyclic structure (monocyclic or polycyclic). More preferably, it is an anion of a carboxylic acid in which some or all of these alkyl groups are substituted with fluorine. The alkyl chain may also contain oxygen atoms. This ensures improved transparency to light below 220 nm, enhances sensitivity and resolution, and improves density dependence and exposure tolerance.

[0498] Examples of anions of fluorinated carboxylic acids include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluorovalerate, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, and the anions of 2,2-bis(trifluoromethylpropionic acid).

[0499] These (G) carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, uranium hydroxide, or ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

[0500] (G) The content of carboxylic acid onium salt in the composition is preferably 0.1 to 20% by mass relative to the total solid content of the photosensitive or radiosensitive linear resin composition, more preferably 0.5 to 10% by mass, and even more preferably 1 to 7% by mass.

[0501] (H) Other additives

[0502] The photosensitive or radiosensitive linear resin composition may, as needed, also contain dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and compounds that promote solubility in the developer (e.g., phenolic compounds with a molecular weight of less than 1000, alicyclic or aliphatic compounds with carboxyl groups).

[0503] Phenolic compounds with a molecular weight of less than 1000 can be easily synthesized by those skilled in the art by referring to methods described in, for example, Japanese Patent Application Publication No. 4-122938, Japanese Patent Application Publication No. 2-028531, US Patent No. 4,916,210, European Patent No. 219294, etc.

[0504] Specific examples of alicyclic or aliphatic compounds with a carboxyl group include carboxylic acid derivatives with steroidal structures such as cholic acid, deoxycholic acid, and lithocholic acid, as well as adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, and cyclohexane dicarboxylic acid, but are not limited to these.

[0505] One method for forming a photosensitive or linearly photosensitive film on a substrate is, for example, coating a photosensitive or linearly photosensitive resin composition onto the substrate. The coating method is not particularly limited; conventionally known methods such as spin coating, spray coating, roller coating, or dip coating can be used, with spin coating being preferred.

[0506] After forming the photosensitive or linearly photosensitive film, the substrate can be heated (prebake (PB)) as needed. This allows for the uniform formation of a film free of insoluble residual solvents. The prebake temperature after forming the photosensitive or linearly photosensitive film in process a is not particularly limited, but is preferably 50–160°C, more preferably 60–140°C.

[0507] The substrate for forming photosensitive or linearly photosensitive films is not particularly limited and can be inorganic substrates such as silicon, SiN, and SiO2; coated inorganic substrates such as SOG (spin-on glass); substrates commonly used in semiconductor manufacturing processes such as IC (integrated circuit), circuit substrate manufacturing processes such as liquid crystals and thermal heads, and other photolithography processes such as photosensitive etching.

[0508] Before forming a photosensitive or linearly photosensitive film, an antireflective film can be pre-coated on the substrate.

[0509] As an anti-reflective film, any of the following can be used: inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon; and organic film types including light absorbers and polymer materials. Furthermore, as an organic anti-reflective film, commercially available organic anti-reflective films such as the DUV30 series and DUV-40 series manufactured by Brewer Science, Inc., AR-2, AR-3, and AR-5 manufactured by Shipley, and the ARC29A series manufactured by NISSAN CHEMICAL INDUSTRIES, LTD. can also be used.

[0510] <Uses of the medicinal liquid>

[0511] The solutions described above are preferably used in semiconductor manufacturing. Specifically, in the manufacturing processes of semiconductor devices, including lithography, etching, ion implantation, and stripping processes, they are used for the treatment of organic materials after each process or before moving to the next process. Specifically, they are preferably used as pre-wetting solutions, developing solutions, rinsing solutions, and stripping solutions. For example, they can also be used for rinsing the edge lines of semiconductor substrates before and after resist coating.

[0512] Furthermore, the aforementioned solution can also be used as a diluent for the resin contained in a resist film forming composition used in semiconductor manufacturing. That is, it can be used as a solvent for resist film forming compositions.

[0513] Furthermore, the above-mentioned solution can also be diluted with other organic solvents and / or water before use.

[0514] Furthermore, the aforementioned solution can be used as a polishing slurry for CMP (Chemical Mechanical Polishing). For example, a liquid containing abrasive particles and oxidants can be used as a CMP polishing slurry. It can also be used as a solvent when diluting a CMP polishing slurry.

[0515] Furthermore, the aforementioned solution can be used as a cleaning solution for cleaning substrates after CMP. It can also be used as a solvent for the aforementioned cleaning solution. The aforementioned cleaning solution can be diluted with other organic solvents and / or water, etc.

[0516] Furthermore, the aforementioned solution can also be used for purposes other than semiconductor manufacturing, and can also be used as a developing solution and rinsing solution for polyimide, sensor resist, lens resist, etc.

[0517] Furthermore, the aforementioned solution can also be used as a solvent for medical or cleaning purposes. It is particularly well-suited for cleaning containers, piping, and substrates (e.g., wafers and glass).

[0518] [Example]

[0519] The present invention will now be described in more detail with reference to the embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the invention should not be limited by the embodiments shown below.

[0520] Purification of pharmaceutical solutions containing organic solvents

[0521] [Examples 1-17 and Comparative Examples 1-5]

[0522] Prepare Figure 7The purification apparatus is shown. Table 1 lists the materials of the filter media housed in the housings of each filter unit within the purification apparatus. Furthermore, the "Type" column indicates whether the housed filter is the first filter or the second filter.

[0523] Specifically, the "Materials" section describes the materials of each filter material. In particular, the first filter material is described layer by layer. The designations "Layer 1" and "Layer 2" indicate that "Layer 1" and "Layer 2" are stacked sequentially from the primary side.

[0524] Regarding the tertiary filter unit, there are cases where it is not used according to the embodiments. In this case, the "tertiary filter unit" column in Table 1 is empty.

[0525] In addition, the abbreviations in the columns of Table 1 are as follows.

[0526] The materials of the first filter material are as follows.

[0527] • “Nylon”: Includes nanofiber layers of nylon

[0528] • "HDPE": Includes nanoporous membrane layers of high-density polyethylene (HDPE)

[0529] • "Ion-exchange nylon": comprising nanofiber layers of nylon with ion-exchange groups

[0530] The materials of the second filter material are as follows.

[0531] • "PTFE": a nanoporous membrane layer comprising polytetrafluoroethylene.

[0532] • "HDPE": Nanoporous membranes containing HDPE

[0533] • “Nylon”: Includes nanofiber layers of nylon

[0534] Furthermore, the type of filter material used in Comparative Example 1 is denoted as "same as the secondary filter," indicating that the housing of the primary filter unit contains the same filter as the secondary filter unit.

[0535] Using the purification apparatus described above, the purified substance containing the solvents listed in Table 1 was purified to obtain a pharmaceutical solution containing the solvent. Additionally, the abbreviations in the "Purified Substance" column of Table 1 refer to the following:

[0536] ·1: Butyl acetate (FUJIFILM Electronic Materials Co., Ltd. (FFEM) product)

[0537] ·2: PGMEA / PGME (30 / 70 (volume / volume) mixture, raw material is FUJIFILM Electronic Materials Co., Ltd. (FFEM) product)

[0538] ·3: Cyclohexanone (FFEM product)

[0539] ·4:4-Methyl-2-pentanol (FFEM product)

[0540] The specific production method is as follows. First, 40L of the purified material is introduced into the manufacturing tank of the purification apparatus described above. Next, a circulating filtration process is performed, in which the purified material, having been purified in each filter, is reintroduced into the manufacturing tank. This operation is repeated 10 times to obtain the pharmaceutical solution.

[0541] <Evaluation of the Defect Inhibition Performance of the Drug Solution>

[0542] The defect suppression performance of the pharmaceutical solution manufactured using the above-mentioned manufacturing apparatus was evaluated using the following methods, and the results are shown in Table 1.

[0543] First, a silicon oxide film substrate with a diameter of 300mm was prepared.

[0544] Next, particles with a diameter greater than 30 nm were detected on the substrate using a wafer surface defect detection device (KLA Tencor SP-5). Then, the constituent factors of the defects were analyzed using a wafer surface defect analysis device (AMAT G6), and the number of defects was evaluated based on the carbon atom content exceeding 75% (this was used as an initial value). Next, the substrate was placed on a spin-jet printer, and while rotating the substrate, various chemical solutions were sprayed onto its surface at a flow rate of 1.5 L / min. Afterward, the substrate was rotated and dried.

[0545] Next, the number of defects was measured using the same method (this was taken as the measured value). Then, the difference between the initial value and the measured value was calculated (measured value - initial value). The results were evaluated based on the following criteria, and the results are shown in Table 1.

[0546] "1": The difference between the initial value and the measured value of the number of defects is less than 10.

[0547] "2": The difference between the initial value and the measured value of the number of defects is 11 to 100.

[0548] "3": The difference between the measured number of defects and the initial value is 101 to 200.

[0549] “4”: The difference between the measured number of defects and the initial value is 201 to 1000.

[0550] "5": The difference between the measured number of defects and the initial value is more than 1001.

[0551] <Determination of the lifespan of filter materials>

[0552] The purified substances were continuously purified using the aforementioned purification apparatus. During the purification process, the purified solutions were recovered for testing at a flow rate of 10,000 kg per cycle. Next, the test solutions were coated onto a 300 mm silicon substrate using a LITHIUS coating / developing machine manufactured by Tokyo Electron Limited for 60 seconds. Then, the number of foreign objects with a diameter of 30 nm or larger was counted on the resulting coated silicon substrate using a SP-5 foreign object detection device manufactured by KLA-Tencor. The flow rate at which the counted value became twice the initial value was taken as the filter material's lifespan.

[0553] The results were calculated as a ratio of the lifetime of filter 1 when filter 1 was used alone, and evaluated against the following benchmarks, as shown in Table 1.

[0554] 1: Lifespan is more than 10 times longer.

[0555] 2: Lifespan is 5 times longer but less than 10 times longer.

[0556] 3: Lifespan is more than twice but less than five times.

[0557] 4: Lifespan is more than 1 time but less than 2 times.

[0558] 5: Lifespan is less than 1 time.

[0559] [Examples 18-20, Comparative Examples 6 and 7]

[0560] Prepared Figure 7 The purification apparatus is shown. Table 2 describes the materials of the filter media housed in the housings of each filter unit within the purification apparatus. "Ra / R0" indicates the Ra / R0 value calculated from the Hansen solubility parameter of the purified material and the second filter media. The meanings of the headings in the other columns are the same as in Table 1.

[0561] The abbreviations for the purified substances are as follows.

[0562] "1": Cyclohexanone

[0563] "2": PGMEA

[0564] "3": Diethyl carbonate

[0565] The materials of the first filter material are as follows.

[0566] • "Hydrophilic HDPE": This includes a nanoporous membrane layer of HDPE that has been hydrophilized through plasma treatment. Additionally, the water contact angle of the filter material surface at 25°C, measured using a contact angle meter, is 50°.

[0567] • "HDPE": Nanoporous membranes containing HDPE

[0568] The materials of the second filter material are as follows.

[0569] • "HDPE": Nanoporous membranes containing HDPE

[0570] First, 40 L of the purified material listed in Table 2 was introduced into the manufacturing tank of the purification apparatus described above. Next, a circulating filtration process was performed, in which the purified material, having been purified in each filter, was reintroduced into the manufacturing tank. This operation was repeated 10 times to obtain the drug solution. The defect-inhibiting performance of the obtained drug solution was evaluated using the same method as described above. The results are shown in Table 2.

[0571] Furthermore, the lifespan of the filter material was determined using the purification apparatus described in Table 2, following the same method described above. The results are shown in Table 2.

[0572] [Purification of Aqueous Drug Solutions]

[0573] [Examples 21-37, Comparative Examples 8 and 9]

[0574] Prepared Figure 7 The purification apparatus is shown. Table 3 describes the materials, etc., of the filter media housed in the housings of each filter unit within the purification apparatus. The meanings of the column headings are the same as in Table 1.

[0575] The materials of the first filter material are as follows.

[0576] • “Nylon”: Includes nanofiber layers of nylon

[0577] • "HDPE1": Includes a nanoporous membrane layer of HDPE that has been hydrophilized through plasma treatment.

[0578] In addition, the water contact angle of the filter material surface at 25°C, as measured by a contact angle meter, is 50°.

[0579] • "HDPE": Nanoporous membranes containing HDPE

[0580] The materials of the second filter material are as follows.

[0581] • "PTFE": This refers to a nanoporous membrane layer composed of polytetrafluoroethylene. In addition, the polytetrafluoroethylene is hydrophilized through plasma treatment, and the water contact angle at 25°C is 45° as measured by a contact angle meter.

[0582] • "HDPE2": Includes a nanoporous membrane layer of HDPE. In addition, HDPE is hydrophilized through plasma treatment, and the water contact angle at 25°C is 50° as measured by a contact angle meter.

[0583] • "PESU": a nanoporous membrane layer including polyethersulfone

[0584] 40 L of the purified material listed in Table 3 was introduced into the manufacturing tank of the purification apparatus described above. Next, a circulating filtration process was performed, in which the purified material, having been purified in each filter, was reintroduced into the manufacturing tank. This operation was repeated 10 times to obtain the pharmaceutical solution.

[0585] Additionally, the abbreviations in the "Purified Material" column of Table 3 represent the following:

[0586] The defect suppression performance of the obtained drug solution was determined using the same method as described above. Furthermore, the lifespan of the filter material was determined using the same method. These results are shown in Table 3.

[0587] • 1: FHD-5 (alkaline aqueous developer)

[0588] ·2: FHD-402 (Alkaline aqueous developer)

[0589] Purification of photosensitive or radiosensitive linear resin compositions

[0590] [Examples 38-48, Comparative Examples 10 and 11]

[0591] First, a photosensitive or radiosensitive linear resin composition 1 was prepared by the following method.

[0592] (Photosensitive or radiosensitive linear resin composition 1)

[0593] The resin synthesized according to the following method: 0.77g

[0594] • Resin Synthesis

[0595] According to the following synthesis scheme, 11.9 g of monomer (1), 8.0 g of monomer (1-2), 15.1 g of monomer (1-3) and 1.12 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 129.0 g of cyclohexanone to obtain a mixture.

[0596] Next, 69.5 g of cyclohexanone was placed in a reaction vessel. Under a nitrogen atmosphere, the mixture was added dropwise over 4 hours to the cyclohexanone in the reaction vessel, which was maintained at 85°C, to obtain a reaction solution. After heating the reaction solution with stirring for 2 hours, the reaction solution was allowed to cool naturally to room temperature. Then, 49.6 g of methanol and 4.9 g of triethylamine were added to the reaction solution. After heating and stirring at 50°C for 18 hours, the reaction solution was allowed to cool naturally to room temperature. Next, 200 g of ethyl acetate and 200 g of water were added to the reaction solution, and the organic layer was recovered by separation. The organic layer was washed three times with water, and the solvent was subjected to vacuum distillation. The remaining solid was dissolved in 200 g of PGMEA (propylene glycol monomethyl ether acetate), and after azeotropic dehydration of the solvent by vacuum distillation, 198.5 g of cyclohexanone was added to obtain a solution. Next, the solution was added dropwise to 2336 g of a mixed solution of n-heptane and ethyl acetate (n-heptane / ethyl acetate = 9 / 1 (mass ratio)), causing the solid to precipitate and then filtering. Next, the filtered solid was washed with 701 g of the mixed solution of n-heptane and ethyl acetate (n-heptane / ethyl acetate = 9 / 1 (mass ratio)). Afterward, the washed solid was dried under reduced pressure to obtain 23.8 g of resin (A-1). 1 H-NMR and 13 C-NMR, the component ratio in the resin was calculated as repeating unit (a) / repeat unit (c) / repeat unit (b) = 30 / 20 / 50 (molar ratio). Furthermore, the resin synthesis method is simplified in the scheme.

[0597] [Chemical Formula 14]

[0598]

[0599] The following acid-generating agent is used: 0.23g

[0600] [Chemical Formula 15]

[0601]

[0602] The following is an acid diffusion control agent: 0.03g

[0603] [Chemical Formula 16]

[0604]

[0605] Solvent:

[0606] PGMEA (Propylene Glycol Monomethyl Ether Acetate): 60g

[0607] PGME (Propylene Glycol Monomethyl Ether): 15g

[0608] Next, preparations were made. Figure 7The purification apparatus is shown. Table 4 describes the materials, etc., of the filter media housed in the housings of each filter unit within the purification apparatus. The meanings of the column headings are the same as in Table 1.

[0609] The materials of the first filter material are as follows.

[0610] • “Nylon”: Includes nanofiber layers of nylon

[0611] • "HDPE": Nanoporous membranes containing HDPE

[0612] The materials used as the second filter material are as follows.

[0613] • "PTFE": Nanoporous membranes containing PTFE

[0614] • "HDPE": Nanoporous membranes containing HDPE

[0615] • “Nylon”: Includes nanofiber layers of nylon

[0616] 40 L of the purified material listed in Table 4 was introduced into the manufacturing tank of the purification apparatus described above. Next, a circulating filtration process was performed, in which the purified material, having been purified in each filter, was reintroduced into the manufacturing tank. This operation was repeated 10 times to obtain the pharmaceutical solution.

[0617] Additionally, the abbreviations in the "Purified Material" column of Table 4 represent the following:

[0618] "1": Photosensitive or radiosensitive linear resin composition 1

[0619] The obtained chemical solution was used to form a resist pattern using the following method, and the occurrence of defects was evaluated. Furthermore, the lifespan of the filter material was determined using the same method.

[0620] <Formation of resist patterns (line and space patterns) / EUV exposure (solvent development)>

[0621] An organic antireflective film forming composition ARC29SR (manufactured by Brewer) was coated onto a silicon wafer and baked at 205°C for 60 seconds to form an antireflective film with a thickness of 86 nm. After coating with the pre-wetting liquid described in Table 4, the above-mentioned solution was coated and baked at 120°C for 60 seconds to form a resist film with a thickness of 40 nm on the silicon wafer.

[0622] Using an EUV exposure apparatus (Exitech Micro Exposure Tool, NA 0.3, quadrupole, outer sigma 0.68, inner sigma 0.36) and an exposure mask (with a line / space width of 1 / 1 (width of the light-transmitting portion) of 10 nm), a silicon wafer with a resist film was patterned. After patterning, the silicon wafer with the exposed resist film was placed face down on a heated plate and baked at 90°C for 60 seconds. The baked resist film was then developed by immersion in a developer solution for 30 seconds and rinsed. Finally, the wafer was rotated at 2000 rpm for 30 seconds to obtain a 1:1 line and space pattern.

[0623] <Evaluation of Pattern Formation>

[0624] After the pattern was formed, the upper surface and the space portion of the line pattern were observed using a length-measuring scanning electron microscope (Hitachi, Ltd. S9380II) to confirm the occurrence of defects in the formed pattern with a linewidth of 10 nm. The observed patterns were classified into 1 to 3, and the results are shown in Table 4.

[0625] “1”: A pattern with a linewidth of 10 nm is formed.

[0626] "2": There is a defect in a part of the pattern.

[0627] “3”: The pattern contains many defects.

[0628] <Evaluation of the lifespan of filter materials>

[0629] The lifespan of the filter material was evaluated using the same method as described above, and the results are shown in Table 4.

[0630] [Table 2]

[0631]

[0632] [Table 3]

[0633]

[0634] [Table 4]

[0635]

[0636] [Table 5]

[0637]

[0638] <Examples 49-69>

[0639] Prepared Figure 7 The purification apparatus is shown. Table 5 describes the materials of the filter media housed in the housings of each filter unit within the purification apparatus. Furthermore, the "Type" column indicates whether the housed filter is the first filter or the second filter.

[0640] Specifically, the "Materials" section describes the materials of each filter material. In particular, the first filter material is described layer by layer. The designations "Layer 1", "Layer 2", and "Layer 3" indicate that "Layer 1", "Layer 2", and "Layer 3" are stacked sequentially from the primary side.

[0641] Regarding the tertiary filter unit, there are cases where it is not used according to the embodiments, in which case the "tertiary filter unit" column in Table 5 is empty.

[0642] Furthermore, in embodiments 62-66 and 68-69, in addition to the tertiary filter unit, a quaternary filter unit is also provided on the secondary side.

[0643] In addition, the abbreviations in the columns of Table 5 are as follows.

[0644] The materials of the first filter material are as follows.

[0645] • "IEX": An ion-exchange membrane with a surface modified with sulfonic acid groups (manufactured by PALL Corporation)

[0646] • "PTFE": A nanoporous membrane layer consisting of polytetrafluoroethylene (manufactured by PALL).

[0647] • “Nylon”: Includes nanofiber layers of nylon

[0648] • "UPE": A nanoporous membrane layer containing ultra-high molecular weight polyethylene

[0649] • "HDPE": Includes nanoporous membrane layers of high-density polyethylene (HDPE)

[0650] The materials of the second filter material are as follows.

[0651] • "PTFE": a nanoporous membrane layer comprising polytetrafluoroethylene.

[0652] • "PP": includes nanoporous membranes made of polypropylene

[0653] • “Oktlex”: A nanoporous membrane layer made of ultra-high molecular weight polyethylene as a matrix, with its surface modified with nylon-based compounds.

[0654] Using the purification apparatus described above, the purified substance containing the solvents listed in Table 5 was purified to obtain a pharmaceutical solution containing the solvent. Additionally, the abbreviations in the "Purified Substance" column of Table 5 represent the following:

[0655] ·1: Butyl acetate (FUJIFILM Electronic Materials Co., Ltd. (FFEM) product)

[0656] ·2: PGMEA / PGME (30 / 70 (volume / volume) mixture, raw material is FUJIFILM Electronic Materials Co., Ltd. (FFEM) product)

[0657] ·3: Isoamyl acetate (FFEM product)

[0658] ·4: Cyclohexanone (FFEM product)

[0659] ·5: PGMEA (FFEM product)

[0660] The specific production method is as follows. First, 40L of the purified material is introduced into the manufacturing tank of the purification apparatus described above. Next, a circulating filtration process is performed, in which the purified material, having been purified in each filter, is reintroduced into the manufacturing tank. This operation is repeated 10 times to obtain the pharmaceutical solution.

[0661] <Evaluation of the Defect Inhibition Performance of the Drug Solution>

[0662] The defect suppression performance of the pharmaceutical solution manufactured using the above-mentioned manufacturing apparatus was evaluated using the following methods, and the results are shown in Table 5.

[0663] First, a silicon oxide film substrate with a diameter of 300mm was prepared.

[0664] Next, particles with a diameter greater than 30 nm were detected on the substrate using a wafer surface defect detection device (KLA Tencor SP-5). Then, the constituent factors of the defects were analyzed using a wafer surface defect analysis device (AMAT G6), and the number of defects was evaluated based on the carbon atom content exceeding 75% (this was used as an initial value). Next, the substrate was placed on a spin-jet printer, and while rotating the substrate, various chemical solutions were sprayed onto its surface at a flow rate of 1.5 L / min. Afterward, the substrate was rotated and dried.

[0665] Next, the number of defects was measured using the same method (this was taken as the measured value). Then, the difference between the initial value and the measured value was calculated (measured value - initial value). The results were evaluated based on the following criteria, and the results are shown in Table 5.

[0666] "0": The difference between the initial value and the measured value of the number of defects is less than 5.

[0667] "1": The difference between the initial value and the measured value of the number of defects is 6 to 10.

[0668] "2": The difference between the initial value and the measured value of the number of defects is 11 to 100.

[0669] "3": The difference between the measured number of defects and the initial value is 101 to 200.

[0670] “4”: The difference between the measured number of defects and the initial value is 201 to 1000.

[0671] "5": The difference between the measured number of defects and the initial value is more than 1001.

[0672] <Determination of the lifespan of filter materials>

[0673] The purified substances were continuously purified using the aforementioned purification apparatus. During the purification process, the purified solutions were recovered for testing at a flow rate of 10,000 kg per cycle. Next, the test solutions were coated onto a 300 mm silicon substrate using a LITHIUS coating / developing machine manufactured by Tokyo Electron Limited for 60 seconds. Then, the number of foreign objects with a diameter of 30 nm or larger was counted on the resulting coated silicon substrate using a SP-5 foreign object detection device manufactured by KLA-Tencor. The flow rate at which the counted value became twice the initial value was taken as the filter material's lifespan.

[0674] The results were calculated as a ratio of the lifetime of filter 1 when filter 1 was used alone, and evaluated against the following benchmarks, as shown in Table 5.

[0675] 0: Lifespan is more than 15 times longer.

[0676] 1: Lifespan is more than 10 times but less than 15 times.

[0677] 2: Lifespan is 5 times longer but less than 10 times longer.

[0678] 3: Lifespan is more than twice but less than five times.

[0679] 4: Lifespan is more than 1 time but less than 2 times.

[0680] 5: Lifespan is less than 1 time.

[0681] In Table 5, "pore size" refers to the pore size of the filter material.

[0682] The "Difference (75% of cumulative pore size - 10% of cumulative pore size)" column represents the difference between the cumulative 75% of the pore size (nm) and the cumulative 10% of the pore size (nm) in the cumulative pore distribution of the filter material (75% of cumulative pore size (nm) - 10% of cumulative pore size (nm)).

[0683] The "Ratio (75% of pore size / 10% of pore size)" column indicates the ratio of the cumulative 75% of pore size (nm) to the cumulative 10% of pore size (nm) in the cumulative pore distribution of the filter material.

[0684] [Table 6]

[0685]

[0686] As shown in the table above, based on the comparison of Examples 49 to 66, the effect is better when there is a triple filter unit (more preferably, when there is a triple filter unit and a quadruple filter unit).

[0687] Furthermore, based on the comparison between Examples 49-52 and 67, the effect is better when the difference (cumulative 75% pore size - cumulative 10% pore size) is 3nm or more.

[0688] Furthermore, according to the comparison of Examples 62-66 and 69, the effect is better when (cumulative 75% pore size / cumulative 10% pore size) is 2.0 to 20.0.

[0689] <Examples 70-83>

[0690] Prepared Figure 7 The purification apparatus is shown. Table 6 describes the materials of the filter media housed in the housings of each filter unit within the purification apparatus. Furthermore, the "Type" column indicates whether the housed filter is the first filter or the second filter.

[0691] Specifically, the "Materials" section describes the materials of each filter material. In particular, the first filter material is described layer by layer. The designations "Layer 1", "Layer 2", and "Layer 3" indicate that "Layer 1", "Layer 2", and "Layer 3" are stacked sequentially from the primary side.

[0692] Regarding the tertiary filter unit, since it is not used in the embodiments, the "tertiary filter unit" column in Table 6 is empty.

[0693] Furthermore, in embodiment 80, in addition to the third filter unit, a fourth filter unit is also provided on the secondary side.

[0694] In addition, the abbreviations in the columns of Table 6 are as follows.

[0695] The materials of the first filter material are as follows.

[0696] • "IEX": An ion-exchange membrane with a surface modified with sulfonic acid groups (manufactured by PALL Corporation)

[0697] • "PTFE": A nanoporous membrane layer consisting of polytetrafluoroethylene (manufactured by PALL).

[0698] • “Nylon”: Includes nanofiber layers of nylon

[0699] • "UPE": A nanoporous membrane layer containing ultra-high molecular weight polyethylene

[0700] • "HDPE1": Includes a nanoporous membrane layer of HDPE that has been hydrophilized through plasma treatment.

[0701] In addition, the water contact angle of the filter material surface at 25°C, as measured by a contact angle meter, is 50°.

[0702] The materials of the second filter material are as follows.

[0703] • "PP": includes nanoporous membranes made of polypropylene

[0704] • "HDPE": Includes nanoporous membrane layers of high-density polyethylene (HDPE)

[0705] • “Oktlex”: A nanoporous membrane layer made of ultra-high molecular weight polyethylene as a matrix, with its surface modified with nylon-based compounds.

[0706] Using the purification apparatus described above, the purified substance containing the solvents listed in Table 6 was purified to obtain a pharmaceutical solution containing the solvent. Additionally, the abbreviations in the "Purified Substance" column of Table 6 represent the following:

[0707] • 1: FHD-5 (alkaline aqueous developer)

[0708] ·2: FHD-402 (Alkaline aqueous developer)

[0709] The specific production method is as follows. First, 40L of the purified material is introduced into the manufacturing tank of the purification apparatus described above. Next, a circulating filtration process is performed, in which the purified material, having been purified in each filter, is reintroduced into the manufacturing tank. This operation is repeated 10 times to obtain the pharmaceutical solution.

[0710] The defect suppression performance of the obtained drug solution was measured using the same method as in Examples 49-69 above. Furthermore, the lifespan of the filter material was measured using the same method as in Examples 49-69 above. These results are shown in Table 6.

[0711] In Table 6, "pore size" refers to the pore size of the filter material.

[0712] The "Difference (Cumulative 75% Pore Size - Cumulative 10% Pore Size)" column represents the difference between the cumulative 75% pore size (nm) and the cumulative 10% pore size (nm) in the cumulative pore distribution of the filter material (cumulative 75% pore size (nm) - cumulative 10% pore size (nm)).

[0713] The "Ratio (75% of pore size / 10% of pore size)" column indicates the ratio of the cumulative 75% of pore size (nm) to the cumulative 10% of pore size (nm) in the cumulative pore distribution of the filter material.

[0714] [Table 7]

[0715]

[0716] Symbol Explanation

[0717] 10 - First filter; 11a, 11b, 11c - Layers; 12, 21 - Filter media; 13, 22 - Core; 14, 23 - Cover; 15, 24 - Liquid inlet; 20 - Second filter; 30 - Filter unit; 31 - Body; 32 - Cover; 33(a), 33(b) - Piping; 34, 53, 57, 62 - Liquid inlet; 35, 54, 58, 63 - Liquid outlet; 41, 42 - Internal piping; 43 - Filter; 50, 60 - Filter unit; 5 1(a)~51(d) - Piping, 52 - Primary filter unit, 56 - Secondary filter unit, 61 - Tertiary filter unit, 70, 80 - Purification device, 71 - Manufacturing tank, 72 - Filling device, 73(a)~73(g) - Piping, 74(a)~74(f) - Valve, 75(a), 75(b) - Piping, 81 - Distillation column, 90 - Manufacturing device, 91 - Mixing device, 92(a)~92(c) - Water storage tank, 93(a), 93(b) - Reaction tank.

Claims

1. A photosensitive or radiosensitive linear resin composition, which is filtered using a filtration device having a first filter unit and a second filter unit independently disposed in a conduit supplying the purified material. The first filter unit includes a first filter that satisfies at least one of the following elements 1 to 3, and a housing that accommodates the first filter. Requirement 1: The filter has filter material comprising two or more layers, each containing different materials. Requirement 2: The filter has filter material comprising two or more layers with different pore structures. Requirement 3: The filter has a filter material comprising a layer of different materials mixed together; The second filter unit includes a second filter, which is different from the first filter, and a housing that houses the second filter.

2. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, The photosensitive or radiosensitive linear resin composition comprises a resin. The resin contains structural units having lactones.

3. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, The photosensitive or radiosensitive linear resin composition comprises a resin. The resin comprises repeating units having phenolic hydroxyl groups, wherein the repeating units having phenolic hydroxyl groups are selected from the following repeating units. 。 4. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, The photosensitive or radiosensitive linear resin composition contains an organic solvent. The organic solvent resin is selected from at least one of the following: alkylene glycol monoalkyl ether carboxylic acid esters, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionic acid esters, cyclic lactones with 4 to 10 carbon atoms, optional monoketone compounds with 4 to 10 carbon atoms, alkylene carbonate esters, alkyl alkoxyacetic acid esters, and alkyl pyruvate esters.

5. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, The filter material of the second filter has a pore size of less than 200 nm.

6. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, The pore size of the filter material in the second filter is smaller than that in the first filter.

7. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, The second filter unit is on the secondary side of the first filter unit. The pore size of the filter material in the second filter is smaller than that in the first filter.

8. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, The second filter unit is configured on the primary side, and the first filter unit is configured on the secondary side.

9. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, The pore size of the filter material in the second filter is greater than or equal to the pore size of the filter material in the first filter.

10. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, Ra is derived from the following formula: Ra is a filter material selected from the group consisting of the filter materials of the first filter and the filter materials of the second filter, whose Hansen solubility parameters δDp, δPp, and δHp, and the interaction radius R0, are related to the Hansen solubility parameters δDs, δPs, and δHs of the purified substance. 2 =4(δDs-δDp) 2 +(δPs-δPp) 2 +(δHs-δHp) 2 In the case indicated, the ratio of Ra to R0 is 1.0 or less.

11. The photosensitive or radiosensitive linear resin composition according to claim 1, wherein, The filter material of the first filter and the filter material of the second filter comprise at least one material selected from the group consisting of nylon, polyethylene, polypropylene, polyfluorocarbon, cellulose, diatomaceous earth, polystyrene, glass and polysulfone.

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