JPWO2020009207A1 - Filter, filter manufacturing method, filtration device, chemical solution manufacturing method - Google Patents

Abstract

The present invention provides a filter capable of producing a chemical solution having excellent defect suppressing properties. Further, a method for producing a filter, a filtration device, and a method for producing a chemical solution are provided. The filter of the present invention is a filter for filtration, and includes a filter body, compounds represented by general formulas (I) to (V), alkanes represented by general formula (X), and general formula (XI). ) And (XII), the first organic compound selected from the group consisting of one or more kinds is contained, and the total content of the first organic compound is 0 with respect to the mass of the filter. .10 to 10000 mass ppt.

Description

The present invention relates to a filter, a method for producing a filter, a filtration device, and a method for producing a chemical solution.

During the manufacture of semiconductor devices, as a pre-wet liquid, resist liquid (resist composition), developing liquid, rinsing liquid, stripping liquid, chemical mechanical polishing (CMP) slurry, cleaning liquid after CMP, etc. Alternatively, a chemical solution containing water and / or an organic solvent is used as a diluent for them.
In recent years, with the advancement of semiconductor products, the above-mentioned chemical solutions used for semiconductor manufacturing are required to have further defect suppressing properties.

As a chemical solution used in the conventional manufacturing process of semiconductor products, Patent Document 1 states, "A method for producing an organic treatment solution for patterning a chemically amplified resist film, which can reduce the generation of particles in a pattern forming technique (paragraph). [0010]) ”is disclosed, and in the above manufacturing method, a“ filtration device having a filtration filter membrane (claim 1) ”is used.

Japanese Unexamined Patent Publication No. 2015-84122

The present inventors have found room for improvement in defect suppression property by using an organic treatment solution (chemical solution) for patterning produced by the above production method.
Therefore, an object of the present invention is to provide a filter capable of producing a chemical solution having excellent defect suppressing properties. Another object of the present invention is to provide a method for producing a filter, a filtration device, and a method for producing a chemical solution.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[1]
It is a filter for filtration
With the filter body
Selected from the group consisting of compounds represented by the general formulas (I) to (V), alkanes represented by the general formula (X), and alkenes represented by the general formulas (XI) and (XII). Contains one or more first organic compounds,
A filter in which the total content of the first organic compound is 0.10 to 10000 mass ppt with respect to the mass of the filter.
[2]
The filter according to [1], wherein the filter further contains one or more of the second organic compounds selected from the group consisting of the compounds represented by the general formulas (VI) to (VIII).
[3]
The total content of the first organic compound is 5.0 mass ppt or more with respect to the mass of the filter, and
Compounds selected from the group consisting of compounds represented by the general formulas (I) to (VIII), alkanes represented by the general formula (X), and alkenes represented by the general formulas (XI) and (XII). The filter according to [2], wherein the total content of the above-mentioned filter is 6500 mass ppt or less with respect to the mass of the filter.
[4]
The above filter
One or more of the compounds selected from the group A consisting of the compounds represented by the general formulas (I) to (VIII), and
It contains an alkane represented by the general formula (X) and one or more compounds selected from the group B consisting of alkanes represented by the general formulas (XI) and (XII), [2] or. The filter according to [3].
[5]
The filter according to [4], wherein the total content of the compounds selected from the group A is 0.10 to 3200 mass ppt with respect to the mass of the filter.
[6]
The filter according to [4] or [5], wherein the total content of the compounds selected from the group B is 1.0 to 1200 mass ppt with respect to the mass of the filter.
[7]
Further, a metal component selected from the group consisting of Al, Ca, Cr, Cu, Fe, K, Mg, Na, Ni, Zn, and Pb is added by mass of 0.10 to 5000 with respect to the mass of the filter. The filter according to any one of [1] to [6], which contains ppt.
[8]
The filter body contains nylon,
The filter according to any one of [4] to [6], which contains one or more compounds selected from the group A and two or more compounds selected from the group B.
[9]
It contains an alkane represented by the general formula (X) and an alkene represented by the general formula (XI).
The content A of the alkane represented by the general formula (X), the content B of the alkene represented by the general formula (XI), and the content C of the alkene represented by the general formula (XII) are based on the mass. The filter according to [8], wherein C <A and C <B.
[10]
The filter body contains polyethylene or polytetrafluoroethylene,
The filter according to any one of [4] to [7], which contains one or more compounds selected from the above group A and an alkane represented by the general formula (X).
[11]
The filter according to any one of [1] to [10], wherein the pore diameter of the filter is 10 nm or less.
[12]
The filter according to any one of [1] to [11], wherein the filter body contains an ion exchange group.
[13]
The filter according to any one of [1] to [12], wherein the filter body contains two or more layers made of different materials.
[14]
The filter according to any one of [1] to [13], wherein the filter body contains an asymmetric porous membrane.
[15]
The filter according to [1] to [14], wherein the filter body is made of a material other than a fluorine-based material.
[16]
The method for manufacturing a filter according to any one of [1] to [15].
Selected from the group consisting of compounds represented by the general formulas (I) to (VIII), alkanes represented by the general formula (X), and alkenes represented by the general formulas (XI) and (XII) 1 A method for producing a filter, which comprises a step of subjecting an untreated filter containing seeds or more to a pretreatment using an organic cleaning solution.
[17]
The organic cleaning solution is propylene glycol monomethyl ether acetate, isopropanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, γ-butyrolactone, diisoamyl. Ether, butyl acetate, isoamyl acetate, 4-methyl-2-pentanol, dimethylsulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone, 2 -Heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, mesitylene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2 -The method for producing a filter according to [16], which contains at least one selected from the group consisting of octanol, ethyl acetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate.
[18]
The method for producing a filter according to [16] or [17], wherein the pretreatment includes a step of immersing the untreated filter in the organic cleaning solution for 3 days or more.
[19]
The method for producing a filter according to any one of [16] to [18], which comprises a step of ultrasonically treating the untreated filter immersed in the organic cleaning liquid and performing the pretreatment.
[20]
The pretreatment includes a step of passing the organic cleaning liquid through the untreated filter having a hollow cylindrical shape.
The method for producing a filter according to any one of [16] to [19], wherein the organic cleaning liquid through which the liquid is passed is 10 kg or more with respect to 1 inch of the cylinder length of the untreated filter.
[21]
Compounds represented by the general formulas (I) to (VIII), alkanes represented by the general formula (X), and alkenes represented by the general formulas (XI) and (XII) in the untreated filter. For the total content of compounds selected from the group consisting of
In the filter after the pretreatment, the compounds represented by the general formulas (I) to (VIII), the alkane represented by the general formula (X), and the general formulas (XI) and (XII) are used. The method for producing a filter according to any one of [16] to [20], wherein the mass ratio of the total content of the compounds selected from the group consisting of represented alkanes is 0.5000 or less.
[22]
The untreated filter before the pretreatment is packed with a packing material in which at least a part of the contact portion with the untreated filter is a fluororesin or stainless steel, [16] to [ 21] The method for manufacturing a filter according to any one of the following items.
[23]
Inflow part, outflow part,
Contains 2 or more filters according to any one of [1] to [15].
Two or more of the above filters are arranged in series between the inflow section and the outflow section.
A filtration device for purifying a liquid to be purified to obtain a chemical liquid, which contains a flow passage from the inflow portion to the outflow portion.
[24]
The filtration according to [23], wherein among the two or more filters, the filter having the largest pore diameter has a pore diameter of 10 to 200 nm, and the filter having the smallest pore diameter has a pore diameter of 1 to 10 nm. apparatus.
[25]
The filtration device according to [23] or [24], which comprises the filter according to [12].
[26]
The filtration device according to any one of [23] to [25], which contains the filter according to [9].
[27]
The filtration device according to any one of [23] to [26], which contains the filter according to [10].
[28]
A method for producing a chemical solution by purifying the solution to be purified to obtain a chemical solution.
A method for producing a chemical solution, which comprises a step of filtering the liquid to be purified using the filter according to any one of [1] to [15] to obtain a chemical solution.
[29]
The above-mentioned liquid to be purified is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, cyclohexanone, methyl methoxypropionate, butyl acetate, γ-butyrolactone, 4-methyl-2-pentanol, propylene glycol monoethyl. Ether, ethyl lactate, cyclopentanone, diisoamyl ether, isoamyl acetate, isopropanol, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone, 2-Heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, mesitylene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, The method for producing a chemical solution according to [28], which contains at least one selected from the group consisting of 2-octanol, ethyl acetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate.

According to the present invention, it is possible to provide a filter capable of producing a chemical solution having excellent defect suppressing properties. Further, a method for producing a filter, a filtration device, and a method for producing a chemical solution can be provided.

It is a schematic diagram which shows the filtration apparatus which concerns on 1st Embodiment of this invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the present invention, "ppm" means "parts-per-million ( ^10-6 )", "ppb" means "parts-per-billion ( ^10-9 )", and "ppt" means "ppt". It means "parts-per-trillion ( ^10-12 )", and "ppq" means "parts-per-quadrillion ( ^10-15 )".
Further, in the notation of a group (atomic group) in the present invention, the notation that does not describe substitution or non-substitution includes a group that does not contain a substituent and a group that contains a substituent as long as the effect of the present invention is not impaired. Include. For example, the "hydrocarbon group" includes not only a hydrocarbon group containing no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group containing a substituent (substituted hydrocarbon group). This point is also synonymous with each compound.
Further, the “radiation” in the present invention means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, electron beams, and the like. Further, in the present invention, light means active light rays or radiation. Unless otherwise specified, the term "exposure" in the present invention includes not only exposure with far ultraviolet rays, X-rays, EUV, etc., but also drawing with particle beams such as electron beams or ion beams.

[filter]
The filter of the present invention is a filter for filtering liquids.
The filter contains a filter body and a first organic compound.
The first organic compound is represented by the compounds represented by the general formulas (I) to (V) described later, the alkane represented by the general formula (X), and the general formulas (XI) and (XII). It is a general term for compounds selected from the group consisting of compounds represented by alkanes.
The total content of the first organic compound is 0.10 to 10000 mass ppt with respect to the mass of the filter.

The mechanism by which the problem of the present invention is solved by using the filter having such a structure is not always clear, but the present inventor speculates about the mechanism as follows. The following mechanism is speculative and is included in the scope of the present invention even when the effect of the present invention is obtained by a different mechanism.
In the semiconductor manufacturing process, even a trace amount of impurities contained in the chemical solution tends to cause various defects and the like.
The various defects are, for example, defects that occur when a chemical solution is applied to a manufacturing process of a semiconductor device. More specific examples are metal residue defects, particulate organic residue defects, and stain-like defects when the chemical solution is used as a pre-wet solution or a rinse solution, and all of these defects can be suppressed. Desired. As another specific example, when the chemical solution is used as the pipe cleaning liquid, the above-mentioned defect that occurs when the pre-wet liquid or the rinsing liquid is transferred through the cleaned pipe and then the pre-wet or the rinsing liquid is performed Therefore, it is required that all of the above defects can be suppressed. As another specific example, there are development defect defects, residue defects, and uniformity defects (defects when the pattern is formed by ArF exposure) when the chemical solution is used as a developer and / or rinse solution for the pattern. ), PLOT defects that are protrusion-like defects, BRIDGE defects that are bridge-like defects between patterns, and GEL defects that are defects based on film-like residues (defects when patterns are formed by EUV exposure). (Example), etc., and it is required that all of these defects can be suppressed.
Since the filter of the present invention contains the first organic compound in a predetermined amount or less, the first organic compound is less likely to be mixed as an impurity in the chemical solution produced by using the filter of the present invention, and the defect suppressing property of the chemical solution is suppressed. Is improved.
Further, since the filter of the present invention contains a predetermined amount or more of the first organic compound, it is possible to prevent other trace components (particularly impurities that easily cause defects) from adhering to the filter. It is possible to prevent the trace components of the above from being mixed into the chemical solution produced by using the filter of the present invention and causing defects in the pattern.
Based on such a mechanism, the present inventors speculate that the resist process using the chemical solution produced by using the filter of the present invention was able to suppress the occurrence of defects in the finally obtained pattern. ..

[Specific organic compounds]
The filter of the present invention includes compounds represented by the general formulas (I) to (V) described later, alkanes represented by the general formula (X), and alkenes represented by the general formulas (XI) and (XII). Contains a first organic compound selected from the group consisting of.
The first organic compound and the compounds represented by the general formulas (VI) to (VIII) described later are collectively referred to as a specific organic compound.
The specific organic compound is usually a liquid or a solid at normal temperature and pressure.

<First organic compound>
The first organic compound comprises compounds represented by the general formulas (I) to (V), alkanes represented by the general formulas (X), and alkenes represented by the general formulas (XI) and (XII). One or more selected from the group.
Hereinafter, each first organic compound will be described.

・ General formula (I)
The compound represented by the general formula (I) is shown below.

In the general formula (I), R ^1a and R ^1c each independently represent an alkyl group which may contain a substituent.
The alkyl group may be linear or branched, and may contain a cyclic structure.
The alkyl group preferably has 1 to 50 carbon atoms, more preferably 10 to 20 carbon atoms. The carbon number of the alkyl group does not include the number of carbon atoms contained in the substituent which may be contained in the alkyl group.
R ^1b represents an alkylene group which may contain a substituent. The carbon number of the alkylene group does not include the number of carbon atoms contained in the substituent which may be contained in the alkylene group.
The alkylene group may be linear or branched, and may contain a cyclic structure.
The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

When the filter contains a compound represented by the general formula (I), the content thereof is preferably 0.10 to 3000 mass ppt and more preferably 1.0 to 1000 mass ppt with respect to the mass of the filter. 1.0 to 200 mass ppt is more preferable, and 1.0 to 80 mass ppt is particularly preferable.
An example is a compound represented by the general formula (I).

・ General formula (II)
The compound represented by the general formula (II) is shown below.
The compound represented by the general formula (II) is a specific organic compound different from the compound represented by the general formula (I).

In the general formula (II), a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group which contains a cycloalkyloxy group as a substituent. Represents. The cyclohexane ring group may contain yet another substituent.
Examples of the substituent which may contain a benzene ring group include an alkyl group, an alkoxy group and an arylcarbonyl group which may contain a substituent.
Examples of the substituent which may be contained in the cyclohexene ring group include an alkenyloxy group which may contain a substituent and a cyclohexene ring group.

When the filter contains a compound represented by the general formula (II), the content thereof is preferably 0.10 to 6000 mass ppt, more preferably 1.0 to 2000 mass ppt, based on the mass of the filter. 1.0 to 400 mass ppt is more preferable, and 1.0 to 160 mass ppt is particularly preferable.
An example is a compound represented by the general formula (II).

・ General formula (III)
The compound represented by the general formula (III) is shown below.
The compound represented by the general formula (III) is a specific organic compound different from the specific organic compounds described above.

・ General formula (III)
In the general formula (III), R ^{3a to} R ^3h each independently represent an alkyl group which may contain a substituent.
R ^3b and R ^3e may be bonded to each other to form a ring, ^{and the group formed by bonding R 3b} and R ^3e to each other is −O− (−Si (R ³ⁱ ) ₂ −O−. ) _a - it is.
a represents an integer of 1 or more. The upper limit of a is not particularly limited, but is often 10 or less.
R ³ⁱ represents an alkyl group which may contain a substituent.
The plurality of R ³ⁱ existing may be the same or different from each other.
The ^{alkyl groups represented by R 3a to} R ³ⁱ may be linear or branched, and may contain a cyclic structure.
The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The carbon number of the alkyl group does not include the number of carbon atoms contained in the substituent which may be contained in the alkyl group.
As the ^{alkyl group represented by R 3a to} R ³ⁱ , an unsubstituted alkyl group is preferable, and a methyl group is more preferable.
It is also preferable that one of R ^3g and R ^3h is an alkyl group containing a substituent. The substituent is preferably a group containing one or more oxyalkylene groups (the alkylene group portion preferably has 2 to 4 carbon atoms, may be linear or branched, and may contain a cyclic structure). ..

When the filter contains a compound represented by the general formula (III), the content thereof is preferably 0.10 to 5000 mass ppt, more preferably 1.0 to 1500 mass ppt with respect to the mass of the filter. 1.0 to 400 mass ppt is more preferable, and 1.0 to 110 mass ppt is particularly preferable.
An example is a compound represented by the general formula (III).

・ General formula (IV)
The compound represented by the general formula (IV) is shown below.
The compound represented by the general formula (IV) is a specific organic compound different from the specific organic compounds described above.

In the general formula (IV), R ^4a represents -N (R ^4c ) R ^4d or -SR ^4e .
R ^4c , R ^4d , and R ^4e independently represent a hydrogen atom or a substituent.
R ^4b represents -NH- or -S-.
Examples of R ^4e include aromatic thio groups.
The aromatic ring group in the aromatic thio group may or may not contain a hetero atom (sulfur atom, nitrogen atom, and / or oxygen atom, etc.), and is preferably contained. .. The aromatic ring group may be monocyclic or polycyclic, and polycyclic is preferable.
The benzothiazole ring group is preferable as the abundant ring group.

When the filter contains a compound represented by the general formula (IV), the content thereof is preferably 0.10 to 2000 mass ppt and more preferably 1.0 to 1000 mass ppt with respect to the mass of the filter. More preferably, 1.0 to 600 mass ppt.
The compound represented by the general formula (IV) is exemplified.

・ General formula (V)
The compound represented by the general formula (V) is shown below.
The compound represented by the general formula (V) is a specific organic compound different from the specific organic compounds described above.

In the general formula (V), Y represents a benzene ring group in which the alkyl group may be substituted, or a group represented by the formula (A). In formula (A), * represents the bond position.

When Y represents a benzene ring group, s represents 1 and L represents a single bond and R ^5a represents an alkyl group which may contain a substituent. The alkyl group may contain a hetero atom (preferably an oxygen atom).
The alkyl group of R ^5a may be linear or branched, and may contain a cyclic structure.
The alkyl group of R ^5a preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The carbon number of the alkyl group of the upper R ^5a does not include the number of carbon atoms contained in the substituent which may be contained in the alkyl group of ^{R 5a.}
The ^{substituent which may be contained in the alkyl group of R 5a} preferably contains an aromatic ring group (preferably a benzene ring group, which may further contain a substituent). The substituent is more preferably an aromatic ester group.
When the alkyl group is substituted on the benzene ring group represented by Y, the alkyl group and R ^5a may be bonded to each other to form a ring. When a plurality of alkyl groups are substituted on the benzene ring group represented by Y, the alkyl groups may be bonded to each other to form a ring.

When Y represents a group represented by the formula (A), s represents 3, L represents a methylene group, and R ^5a independently represents an alkyl group.
In this case, ^{the alkyl group of R 5a} preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms.

When the filter contains a compound represented by the general formula (V), the content thereof is preferably 0.10 to 2000 mass ppt, more preferably 1.0 to 1500 mass ppt with respect to the mass of the filter. 5.0 to 250 mass ppt is more preferable, and 5.0 to 60 mass ppt is particularly preferable.
An example is a compound represented by the general formula (V).

・ General formula (X)
The alkane represented by the general formula (X) is shown below.
The alkane represented by the general formula (X) is a specific organic compound different from the specific organic compounds described above.

In the general formula (X), j represents an integer of 12 to 50. The two js have the same value. The alkane may be linear or branched. On the other hand, the alkane does not contain a cyclic structure. That is, the above alkane is not a cycloalkane.

When the filter contains an alkane represented by the general formula (X), the content thereof is preferably 0.10 to 3000 mass ppt, more preferably 1.0 to 600 mass ppt, based on the mass of the filter. 1.0 to 315 mass ppt is more preferable, and 1.0 to 90 mass ppt is particularly preferable.

・ General formula (XI)
The alkene represented by the general formula (XI) is shown below.
The alkene represented by the general formula (XI) is a specific organic compound different from the specific organic compounds described above.

In the general formula (XI), k represents an integer of 12 to 50. The two k are the same value.
The alkene represented by the general formula (XI) is an alkene containing one C = C double bond in the molecule.
The alkene may be linear or branched. On the other hand, the alkene does not contain a cyclic structure.

When the filter contains an arcene represented by the general formula (XI), the content thereof is preferably 0.10 to 9000 mass ppt, more preferably 0.10 to 3000 mass ppt, based on the mass of the filter. 1.0 to 600 mass ppt is more preferable, and 1.0 to 250 mass ppt is particularly preferable.

・ General formula (XII)
The alkene represented by the general formula (XII) is shown below.
The alkene represented by the general formula (XII) is a specific organic compound different from the specific organic compounds described above.

n represents an integer of 30 to 50.
m represents an integer of 20 to 90 and 2n-2 or less.
The alkene represented by the general formula (XII) is an alkene containing two or more C = C double bonds in the molecule.
When the alkene represented by the general formula (XII) contains x C = C double bonds, m takes a value of "2n + 2-2x".
The alkene may be linear or branched. On the other hand, the alkene does not contain a cyclic structure.

When the filter contains an arcene represented by the general formula (XII), the content thereof is preferably 0.10 to 4000 mass ppt, more preferably 1.0 to 1000 mass ppt with respect to the mass of the filter. 1.0 to 350 mass ppt is more preferable, and 1.0 to 70 mass ppt is particularly preferable.
Examples of the alkene represented by the general formula (XII) include squalene (C ₃₀ H ₅₀ ), lycopene (C ₄₀ H ₅₆ ), neurosporene (C ₄₀ H ₅₈ ), phytoene (C ₄₀ H ₆₄ ), or phytoene. Phytoene (C ₄₀ H ₆₂ ) can be mentioned.

The total content of the first organic compound is 0.10 to 10000 mass ppt, preferably 1.0 to 8000 mass ppt, more preferably 5.0 to 2500 mass ppt, with respect to the mass of the filter. 0 to 850 mass ppt is particularly preferable.
If the total content of the first organic compound is 1.0 mass ppt or more (preferably 5.0 mass ppt or more) with respect to the mass of the filter, the filter can use the second organic compound described later in the environment (preferably 5.0 mass ppt or more). (Atmosphere, etc.) It is considered that it is difficult to excessively adsorb from the middle to the medium, and the defect suppressing property of the produced chemical solution is more excellent. If the total content of the first organic compound is 8000 mass ppt or less (preferably 2500 mass ppt or less, more preferably 850 mass ppt or less) with respect to the mass of the filter, the chemical solution produced contains the first organic compound derived from the filter. 2 It is considered that organic compounds are less likely to be mixed and the produced chemical solution has more excellent defect suppressing property.
When the filter contains a plurality of types of first organic compounds represented by different general formulas, at least one of the first organic compounds represented by each general formula has a range of preferable contents described above. It is preferable to satisfy, and it is more preferable that two or more kinds satisfy the above-mentioned preferable content range.

<Second organic compound>
Further, the filter preferably contains, as the specific organic compound, one or more of the second organic compounds selected from the group consisting of the compounds represented by the general formulas (VI) to (VIII).
Hereinafter, each second organic compound will be described.

・ General formula (VI)
The compounds represented by the general formula (VI) are shown below.
The compound represented by the general formula (VI) is a specific organic compound different from the specific organic compounds described above.

In the general formula (VI), R ^6a represents an alkyl group or a hydrogen atom which may have a substituent.
R ^6b and R ^6c independently represent a hydrogen atom, -AL-O-R ^6d , -CO-R ^6e , or -C (OH) -R ^6f , respectively.
AL represents an alkylene group (preferably 1 to 6 carbon atoms) which may contain a substituent.
R ^6d , R ^6e , or R ^6f each independently represent a substituent (preferably an alkyl group that may further contain a substituent).
The ^{alkyl groups, which may contain substituents represented by R 6a} , R ^6d , R ^6e , and R ^6f , may independently be linear or branched and contain a cyclic structure. You may.
The alkyl group preferably has 1 to 50 carbon atoms, more preferably 1 to 20 carbon atoms. The carbon number of the alkyl group does not include the number of carbon atoms contained in the substituent which may be contained in the alkyl group.
Examples of the substituent that the alkyl group may contain include a hydroxyl group, an alkyl ester group, and an alkyl vinyl group (preferably, the alkyl group portion has 3 to 12 carbon atoms).
If R ^6d there are a plurality, it may be different from each R ^6d same presence of a plurality. If R ^6e there are a plurality, it may be different from each R ^6e same presence of a plurality. If R ^6f there are a plurality, it may be different from each R ^6f same presence of a plurality.
Two combinations selected from the group consisting of ^{substituents R 6d} , R ^6e , and R ^6f which may be contained in the alkyl group represented by R ^{6a , two R 6d} each other, two R ^6e each other. Or, the two R ^6fs may be bonded to each other to form a ring.
Two combinations selected from the group consisting of ^{substituents R 6d} , R ^6e , and R ^6f which may be contained in the alkyl group represented by R ^{6a , two R 6d} each other, two R ^6e each other. or a group together two ^{R 6f} is formed by bonding to each ^{other, -O -, - NR 6g -} (R 6g substituent), and, one or more selected from the group consisting of -NHCO- It is preferable that the linking group of is contained.
At ^{least one of R 6a} , R ^6b , or R ^6c is a non-hydrogen atom.

When the filter contains a compound represented by the general formula (VI), the content thereof is preferably 0.10 to 20000 mass ppt, more preferably 1.0 to 4000 mass ppt with respect to the mass of the filter. 1.0 to 1000 mass ppt is more preferable, and 1.0 to 300 mass ppt is particularly preferable.
The compound represented by the general formula (VI) is exemplified.
In the following examples, AL represents an alkylene group having 1 to 10 carbon atoms and may contain a substituent, and q represents an integer of 4 to 6.

・ General formula (VII)
The compound represented by the general formula (VII) is shown below.
The compound represented by the general formula (VII) is a specific organic compound different from the specific organic compounds described above.

In the general formula (VII), R ^7a and R ^7b each independently represent an alkyl group which may contain a substituent.
The alkyl group may be linear or branched, and may contain a cyclic structure.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. The carbon number of the alkyl group does not include the number of carbon atoms contained in the substituent which may be contained in the alkyl group.
As the substituent, for example, an aromatic ring group (which may further contain a substituent, preferably a phenyl group) is preferable.

When the filter contains a compound represented by the general formula (VII), the content thereof is preferably 0.10 to 30,000 mass ppt, more preferably 1.0 to 5000 mass ppt, based on the mass of the filter. 1.0 to 395 mass ppt is more preferable, and 1.0 to 90 mass ppt is particularly preferable.
The compound represented by the general formula (VII) is exemplified.

・ General formula (VIII)
The compound represented by the general formula (VIII) is shown below.
The compound represented by the general formula (VIII) is a specific organic compound different from the specific organic compounds described above.

一般式（ＶＩＩＩ）中、Ｒ^８ａ〜Ｒ^８ｃは、それぞれ独立に、水素原子、置換基を含有していてもよいアルキル基、又は、置換基を含有していてもよいベンゼン環基を表す。
Ｒ^８ａ〜Ｒ^８ｃのうち、１つ以上（好ましくは２つ以上は）置換基を含有していてもよいアルキル基、又は、置換基を含有していてもよいベンゼン環基であるのが好ましい。
上記アルキル基は、直鎖状でも分岐鎖状でもよく、環状構造を含有していてもよい。
上記アルキル基の炭素数は１〜２０が好ましく、１〜５がより好ましい。なお、上記アルキル基の炭素数は、アルキル基が含有していてもよい置換基が含有する炭素原子の数を含まない。上記置換基としては、アルコキシ基（好ましくは炭素数２〜６）又はハロゲン原子（フッ素原子、塩素原子、臭素原子、又は、ヨウ素原子等）が好ましい。
上記ベンゼン環基が含有していてもよい置換基としては、アルキル基（好ましくは炭素数２〜１０）が好ましい。

In the general formula (VIII), R ^{8a to} R ^8c independently represent a hydrogen atom, an alkyl group which may contain a substituent, or a benzene ring group which may contain a substituent.
Of R ^{8a to} R ^8c , an alkyl group which may contain one or more (preferably two or more) substituents, or a benzene ring group which may contain a substituent is preferable. ..
The alkyl group may be linear or branched, and may contain a cyclic structure.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms. The carbon number of the alkyl group does not include the number of carbon atoms contained in the substituent which may be contained in the alkyl group. As the substituent, an alkoxy group (preferably 2 to 6 carbon atoms) or a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) is preferable.
As the substituent which may be contained in the benzene ring group, an alkyl group (preferably 2 to 10 carbon atoms) is preferable.

When the filter contains a compound represented by the general formula (VIII), the content thereof is preferably 0.10 to 20000 mass ppt, more preferably 1.0 to 10000 mass ppt, based on the mass of the filter. 1.0 to 8000 mass ppt is more preferable, 1.0 to 1000 mass ppt is particularly preferable, and 1.0 to 300 mass ppt is most preferable.
The compound represented by the general formula (VIII) is exemplified.

The total content of the second organic compound is preferably 0.10 to 200,000 mass ppt, more preferably 1.0 to 9000 mass ppt, particularly preferably 1.0 to 3000 mass ppt, relative to the mass of the filter. .0 to 750 mass ppt is most preferred.
When the filter contains a plurality of types of second organic compounds represented by different general formulas, at least one of the first organic compounds represented by each general formula has a range of preferable contents described above. It is preferable to satisfy, and it is more preferable that two or more kinds satisfy the above-mentioned preferable content range.

<Group A, Group B>
The specific organic compound can be classified into a specific organic compound of group A and a specific organic compound of group B, apart from the classification of the first organic compound and the second organic compound.
The specific organic compound of the group A is a compound selected from the group consisting of the compounds represented by the general formulas (I) to (VIII), and the specific organic compound of the group B is represented by the general formula (X). It is a compound selected from the group consisting of alkanes and alkenes represented by the general formulas (XI) and (XII).
The filter preferably contains both one or more specific organic compounds of group A and one or more specific organic compounds of group B.

When the filter contains a specific organic compound of Group A, the total content thereof is preferably 0.10 to 100,000 mass ppt, more preferably 0.10 to 10000 mass ppt, and 0.1 to 0.10 mass ppt with respect to the mass of the filter. ~ 3200 mass ppt is more preferable, 1.0 to 1000 mass ppt is particularly preferable, and 1.0 to 1200 mass ppt is most preferable.
When the filter contains a specific organic compound of Group B, the total content thereof is preferably 0.10 to 50,000 mass ppt, more preferably 0.10 to 10000 mass ppt, 1.0 to 10000 mass ppt with respect to the mass of the filter. ~ 1200 mass ppt is more preferable, 1.0 to 1000 mass ppt is particularly preferable, and 1.0 to 500 mass ppt is particularly preferable.

In the filter, the total content of the specific organic compound of group A and the specific organic compound of group B (that is, the compounds represented by the general formulas (I) to (VIII), the alkane represented by the general formula (X), and , The total content of compounds selected from the group consisting of alkanes represented by the general formulas (XI) and (XII)) is preferably 0.1 mass ppt or more at the lower limit with respect to the mass of the filter. More preferably, the mass is ppt or more, and more preferably 5 mass ppt or more. The upper limit is preferably 1,000,000 mass ppt or less, more preferably 17,000 mass ppt or less, further preferably 10000 mass ppt or less, particularly preferably 6500 mass ppt or less, and most preferably 1600 mass ppt or less.

In the present specification, the content of the specific organic compound in the filter is measured by the following method.
First, the dried filter is immersed in PGMEA (propylene glycol monomethyl ether acetate) heated under reflux conditions for 1 hour to elute the specific organic compound in the filter into PGMEA (eluting treatment).
At this time, a high-purity grade is used for the PGMEA to be immersed (also, this amount is defined as zero based on the amount of impurities contained at this time). The amount (mass) of PGMEA in which the filter is immersed is 10 to 30 times the mass of the filter to be measured.
Before and after the elution treatment, the amount and type of the specific organic compound contained in each PGMEA was measured by the GC / MS (gas chromatography-mass spectrometry) method, and the amount of each specific organic compound in the PGMEA increased by the elution treatment was measured. , Defined as the amount of each specific organic compound contained in the filter to be measured. More specifically, "(content of each specific organic compound of PGMEA after being subjected to treatment)-(content of each specific organic compound of PGMEA before being subjected to treatment)" is included in the filter specified in the present application. It is the content of each specific organic compound in.

[Metal component]
The filter may contain a metal component.
In the present invention, the metal component includes metal particles and metal ions. For example, the content of the metal component indicates the total content of the metal particles and the metal ions.
The filter may contain either metal particles or metal ions, or may contain both. The filter preferably contains both metal particles and metal ions.

The metal elements in the metal component include, for example, Al (aluminum), B (boron), Ba (barium), Ca (calcium), Cd (cadmium), Co (cobalt), Cr (chromium), Cu (copper), Fe (iron), K (potassium), Li (lithium), Mg (magnesium), Mn (manganese), Mo (molybdenum), Na (sodium), Ni (nickel), P (phosphorus), Pb (lead), Examples thereof include Sb (antimony), Si (silicon), Ti (titanium), V (vanadium), and Zn (zinc).
Among them, the metal element in the metal component is preferably one or more selected from the group consisting of Al, Ca, Cr, Cu, Fe, K, Mg, Na, Ni, Zn, and Pb. Hereinafter, these metal elements are also referred to as specific metal elements. Further, the metal component, the metal particle, and the metal ion containing the specific metal element are also referred to as the specific metal component, the specific metal particle, and the specific metal ion, respectively.

The metal particles may be a simple substance, an alloy, other metal compounds, or may be present in a form in which a metal (including a metal compound) is associated with an organic substance.
The metal component may be a metal component unavoidably contained in the filter, a metal component unavoidably contained during the production, storage, and / or transfer of the treatment liquid, or may be intentionally added. Good.

When the filter contains a specific metal component, the content thereof is preferably 0.10 to 30,000 mass ppt, preferably 0.10 to 30,000, based on the total mass of the chemical solution, from the viewpoint of more excellent defect suppression property of the obtained chemical solution. 5000 mass ppt is more preferable, 1.0 to 5000 mass ppt is further preferable, 1.0 to 1500 mass ppt is particularly preferable, and 1.0 to 300 mass ppt is most preferable.
When the content of the specific metal component is 0.1 mass ppt or more, the metal forms a coarse aggregate and is repelled by centrifugal force, and as a result, the defect suppressing property can be further improved.
Further, when the content of the specific metal component is less than 30,000 mass ppt, it is easy to avoid an increase in the occurrence of defects derived from the metal component.

When the filter contains a specific metal ion, the content thereof is preferably 0.10 to 20000 mass ppt, preferably 0.10 to 2500, based on the mass of the filter, from the viewpoint of more excellent defect suppression property of the obtained chemical solution. The mass ppt is more preferable, 1.0 to 2500 mass ppt is further preferable, and 1.0 to 800 mass ppt is particularly preferable.
When the filter contains specific metal particles, the content thereof is preferably 0.10 to 5000 mass ppt, preferably 0.10 to 1000, based on the mass of the filter, from the viewpoint of more excellent defect suppression property of the obtained chemical solution. The mass ppt is more preferable, 1.0 to 1000 mass ppt is further preferable, and 1.0 to 400 mass ppt is particularly preferable.

The types and contents of the metal ions and metal particles in the filter are the same as the elution treatment in which the specific organic compound in the filter is eluted into PGMEA, and the metal components in the filter are transferred to PGMEA. ..
Before and after the treatment, each metal component in the PGMEA was measured using an SNP-ICP / MS (single nano-particle inductively coupled plasma mass spectrometery. For example, Agillent 8900) apparatus, and the amount of each metal component in the PGMEA increased by the treatment. , Defined as the amount of each metal component contained in the filter to be measured.

[Structure of filter body]
The filter contains a filter body. The filter body is typically porous, and the liquid to be purified by the filter of the present invention passes through the pores contained in the filter body.

<Pore diameter of filter (pore diameter of filter body)>
The pore diameter of the filter is not particularly limited, and a filter having a pore diameter usually used for filtering an object to be purified, which will be described later, can be used. Among them, the pore diameter of the filter is preferably 200 nm or less, more preferably 20 nm or less, still more preferably 10 nm or less, in that the number of particles (metal particles or the like) contained in the chemical solution can be easily controlled within a desired range. The lower limit is not particularly limited, but generally 1 nm or more is preferable from the viewpoint of productivity.
When a plurality of filters are used, it is preferable that at least one filter satisfies the above range.
In the present specification, the pore diameter and the pore diameter distribution of the filter are isopropanol (IPA) or HFE-7200 (“Novec 7200”, manufactured by 3M, Hydrofluoroether, C ₄ F ₉ OC _2). H ₅₎ means a pore size and pore size distribution determined by the bubble point of the.
Normally, the pore diameter of the filter body and the pore diameter of the filter match.

<Material of filter body>
The material component of the filter body is not particularly limited. When the material contained in the filter body is a resin, a copolymer such as nylon (for example, 6-nylon and 6,6-nylon); polyethylene, and a polyolefin such as polypropylene; polystyrene; polyimide (including polyamideimide) Poly (meth) acrylate; polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene / tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and , Polyfluorocarbon such as polyvinyl fluoride; polyvinyl alcohol; polyester; cellulose; cellulose acetate and the like. Among them, nylon (preferably 6,6-nylon), polyolefin (preferably polyethylene), in that the obtained chemical solution contains more excellent solvent resistance and more excellent defect suppression property. It is preferable to contain at least one selected from the group consisting of poly (meth) acrylate and polyfluorocarbon (particularly, polytetrafluoroethylene (PTFE) and perfluoroalkoxy alkane (PFA) are preferable). These polymers can be used alone or in combination of two or more.
In addition to the resin, diatomaceous earth, glass, or the like may be used.

The polyimide (including polyamide-imide) that may be contained in the filter body preferably has an imidization ratio of 1.0, more preferably 1.4 or more. The upper limit value is not particularly limited, but is generally preferably 2.0 or less.
The "imidization rate" is defined as the value obtained by dividing the area of the peak representing the imide bond measured by the FT-IR (Fourier transform infrared spectrometer) device by the area of the peak representing benzene also measured by the FT-IR device. ..

The polyimide preferably includes a communication hole having a B value of 15 nm or less, which is obtained by a method described later. In the present specification, the “B value” means a number (unit: nm) calculated by the following method. To do.
First, adsorption molecules are adsorbed and desorbed on polyimide to obtain an adsorption isotherm. Then, from the adsorption isotherm obtained, based on the following equation (1) is calculated _{[P / {V a (P} 0 -P)}], is plotted against the equilibrium relative pressure (P / _{P 0).} Then, this plot is regarded as a straight line, and the slope s (= [(C-1) / ( _Vm・ C)]) and the intercept i (= [1 / ( _Vm・ C)]) are based on the least squares method. Is calculated. _{Then, V m} and C are calculated from the obtained slopes s and intercept i based on the formulas (2-1) and (2-2). Further, the specific surface area A is calculated from _{V m based on the formula (3).}
Next, the adsorption data of the obtained adsorption isotherm is linearly interpolated, and the adsorption amount at the relative pressure set by the pore volume calculation relative pressure is obtained. The total pore volume V is calculated from this adsorption amount.
This is generally based on the theory of a series of calculation methods for specific surface area called "BET (Brunauer, Emmet, Teller) method". In carrying out the above method, matters not described in the present specification conform to JIS R 1626-1996 "Method for measuring specific surface area by gas adsorption BET method of fine ceramic powder".

[P / {V _a (P ₀ −P)}]
= [1 / ( _Vm・ C)] + [(C-1) / ( _Vm・ C)] (P / P ₀ ) (1)
V _m = 1 / (s + i) (2-1)
C = (s / i) + 1 (2-2)
_{A = (V m · L ·} σ) / 22414 (3)

However,
V _a : Adsorption amount V _m : Adsorption amount of monolayer P: Pressure at equilibrium of adsorbed molecule P ₀ : Saturated vapor pressure of adsorbed molecule L: Avocadro number σ: Adsorption cross-sectional area of adsorbed molecule.

The B value (nm) is calculated from the formula [4V / A] based on the obtained specific surface area A and total pore volume V after calculating the specific surface area A and total pore volume V based on the above method. The value. The B value (nm) has a significance as a pore diameter inferred from the measurement result of the BET method.

It is also preferable that the filter body contains a copolymer containing a tetrafluoroethylene-based repeating unit and another repeating unit.
The copolymer containing a tetrafluoroethylene-based repeating unit and another repeating unit is not particularly limited, and is, for example, a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (Poly (PTFE-CO-PFVAE). )), Tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and mixtures thereof. PFA Teflon® is an example of a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer in which alkyl is predominantly or wholly propyl. FEP Teflon® is an example of a tetrafluoroethylene-hexafluoropropylene copolymer. Both are manufactured by DuPont. Neoflon (trademark) PFA (Daikin Industries) is a polymer similar to DuPont's PFA Teflon®. U.S. Pat. No. 5,463,006 describes a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer whose alkyl group is predominantly methyl. Hyflon (registered trademark) poly (PTFE-CO-PFVAE) 620, available from Ausimont USA, Inc., Thorofare, NJ, is also preferred.

A filter body containing a copolymer containing a tetrafluoroethylene-based repeating unit and another repeating unit may contain a copolymer containing a tetrafluoroethylene-based repeating unit and another repeating unit. , Pore diameter, pore structure, etc. are not particularly limited, and a film formed by using hollow fibers (hollow fiber film) is preferable.

The outer or inner surface of the hollow fiber membrane can be skinned or unskinned. The skin is a thin, dense surface layer that is integral with the substrate of the membrane. In the case of skinned membranes, most of the flow resistance due to the membrane is in the thin skin. The surface skin may contain pores that form a continuous porous structure of the substrate, or may be a non-porous, complete film. The asymmetry is related to the uniformity of the pore size across the thickness of the membrane, which in the case of hollow fibers corresponds to the porous wall of the fibers. The asymmetric membrane has a structure in which the pore diameter is a function of the position in the cross section. Another method of defining asymmetry is the ratio of the pore size on one surface to the pore size on the other surface.
As a method for producing a material component composed of a hollow fiber membrane using a copolymer containing such a tetrafluoroethylene-based repeating unit and another repeating unit, for example, JP-A-2015-61727 is described. Can be referred to.

When the filter body contains nylon, the filter preferably contains one or more specific organic compounds of group A and two or more specific compounds of group B described above.
In this case, the filter body preferably contains at least an alkane represented by the general formula (X) and an alkene represented by the general formula (XI). Further, in the filter, the content of the alkane represented by the general formula (X) is A, the content of the alkene represented by the general formula (XI) is B, and the content of the alkene represented by the general formula (XII). Is C, and it is preferable that the relationship of C <A and C <B is satisfied on a mass basis.

When the filter body contains polyethylene or PTFE, the filter preferably contains one or more of the above-mentioned specific organic compounds of Group A and an alkane represented by the general formula (X).

Further, the filter body may be surface-treated. The surface treatment method is not particularly limited, and a known method can be used. Examples of the surface treatment method include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, sintering and the like.

Plasma treatment is preferable because the surface of the filter body is made hydrophilic. The water contact angle on the surface of the filter body 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. , 30 ° or less is more preferable.

As the chemical modification treatment, a method of introducing an ion exchange group into the base material is preferable.
That is, the filter body may use each of the above-mentioned materials as a base material, and an ion exchange group may be introduced into the base material. Typically, a filter body including a layer containing a base material containing an ion exchange group on the surface of the base material is preferable (such a form is also simply referred to as "the filter body contains an ion exchange group" below. The same is based on the same intention in expression). The surface-modified base material is not particularly limited, and it is preferable to introduce an ion exchange group into the polymer because it is easier to produce.

Examples of the ion exchange group include a sulfonic acid group, a carboxy group, a phosphoric acid group and the like as a cation exchange group, and a quaternary ammonium group and the like as an anion exchange group. The method for introducing the ion exchange group into the polymer is not particularly limited, and examples thereof include a method in which a compound containing an ion exchange group and a polymerizable group is reacted with the polymer and grafted.

The method for introducing the ion exchange radical is not particularly limited, but the fibers of the above resin are irradiated with ionizing radiation (α-ray, β-ray, γ-ray, X-ray, electron beam, etc.) and the active portion (active portion (alpha ray, β ray, γ ray, X ray, electron beam, etc.) Radicals) are generated. The resin after irradiation is immersed in a monomer-containing solution to graft-polymerize the monomer on the substrate. As a result, a polymer in which this monomer is bonded to the polyolefin fiber as a graft polymerization side chain is produced. The resin containing the produced polymer as a side chain is contact-reacted with a compound containing an anion exchange group or a cation exchange group, and an ion exchange group is introduced into the graft-polymerized side chain polymer to produce a final product. can get.

Further, the filter body may have a configuration in which a woven fabric or non-woven fabric having an ion exchange group formed by a radiation graft polymerization method is combined with a conventional glass wool, woven fabric, or a non-woven fabric filter material.

When the filter body containing an ion exchange group is used, it is easy to control the content of the particles containing a metal atom in the chemical solution in a desired range. The material of the filter containing an ion exchange group is not particularly limited, and examples thereof include polyfluorocarbon and a material in which an ion exchange group is introduced into polyolefin, and a material in which an ion exchange group is introduced into polyfluorocarbon is more preferable.
The pore diameter of the filter containing the filter body containing the ion exchange group is not particularly limited, but is preferably 1 to 30 nm, more preferably 5 to 20 nm. When a plurality of filters are used, the filter using the filter body containing the ion exchange group may also serve as the filter containing the minimum pore diameter, or may be used separately from the filter containing the minimum pore diameter. You may. Among them, in that the defect suppressing property of the obtained chemical solution is more excellent, when a plurality of filters are used in the filtration step described later, a filter using a filter body containing an ion exchange group and a filter containing no ion exchange group are the minimum. It is preferable to use a filter that uses a filter body containing a pore diameter.

The material for which the filter body of the filter containing the minimum pore diameter is used is not particularly limited, but from the viewpoint of solvent resistance and the like, generally at least one selected from the group consisting of polyfluorocarbon and polyolefin is preferable. Polyolefins are more preferred.

Therefore, when a plurality of filters are used, the filter body of the filter may be made of a different material for each filter, and is composed of, for example, polyolefin, polyfluorocarbon, polyamide, and a material into which an ion exchange group is introduced. Two or more types of filters using a filter body using a material selected from the group may be used.

The filter (filter body) may contain a coating layer.
The filter body containing the coating layer contains, for example, a porous base material made of polyfluorocarbon and a coating layer containing a resin containing a hydrophilic group arranged so as to cover the porous base material. The filter body A can be mentioned. It is preferable that the entire surface of the porous substrate is covered with the coating layer, but there may be a part of the surface that is not covered with the coating layer. The surface also includes the surface of the pores of the porous base material.
Polyfluorocarbons include polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene / tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyfluorinated vinylidene, and polyfluoride. Examples thereof include vinyl, and polytetrafluoroethylene (PTFE) is preferable. As the polyfluorocarbon, commercially available polyfluorocarbon or the like as a porous substrate made of PTFE can be appropriately used.
The method for producing the filter body A is not particularly limited, but typically, a coating layer forming composition containing a resin containing a hydrophilic group in a porous base material made of polyfluorocarbon (for example, PTFE) and the above-mentioned porous material. A method of forming a coating layer on the surface of the porous base material (including the surface inside the pores) by contacting with the quality base material (for example, coating and / or spraying) is preferable.

The coating layer contains a resin containing a hydrophilic group. The resin is not particularly limited, and known resins can be used. Of these, polynorbornene or a copolymer thereof is preferable from the viewpoint of solvent resistance and the like.
The hydrophilic group is not particularly limited, but for example, a hydroxyl group, an ether group, an oxyalkylene group, a polyoxyalkylene group, a carboxylic acid group, an ester group, a carbonate ester group, a thiol group, a thioether group, a phosphoric acid group, and a phosphoric acid. Examples thereof include an ester group, an amide group, an imide group, and a group combining these (for example, a group containing a thioether group and a hydroxyl group), and a polyoxyalkylene group is preferable in that the effect of the present invention is more excellent. ..
As a method for producing the filter body A, for example, the descriptions in JP-A-2016-194038 and JP-A-2016-199733 can be referred to.

The filter body containing the coating layer contains, for example, a porous base material made of polyfluorocarbon and a coating layer containing a resin containing an adsorptive group arranged so as to cover the porous base material. It may be the filter body B. It is preferable that the entire surface of the porous substrate is covered with the coating layer, but there may be a part of the surface that is not covered with the coating layer. The surface also includes the surface of the pores of the porous base material.
Examples of the above-mentioned polyfluorocarbon include the same examples as those described above.
The method for producing the filter body B is not particularly limited, but typically, a composition for forming a coating layer containing a resin containing an adsorptive group on a porous substrate made of polyfluorocarbon (for example, PTFE) is used. , A method of contacting the composition for forming a coating layer with the porous substrate (for example, coating and / or spraying) to form a coating layer on the surface of the porous substrate (including the surface inside the pores). preferable.

The coating layer contains a resin containing an adsorptive group. The resin is not particularly limited, and known resins can be used. The adsorptive group is not particularly limited, but is an ether group, a hydroxyl group, a thioether group, a thiol group, a quaternary ammonium group (quaternary ammonium base), a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonium group and a diester group. , And groups containing these. Among them, an ether group, a hydroxyl group, a thioether group, a thiol group, a quaternary ammonium group, a carboxylic acid group, and a sulfonic acid group are mentioned in that the effect of the present invention is more excellent. A group containing at least one selected from the group consisting of is preferable. Of these, a group containing a thioether group and further containing at least one selected from the group consisting of an ether group, a hydroxyl group, a thiol group, a quaternary ammonium group, a carboxylic acid group, and a sulfonic acid group is preferable.
The resin may contain one type of adsorptive group alone, or may contain two or more types.

The adsorptive group is not particularly limited, but a group represented by ^{* -SL (R 1} ) _m (R ² ) _{n-m-1 is more preferable.} In the above formula, L is an n (n is an integer of 2 or more) valent linking group, and R ¹ is a group consisting of a hydroxyl group, a thiol group, a quaternary ammonium group, a carboxylic acid group, and a sulfonic acid group. It is at least one group selected from the above, and R ² represents a hydrogen atom or a monovalent organic group. Further, * represents a coupling position, and m represents an integer of 0 or more and n-1 or less.
As a method for producing the filter body B, for example, the descriptions of JP-A-2017-0022173, JP-A-2016-29146, JP-A-2016-196625, and JP-A-2016-194040 can be referred to.

The filter body containing the coating layer contains, for example, a porous base material made of polytetrafluoroethylene and a coating layer containing a fluorinated ionomer arranged so as to cover the porous base material. The fluorinated ionomer may be a filter body C containing at least two types of monomer units, which will be described later, and at least one type selected from the group consisting of iodine atoms and bromine atoms.
The above-mentioned two kinds of monomer units are an ethylene group and a functional group that can be converted into a hydrophilic group selected from the group consisting of _{-SO 2 F, -COOR, -COF, and a combination thereof, and R.} Is a fluorinated monomer unit containing a functional group which is a C _{1 to} C ₂₀ alkyl radical or a C _{6 to} C ₂₀ aryl radical; and the following formulas (OF-1) and (OF-2). , And a monomer unit derived from at least one bis-olefin selected from the group consisting of the formula (OF-3).

Wherein (OF-1), j is an integer of 2 to 10, R1, R2, R3, R4 are the same or may be different from each other, H, F, _or, C 1 -C ₅ alkyl group, It is a perfluoroalkyl group or a fluoroalkyl group.

式（ＯＦ−２）中、複数あるＡは、それぞれ、同一又は互いに異なってもよく、それぞれ独立に、Ｆ、Ｃｌ、及び、Ｈからなる群より選択され、複数あるＢは、同一又は互いに異なってもよく、それぞれ独立して、Ｆ、Ｃｌ、Ｈ、及び、ＯＲＢからなる群より選択され、ここで、ＲＢは、少なくとも部分的に、フッ素化又は塩素化され得る分枝状若しくは直鎖状のアルキルラジカルであり、Ｅは、エーテル結合で挿入され得る、必要に応じてフッ素化されている、２〜１０個の炭素原子を含有する二価の基である。

In the formula (OF-2), a plurality of A's may be the same or different from each other, and each of them is independently selected from the group consisting of F, Cl, and H, and a plurality of B's are the same or different from each other. It may be independently selected from the group consisting of F, Cl, H, and ORB, where the RB is branched or linear, which can be at least partially fluorinated or chlorinated. Is an alkyl radical of, E is a divalent group containing 2-10 carbon atoms, optionally fluorinated, that can be inserted with an ether bond.

In formula (OF-3), E, A, and B are the same as the definitions of the respective symbols in formula (OF-2), and R5, R6, and R7 may be the same or different from each other, and H. , F, or C _{1 to} C ₅ alkyl group, perfluoroalkyl group, or fluoroalkyl group.
As a method for producing the filter body C, for example, the description in JP2012-522882A can be referred to.

The filter body containing the coating layer includes a porous base material made of PTFE and a non-crosslinked coating layer containing a perfluorosulfone (PFSA) acid polymer formed so as to cover the porous base material. It may be D.
The porous substrate contained in the filter body D may have a region not covered by the non-crosslinked coating layer, but the surface of the porous substrate (including the surface of the pores communicating from the outermost surface of the porous film). It is preferable that the whole is covered with a non-crosslinked coating layer.

The porous base material made of polytetrafluoroethylene is not particularly limited, and a commercially available porous base material or the like as a porous base material made of PTFE can be appropriately used.

The PFSA polymer dispersion liquid for forming the coating layer is not particularly limited, but from Solvay Specialty Polymers (Borger, Texas) to AQUIVION (registered trademark) PFSA (for example, Aquivion PFSA D83-24B, Aquivion PFSA). and Akuivion PFSA D79-20BS) available as this is tetrafluoroethylene and sulfonyl fluoride vinyl ether _{(SFVE) F 2 C = CF} -O-CF 2 -CF 2 -SO 2 F short side chains (SSC ) Is based on the copolymer. The ionomer dispersion contains its sulfonic acid form. As the PFSA polymer dispersion, DuPont (registered trademark) Nafion (registered trademark) PFSA polymer dispersion is also preferable.

When forming the coating, the content of PFSA in the coating solution can be adjusted as appropriate. Generally, the content is preferably in the range of 0.10 to 3% by mass, more preferably 0.12 to 2.2% by mass, based on the total mass of the coating solution.

The method for forming the coating on the base material is not particularly limited, and examples thereof include a method of immersing the base material in the coating liquid and a method of spraying the coating liquid on the base material.

It is also preferable that the filter body contains two or more layers. The two or more layers may be the same or different.
Specific examples of the combination of two or more layers include a first layer made of a porous substrate made of PTFE containing a first hydrophilic group on the surface, and the first hydrophilic group arranged on the first layer. Examples thereof include a laminated structure containing a second layer made of a porous substrate made of PTFE having a different second hydrophilic group on the surface.

The method for forming the PTFE porous base material (membrane) containing the hydrophilic group on the surface is not particularly limited, and the first hydrophilic group and / or the second is formed on the surface of the unmodified PTFE porous membrane. Examples include a method of binding hydrophilic groups.
The method for introducing a hydrophilic group into an unmodified porous substrate made of PTFE is not particularly limited, but a method in which an unmodified PTFE is used as a substrate and a hydrophilic group is introduced into the substrate is preferable.
The method for introducing the hydrophilic group is not particularly limited, but the porous film made of PTFE is irradiated with ionizing radiation (α-ray, β-ray, γ-ray, X-ray, electron beam, etc.) and activated in the PTFE resin. Generates parts (radicals). The irradiated PTFE resin is immersed in a solution containing a compound containing a predetermined functional group to bond the compound to a substrate. At this time, in the form in which the resin is immersed in the monomer containing a functional group, the monomer containing a functional group is graft-polymerized on the main chain of the resin. As a result, this monomer binds to the polyolefin fiber as a graft polymerization side chain.

In addition to the above, hydrophilic groups may be introduced into the PTFE porous substrate by plasma treatment, frame treatment, or the like.

The first hydrophilic group and the second hydrophilic group are not particularly limited, but for example, a hydroxyl group, a (poly) ether group, an oxyalkylene group, a polyoxyalkylene group, a carboxylic acid group, a boronic acid group, and a phosphonic acid group. , Sulphonic acid group, amino group, quaternary ammonium group, imidazolium group, pyridinyl group, ester group, carbonate ester group, thiol group, thioether group, phosphoric acid group, phosphoric acid ester group, amide group, imide group, ) Fluoroalkyl groups and groups combining these groups are mentioned. Among them, polyether groups, hydroxyl groups, thioether groups, thiol groups, quaternary ammonium groups, carboxylic acid groups, sulfonic acid groups, and combinations thereof. It is preferably at least one selected from the group consisting of groups.

<Pore structure of filter body>
The pore structure of the filter body (in other words, the pore structure of the material component contained in the filter body) is not particularly limited, and may be appropriately selected depending on the components in the product to be purified, which will be described later. In the present specification, the pore structure of the filter body means the pore size distribution, the positional distribution of the pores in the filter body, the shape of the pores, etc., and typically the filter body (or the filter body). It can be controlled by the manufacturing method of the material component contained in the filter body).
For example, a porous film can be obtained by sintering a powder such as a resin to form a porous film, and a fiber film can be obtained by forming by a method such as electrospinning, electroblowing, or melt blowing. These have different pore structures.

A "porous membrane" is a membrane that retains components in an object to be purified, such as gels, particles, colloids, cells, and polyoligomers, while components that are substantially smaller than the pores pass through the pores. Means. Retention of components in the object to be purified by the porous membrane may depend on operating conditions, such as surface velocity, surfactant use, pH, and combinations thereof, and the pore size of the porous membrane. It may depend on the structure, the size of the particles to be removed, and the structure (hard particles, gel, etc.).

If the object to be purified contains negatively charged particles, the polyamide acts as a non-sieving membrane for the removal of such particles. Typical non-sieving membranes include, but are not limited to, nylon membranes such as nylon-6 membranes and nylon-6,6 membranes.
In addition, the holding mechanism by "non-sieve" used in this specification refers to the holding caused by the pressure drop of the filter or the mechanism such as interference, diffusion and adsorption which is not related to the pore size.

Non-sieve retention includes retention mechanisms such as obstruction, diffusion and adsorption that remove particles to be removed in the object to be purified, regardless of filter pressure drop or filter pore size. The adsorption of particles on the surface of the material component can be mediated by, for example, van der Waals force and electrostatic force between molecules. Interfering effects occur when particles moving through a non-sieving membrane layer containing meandering paths cannot change direction fast enough to avoid contact with the non-sieving membrane. Particle transport by diffusion results primarily from the random or Brownian motion of small particles, which creates a certain probability that the particles will collide with the filter media. In the absence of repulsive force between the particles and the filter, the non-sieve retention mechanism can be active.

The UPE (ultra high molecular weight polyethylene) film that the filter body may contain is typically a sieving film. The sieving membrane means a membrane that captures particles mainly through a sieving mechanism, or a membrane that is optimized for capturing particles through a sieving mechanism.
Typical examples of sieving membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes.
The "sieve holding mechanism" refers to holding the result when the particles to be removed are larger than the pore size of the porous membrane. Sieve retention is improved by forming a filter cake (aggregation of particles to be removed on the surface of the membrane). The filter cake effectively fulfills the function of a secondary filter.

The material of the fiber film is not particularly limited as long as it is a polymer capable of forming the fiber film. Examples of the polymer include polyamide and the like. Examples of the polyamide include nylon 6, nylon 6, 6 and the like. The polymer forming the fiber film may be poly (ether sulfone). When the fibrous membrane is on the primary side of the porous membrane, the surface energy of the fibrous membrane is preferably higher than that of the polymer that is the material of the porous membrane on the secondary side. Such combinations include, for example, the case where the material of the fiber membrane is nylon and the porous membrane is polyethylene (UPE).

The method for producing the fiber film is not particularly limited, and a known method can be used. Examples of the method for producing the fiber film include electrospinning, electroblowing, and melt blowing.

The pore structure of the porous membrane (for example, a porous membrane containing UPE and PTFE and the like) is not particularly limited, and examples of the shape of the pores include a lace shape, a string shape, a node shape, and the like. Be done.
The distribution of the size of the pores in the porous membrane and the distribution of the positions in the membrane are not particularly limited. The size distribution may be smaller and the distribution position in the film may be symmetrical. It is also preferable that the filter body contains a membrane having a larger size distribution and an asymmetric distribution position in the membrane (the above membrane is also referred to as an "asymmetric porous membrane"). In an asymmetric porous membrane, the size of the pores varies within the membrane. Above all, the asymmetric porous membrane preferably has an asymmetric pore size distribution with respect to the thickness direction (filtration direction). Typically, the pore size increases from one surface of the membrane to the other surface of the membrane. At this time, the surface on the side with many pores having a large pore diameter is called the "open side", and the surface on the side with many pores with a small pore diameter is also called the "tight side".
Further, as the asymmetric porous membrane, for example, a membrane in which the size of the pores is minimized at a certain position within the thickness of the membrane (this is also referred to as “hourglass shape”) can be mentioned.
When an asymmetric porous membrane is used and the primary side has a larger size pore, in other words, the primary side has an open side, a prefiltration effect can be produced.

As the asymmetric porous membrane, for example, a membrane containing an asymmetric porous membrane made of UPE and a graft chain bonded to the surface of the asymmetric porous membrane is preferable. Further, it is preferable that at least a part of the above-mentioned graft chain contains a neutral group or an ion exchange group.
For a membrane containing an asymmetric porous membrane made of UPE and a graft chain bonded to the surface of the asymmetric porous membrane, for example, the description in JP-A-2017-536232 may be referred to.

The porous film may contain a thermoplastic polymer such as PESU (polyether sulfone), PFA (perfluoroalkoxy alkane, copolymer of ethylene tetrafluoride and perfluoroalkoxy alkane), polyamide, and polyolefin. , Polytetrafluoroethylene and the like may be contained.
Among them, ultra-high molecular weight polyethylene is preferable as the material of the porous membrane. Ultra-high molecular weight polyethylene means thermoplastic polyethylene containing extremely long chains, and has a molecular weight of 1 million or more, typically 2 to 6 million.

<Support layer>
The material containing the composition and structure as described above preferably constitutes a member (also referred to as a “filtration layer”) used for exerting the filtration capacity of the filter body, and the filter body as described above is this. In addition to such a filtration layer, it is preferable to contain a support layer.
For example, when it is difficult to process the support layer into a desired shape with a filter body composed of only a filtration layer, the support layer is laminated with the filtration layer to impart appropriate rigidity to the filter to improve processability.
Further, the filter body may contain only one filtration layer, or may contain two or more layers. Similarly, the filter body may contain only one support layer or two or more layers. The support layer may be provided on only one side (primary side or secondary side of filtration) or both sides of the filtration layer. When the filter body contains two or more filtration layers, the filtration layers and the support layers may be provided alternately.
As the material of the support layer, for example, polyolefin (polyethylene (including UPE), polypropylene, etc.), PTFE, PFA, or polyester can be used.

The filter body preferably contains two or more layers, each made of a different material.
Examples of the filter body containing two or more layers made of different materials include a filter in which the filter body has a filtration layer and a support layer, and the filtration layer and the support layer are made of different materials.
Further, in the filter body containing two or more layers made of different materials, the filter body has a filtration layer and a support layer, the filtration layer and the support layer are both made of the same material, and the surface of the filtration layer is grafted. It may be a filter in which a graft layer, which is a material different from the filtration layer and the support layer, is formed.
In addition, the filter body containing two or more layers made of different materials has a layer that also serves as a filtration layer and a support layer, and the surface thereof is grafted to serve as a filtration layer and a support layer. A filter on which a graft layer, which is a material different from the layer that also serves as a layer, is formed may be used.

Further, the filter body is preferably made of a material other than the fluorine-based material.
When the filter body is made of a material other than the fluorine-based material, for example, the filtration layer and the support layer of the filter body are both made of a material other than the fluorine-based material (fluorine resin such as PTFE, PFA, and PESU). Can be mentioned.
In other words, in the filter body made of a material other than the fluorine-based material, for example, the filtration layer and the support layer are both made of a material other than the fluorine-based material (polyolefin (including UPE), polypropylene, etc.), polyester, and / Or, polyamide (nylon 6, nylon 6, 6, etc.) is preferable. The filtration layer of the filter body made of a material other than the fluorine-based material may be grafted (preferably using non-fluorine-based repeating units).
In the filter body made of a material other than the fluorine-based material, the elution of components from the filter is likely to be reduced, and the defect suppressing property of the manufactured chemical solution (particularly the pattern defect suppressing property when a pattern is formed by EUV exposure) is more excellent. ..

[Manufacturing method of filter]
As a method for producing a filter of the present invention, for example, it is preferable to include a step of pretreating an untreated filter containing one or more specific organic compounds with an organic cleaning solution.
The untreated filter is, for example, a filter available on the market, and usually, the surface and / or the inside of the untreated filter contains a first organic compound exceeding the content allowed by the present invention.
Hereinafter, the filter to be preprocessed (unprocessed filter) is also referred to as a processed filter.

The filter to be processed may be obtained from the market as described above. When such a filter to be processed is put on the market, the filter to be processed is often packed with a packing material, such as being put in a packing bag and sealed for the purpose of avoiding contamination or the like. At this time, if the portion (contact portion) of the packaging material that can come into contact with the filter to be processed in the packed state is polyolefin (polyethylene containing high-density polyethylene, etc.), the contact portion is fluororesin or stainless steel. Compared with the case of steel, the above-mentioned specific organic compound and / or other impurity components are more likely to adhere to the filter to be treated and cause contamination.
Therefore, the filter to be treated before the pretreatment is excellent in reducing the cost required for the pretreatment and / or in suppressing defects of the chemical solution produced by using the finally obtained filter. It is preferable that at least a part of the contact portion with the filter to be treated is packed with a packing material made of a fluororesin or stainless steel.
If at least a part of the contact portion is a fluororesin or stainless steel, contamination to the filter to be treated can be reduced, and the present invention obtained by pretreating the filter to be treated packed with such a packing material. The effect of the present invention realized by the filter of is also more excellent.
In other words, the filter of the present invention is a filter obtained by pretreating a filter to be treated, in which at least a part of a contact portion with the filter to be treated is packed with a packing material having a fluorine-based purpose or stainless steel. It is also preferable to have it.

Examples of the fluororesin at the contact portion include fluororesins such as PTFE and PFA.
Examples of the stainless steel in the contact portion include stainless steel described later as a corrosion resistant material, and among them, stainless steel (EP-SUS) in which the contact portion is electropolished is preferable.
The area of the contact portion, which is a fluororesin and / or stainless steel, is preferably 50 to 100%, more preferably 90 to 100%, still more preferably 99 to 100%, based on the total area of the contact portion.
The form of the packing material is not particularly limited, and may be a bag form or a capsule form.
The packing material need only have at least a part of the contact portion made of fluorine-based resin and / or stainless steel, and the entire packing material may be made of fluorine-based resin and / or stainless steel, or may be combined with other materials. It may be a composite material of. For example, a composite material having a layer structure in which the contact portion is made of a fluororesin and / or stainless steel and the contact portion is made of a fluororesin and / or stainless steel other than the contact portion may be used.
Even when the filter of the present invention (for example, the filter to be treated after being pretreated) is packed with a packing material and stored or distributed, the packing material having the structure of the contact portion having the above-mentioned structure is used. It is preferably packed.
The filter to be processed, which is packed with a packing material, may be appropriately cleaned before being packed.

The type of the organic cleaning liquid used for the pretreatment is not particularly limited, and a known organic solvent can be used as the main component. In the present specification, the main component means a component contained in an amount of 99.9% by mass or more based on the total mass of the organic cleaning liquid, and more preferably 99.99% by mass or more.
The organic solvent may contain, for example, an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, an alkyl lactate ester, an alkyl alkoxypropionate, a cyclic lactone (preferably having 4 to 10 carbon atoms), and a monoketone which may contain a ring. Examples include compounds (preferably 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, dialkyl sulfoxides, cyclic sulfones, dialkyl ethers, monohydric alcohols, glycols, alkyl acetate esters, N-alkylpyrrolidone and the like. Be done.

Among them, the organic cleaning liquids are propylene glycol monomethyl ether acetate, isopropanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, γ-butyrolactone, and di. Isoamyl ether (isoamyl ether), butyl acetate, isoamyl acetate, 4-methyl-2-pentanol, dimethylsulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, Cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, mesitylene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, It preferably contains one or more selected from the group consisting of 1-octanol, 2-octanol, ethyl acetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate.

The pretreatment preferably includes, for example, a step of immersing the filter to be treated in the organic cleaning liquid and / or a step of passing the organic cleaning liquid through the filter to be treated.

When the pretreatment includes a step of immersing the filter to be treated in the organic cleaning liquid, as a method of immersing the filter to be treated in the organic cleaning liquid, the immersion container is filled with the organic cleaning liquid, and the filter to be treated is added to the organic cleaning liquid. A method of dipping can be mentioned.
As the immersion container, a housing contained in the filter unit can also be used in the filtration device described later. That is, there is a method in which the filter to be processed is housed in the housing contained in the filtration device (preferably in the state of being contained in the cartridge with a filter described later), the housing is filled with the immersion liquid, and the mixture is allowed to stand in that state. Can be mentioned.
In addition to the above, an immersion container is prepared separately from the housing containing the purification device (that is, an immersion container is prepared outside the purification device), and the separately prepared immersion container is filled with an organic cleaning solution and coated. Another method is to immerse the treatment filter.
Above all, a method of filling the immersion container prepared outside the filtration device with the organic cleaning liquid and immersing the filter to be treated in the organic cleaning liquid is preferable in that impurities eluted from the filter to be treated do not mix into the filtration device.

The shape and size of the immersion container can be appropriately selected depending on the number and size of the filters to be immersed, and are not particularly limited.
The material of the immersion container is not particularly limited, but it is preferable that at least the wetted portion is formed of a corrosion-resistant material described later.
The materials of the immersion container include polyfluorocarbon (PTFE, PFA: perfluoroalkoxy alkane, and PCTFE: polychlorotrifluoroethylene, etc.), PPS (polyphenylene sulfide), POM (polyoxymethylene), and polyolefin. It is preferable to contain at least one selected from the group consisting of (PP, PE, etc.), and more preferably to contain at least one selected from the group consisting of polyfluorocarbon, PPS, and POM. , Polyfluorocarbon is more preferable, and at least one selected from the group consisting of PTFE, PFA, and PCTFE is particularly preferable, and PTFE is most preferable to be contained.
Further, the immersion container is preferably washed before use, and is preferably washed using an organic washing liquid (so-called co-washing) at the time of washing.

The immersion time is, for example, preferably 1 day or longer, more preferably 3 days or longer, further preferably 1 week or longer, and particularly preferably 1 month or longer. The upper limit is not particularly limited, but is usually less than one year.
The temperature of the organic cleaning liquid during the dipping treatment is preferably room temperature (23 ° C.) or higher, more preferably 35 ° C. or higher. The upper limit is not particularly limited, but is usually lower than the boiling point of the organic cleaning solution used.

Further, the filter to be treated may be subjected to ultrasonic treatment continuously or temporarily during immersion.
For example, when the filter body is used in the form of a hollow cylinder (for example, when the filter is used in a state of being contained in a cartridge with a filter described later), the ultrasonic output is the filter of the cartridge with the filter (processed). The filter) has a cylinder length of 1 inch, preferably 50 kW or more, more preferably 80 kW or more, and further preferably 100 kW or more. The upper limit is not particularly limited, but is usually 200 kW.
The ultrasonic treatment time is, for example, preferably 5 minutes or more, more preferably 15 minutes or more, further preferably 1 hour or more, and particularly preferably 3 hours or more. The upper limit is not particularly limited, but is usually less than 10 hours.

When the pretreatment includes a step of passing an organic cleaning liquid through the filter to be treated, for example, the filter is housed in the housing of the filter unit of the filtration device described later (preferably in a state of being contained in a cartridge with a filter). , A method of introducing an organic cleaning liquid into the housing and passing the organic cleaning liquid through the main body of the filter to be treated can be mentioned.

At the time of cleaning, the specific organic compound or the like contained in the filter to be treated is transferred (typically dissolved) to the organic cleaning liquid. Therefore, it is preferable that the organic cleaning liquid once passed through the filter is not used for cleaning again, but is discharged to the outside of the filtration device described later. In other words, it is preferable not to perform circulation cleaning.

As another form of the method of passing an organic cleaning liquid through the filter to be processed for cleaning, there is a method of cleaning the filter to be processed using a cleaning device. In the present specification, the cleaning device means a device different from the filtration device provided outside the filtration device. The form of the cleaning device is not particularly limited, but a device having the same configuration as the filtration device can be used.

When the pretreatment includes a step of passing an organic cleaning liquid through the filter body to be treated, the amount of the liquid to be passed is, for example, when the filter body to be treated has a hollow cylindrical shape (typically, a filter unit). When a cartridge with a filter containing a filter to be treated is stored in the housing of the above, and an organic cleaning liquid is passed therethrough), 10 kg or more is preferable, and 50 kg or more is more preferable with respect to 1 inch of the cylinder length of the filter body to be treated. 300 kg or more is more preferable, and 500 kg or more is particularly preferable.
The temperature of the organic cleaning liquid to be passed is preferably room temperature (23 ° C.) or higher, more preferably 35 ° C. or higher. The upper limit is not particularly limited, but is usually lower than the boiling point of the organic cleaning solution used.

In the pretreatment, the ratio of the content of the specific organic compound contained in the filter after the pretreatment (also referred to as "cleanliness") to the total content of the specific organic compound contained in the filter to be treated (untreated filter) is , 0.5000 or less, more preferably 0.1000 or less, further preferably 0.0300 or less, and 0.0100 or less. It is particularly preferable to carry out so as to. The lower limit is not particularly limited, but is usually 0.00001 or more.

[Filtration device]
The filter of the present invention is preferably installed in a filtration device for use.
The filtration device contains the filter of the present invention and is preferably used for purifying the liquid to be purified to produce a chemical liquid.
For example, the filtration device contains an inflow portion, an outflow portion, and one or more (preferably 2 or more, more preferably 2 to 6, more preferably 3 to 4, particularly preferably 4) filters of the present invention. However, it is preferable that each filter is arranged in series between the inflow portion and the outflow portion and includes a flow passage from the inflow portion to the outflow portion.
In the filtration device, a plurality of filters may be arranged in parallel. In this case, regardless of whether the liquid to be purified passes through any flow path from the inflow portion to the outflow portion, the amount of the liquid to be purified is 1 or more (preferably 2 or more, more preferably 2 to 6, still more preferably 3 to 4, in particular. It is preferably configured to pass through the filter of the present invention in 4). That is, the filtration device may combine both a parallel arrangement and a series arrangement of a plurality of filters.

When two or more filters are arranged in series in a filtration device, the pore diameter of at least one filter (preferably the filter having the largest pore diameter) among the two or more filters arranged in series is 10 to 200 nm. The pore diameter of the filter having the smallest pore diameter is preferably 1 to 10 nm.

Further, among the two or more filters arranged in series, the filter body of at least one filter preferably contains an ion exchange group.
Further, among the two or more filters arranged in series, the filter body of at least one filter is a filter body containing nylon, and the at least one filter is an alkane represented by the general formula (X). , An alkene represented by the general formula (XI), and an alkane content A represented by the general formula (X), an alkene content B represented by the general formula (XI), and It is also preferable that the alkene content C represented by the general formula (XII) is C <A and C <B on a mass basis.
Further, among the two or more filters arranged in series, the filter body of at least one filter contains polyethylene or polytetrafluoroethylene, and the at least one filter is selected from the above-mentioned group A. It is also preferable to contain a compound and an alkane represented by the general formula (X).
Further, among the two or more filters arranged in series, at least one (preferably more than half of the two or more filters, more preferably more than half of the two or more filters) has a fluorine-based filter body. It is also preferable that the filter body is made of a material other than the material.

Hereinafter, a filtration device containing the filter of the present invention will be described. In the following description, at least the filter A is the filter of the present invention, and other filters (for example, the filter BU) may use filters other than the filter of the present invention.
However, it is preferable that at least two filters of the present invention are arranged in series between the inflow portion and the outflow portion of the filtration device, and the filters in the filtration device are all the filters of the present invention. preferable.

<First Embodiment>
FIG. 1 is a schematic view showing a filtration device according to the first embodiment of the present invention.
The filtration device 100 is a filtration device in which a filter 103 (filter A) and a filter 104 (also referred to as a filter BU) different from the filter 103 are arranged in series between the inflow section 101 and the outflow section 102 via a pipe 105. Is.
The inflow section 101, the filter 104, the pipe 202, the filter 103, and the outflow section 102 are configured so that the liquid to be purified can flow inside each of the inflow portion 101, the filter 104, the pipe 202, the filter 103, and the outflow portion 102. Path) is formed.

The form of the inflow section 101 and the outflow section 102 is not particularly limited as long as the liquid to be purified can be introduced into the filtration device and discharged, but typically, a hollow containing an inlet and an outlet. Cylindrical piping (inflow part and outflow part) and the like can be mentioned. Hereinafter, a form in which the outflow portion and the inflow portion are pipes will be described as an example.
The form of the inflow section 101, the pipe 105, and the outflow section 102 is not particularly limited, but typically includes a hollow cylindrical form in which the liquid to be purified is formed so as to be able to flow. These materials are not particularly limited, but the wetted part (the part that the liquid to be purified may come into contact with when filtering the liquid to be purified) uses a corrosion-resistant material described later as a material component (constituent component). It is preferable to contain it. In other words, it is preferably formed using a corrosion resistant material described later.

The liquid to be purified introduced from the inflow portion 101 of the filtration device 100 circulates in the filtration device 100 along the flow path S1, and is sequentially filtered by the filter 103 (filter A) and the filter 104 (filter BU) between them. Then, it is discharged from the outflow portion 102 to the outside of the filtration device 100. The form of the liquid to be purified will be described later.
The filtration device 100 has a pump (not shown) on the flow passage S1 (for example, the inflow portion (101), the pipe (105), the outflow portion (102), etc.) for the purpose of circulating the liquid to be purified. It may contain a damper, a valve and the like. The method of circulating the liquid to be purified through the flow passage in the filtration device 100 is not limited to the above, and a method of introducing the pressurized liquid to be purified into the inflow portion may be used.

The form of the filter 103 (filter A) and the filter 104 (filter BU) is not particularly limited. Examples of the form of the filter A and the filter BU include a planar shape, a pleated shape, a spiral shape, a hollow cylindrical shape, and the like. Among them, in terms of excellent handleability, it is typically wound around a core material and the core material, which is formed of a material that allows the liquid to be purified to permeate and / or has a structure that allows the liquid to be purified to permeate. It is preferable to form a cartridge with a filter (filter cartridge) containing a filter arranged on the core material in a rotated form. In this case, the material of the core material is not particularly limited, but it is preferably formed from a corrosion-resistant material described later.
The core material is not a component of the filter.

The method of arranging the filter is not particularly limited, but typically, in a housing (not shown) including at least one inlet and at least one outlet, and at least one flow path is formed between the inlet and the outlet. It is preferable to configure the filter unit arranged in. In that case, the filter is arranged across the flow path within the housing. The flow path formed in the housing forms a part of the flow path S1, and the liquid to be purified is filtered by a filter arranged so as to cross the flow path S1 when flowing through the flow path S1.

The material of the housing is not particularly limited, and examples thereof include any suitable hard impermeable material including any impermeable thermoplastic material compatible with the liquid to be purified. For example, the housing can be made from a metal such as stainless steel, or a polymer. In certain embodiments, the housing is a polymer such as polyacrylate, polypropylene, polystyrene, or polycarbonate.
Further, in terms of obtaining a filtration device containing more excellent effects of the present invention, at least a part of the wetted portion of the housing, preferably 90% with respect to the surface area of the wetted portion, more preferably the wetted portion. 99% of the surface area is preferably made of a corrosion resistant material described later. In the present specification, the wetted portion means a portion (however, excluding the filter itself) that the liquid to be purified may come into contact with, and means an inner wall or the like of a unit such as a housing.

(Filter BU)
The filter BU is a filter arranged in series on the flow path. The filter BU is a filter arranged in series with the filter A on the upstream side of the filter A on the flow path.
It is preferable that the filter A and the filter BU are different filters. In the present specification, the filter different from the filter A means a filter in which at least one selected from the group consisting of the filter A and the material, the pore diameter, and the pore structure is different.
Among them, the filter BU is preferably different from the filter A in at least one selected from the group consisting of the pore diameter and the material, and at least the materials are different, in that a filtration device containing the more excellent effect of the present invention can be obtained. Is preferable.
In the present specification, the materials of the filter A and the filter BU are different when the components (material components) contained in each filter are different; when the filter is made of resin, the surface of the filter is different due to the difference in surface treatment. The case where the type of the substituent arranged in is different is typically included.

The pore diameter of the filter BU is not particularly limited, and any pore diameter may be contained as the filter used in the filtration device. Above all, the filter BU preferably contains a pore diameter larger than that of the filter A in that a chemical solution containing more excellent defect inhibitory properties can be obtained. Among them, the pore diameter of the filter BU is preferably 200 nm or less, preferably 10 nm or more, and more preferably 20 nm or more.
According to the study by the present inventors, when a filtration device in which the filter BU having a pore diameter of 20 nm or more is arranged on the upstream side of the filter A in the flow passage S1, the filter A is less likely to be clogged. It is known that the life of the filter A can be extended. As a result, a filtration device capable of stably providing a chemical solution containing more excellent defect suppressing property can be obtained.

In particular, when the filtration device contains a plurality of filter BUs, the pore diameter of the filter BUs arranged on the most upstream side in the flow passage is preferably 20 nm or more, more preferably 50 nm or more, and preferably 200 nm or less. When the pore diameter of the filter BU (which may be the filter C described later) arranged on the most upstream side of the flow passage is within the above range, the life of the filter is further improved, and as a result, excellent defect suppression property is obtained. It is preferable that the contained chemical solution can be stably produced.

Although the filtration device of FIG. 1 contains one filter BU, the filtration device according to the present embodiment may contain a plurality of filter BUs. In that case, the relationship between the pore diameters of the plurality of filter BUs is not particularly limited, but the pore diameters of the filter BUs arranged most upstream on the flow path are easy to obtain in that a chemical solution containing more excellent defect suppressing properties can be obtained. Is preferably the maximum. In this way, the life of the filter (including the filter A) arranged downstream of the most upstream filter BU can be extended, and as a result, the chemical solution containing better defect suppression property can be stably provided. The device is obtained.

When at least one filter BU among one or more filter BUs contained in the filtration device contains a resin containing an ion exchange group as a material component, metal impurities (for example, metal) contained in the liquid to be purified As a result, the content of metal ions in the obtained chemical solution can be reduced because it contains a stronger interaction with ions, etc.), and the obtained chemical solution contains more excellent uniform performance of the pattern width.

[Manufacturing method of chemical solution]
The method for producing a chemical solution according to an embodiment of the present invention is a method for producing a chemical solution in which a chemical solution to be purified is purified to obtain a chemical solution, and the filter of the present invention described above (a filtration device containing the filter of the present invention). It contains a filtration step of filtering the liquid to be purified using the above to obtain a chemical liquid.

<Liquid to be purified>
The liquid to be purified to which the method for producing a chemical solution according to the embodiment of the present invention can be applied is not particularly limited, but preferably contains a solvent. Examples of the solvent include an organic solvent and water, and it is preferable that the solvent contains an organic solvent. In the following, the content of the organic solvent (the total content when a plurality of organic solvents are contained) exceeds 50% by mass with respect to the total mass of the solvent contained in the liquid to be purified. The purified liquid and the aqueous purified liquid having a water content of more than 50% by mass with respect to the total mass of the solvent contained in the liquid to be purified will be described separately.

(Organic solvent-based purified liquid)
-Organic solvent The organic solvent-based purified liquid contains a solvent, and the content of the organic solvent is more than 50% by mass with respect to the total mass of the solvent contained in the liquid to be purified.
The organic solvent-based purified liquid contains an organic solvent. The content of the organic solvent in the organic solvent-based purified liquid is not particularly limited, but is generally preferably 99.0% by mass or more with respect to the total mass of the organic solvent-based purified liquid. The upper limit value is not particularly limited, but is generally preferably 99.999999% by mass or less.
One type of organic solvent may be used alone, or two or more types may be used in combination. When two or more kinds of organic solvents are used in combination, the total content is preferably within the above range.

In the present specification, the organic solvent is intended to be a liquid organic compound contained in a content exceeding 10,000 mass ppm per component with respect to the total mass of the liquid to be purified. That is, in the present specification, the liquid organic compound contained in excess of 10,000 mass ppm with respect to the total mass of the liquid to be purified corresponds to an organic solvent.
In addition, in this specification, a liquid means that it is a liquid at 25 ° C. and an atmospheric pressure.

The volume resistivity of the organic solvent-based purified liquid (or the manufactured chemical liquid) may be 500,000,000 Ωm or more.
The volume resistivity of the organic solvent-based purified liquid (or the manufactured chemical solution) can be measured using, for example, a volume resistivity meter SME-8310 manufactured by Hioki Denki Co., Ltd. or a super-insulation meter SM-8220.

The type of the organic solvent as the liquid to be purified is not particularly limited, and a known organic solvent can be used. The organic solvent may contain, for example, an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, an alkyl lactate ester, an alkyl alkoxypropionate, a cyclic lactone (preferably having 4 to 10 carbon atoms), and a monoketone compound which may contain a ring. (Preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, dialkyl sulfoxide, cyclic sulfone, dialkyl ether, monohydric alcohol, glycol, alkyl acetate ester, N-alkylpyrrolidone and the like can be mentioned. ..
As the organic solvent, for example, the organic solvents described in JP-A-2016-57614, JP-A-2014-219664, JP-A-2016-138219, and JP-A-2015-135379 are used. May be good.

Organic solvents include, for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, cyclohexanone, methyl methoxypropionate, butyl acetate, γ-butyrolactone, 4-methyl-2-pentanol, propylene glycol monoethyl. Ether, ethyl lactate, cyclopentanone, diisoamyl ether (isoamyl ether), isoamyl acetate, isopropanol, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, Cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, mesitylene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, One or more selected from the group consisting of 1-octanol, 2-octanol, ethyl acetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate is preferable.

The type and content of the organic solvent in the liquid to be purified can be measured using a gas chromatograph mass spectrometer.

The organic solvent as the liquid to be purified preferably has a Hansen solubility parameter distance of 3 to 20 MPa ^0.5 (more preferably 5 to 20 MPa ^0.5 ) with respect to Eikosen, for example.
When two or more kinds of organic solvents are used, it is preferable that at least one kind satisfies the range of the Hansen solubility parameter.
When two or more kinds of organic solvents are used, it is preferable that the weighted average value of the Hansen solubility parameter based on the molar ratio of the content of each organic solvent satisfies the range of the Hansen solubility parameter.

For example, it is also preferable that the organic solvent-based purified liquid is only an organic solvent that substantially satisfies the range of the Hansen solubility parameter from the viewpoint of more excellent defect suppressing property of the chemical solution. The organic solvent-based purified liquid is only an organic solvent that substantially satisfies the range of the Hansen solubility parameter. The content of the organic solvent that satisfies the range of the Hansen solubility parameter is based on the total mass of the organic solvent. It means that it is 99% by mass or more (preferably 99.9% by mass or more).

Further, for example, it is also preferable that the organic solvent-based purified liquid is a mixed solvent containing both an organic solvent satisfying the range of the Hansen solubility parameter and an organic solvent not satisfying the range of the Hansen solubility parameter.
In this case, the organic solvent-based purified liquid (mixed solvent) contains an organic solvent satisfying the above range of the Hansen solubility parameter with respect to the total mass of the organic solvent-based purified liquid from the viewpoint of more excellent defect suppression property of the obtained chemical solution. 20 to 80% by mass (preferably 30 to 70% by mass) of an organic solvent containing 20 to 80% by mass (preferably 30 to 70% by mass) and not satisfying the above range of the Hansen solubility parameter with respect to the total mass of the organic solvent-based purified liquid. It is preferably contained (30 to 70% by mass).
When the content of the organic solvent satisfying the range of the Hansen solubility parameter and the content of the organic solvent not satisfying the range of the Hansen solubility parameter are equal to or higher than a certain level, the organic solvent not satisfying the range of the Hansen solubility parameter is specified. Compared with the case where the amount is out of the range (for example, 1% by mass or more and less than 20% by mass or more than 80% by mass with respect to the total mass of the mixed solvent), the affinity of the chemical solution for the metal-based material and the organic-based material is improved. It can be adjusted to an appropriate range, and it is considered that the effect of the present invention is more excellent.
In this case, the total content of the organic solvent satisfying the Hansen solubility parameter range and the organic solvent not satisfying the Hansen solubility parameter range is 99.0 with respect to the total mass of the organic solvent-based purified liquid. The mass% or more is preferable. The upper limit value is not particularly limited, but is generally preferably 99.999999% by mass or less.
Incidentally, in an organic solvent which does not satisfy the range of the Hansen solubility parameter, the distance of Hansen parameters for eicosene is, ^{0 MPa 0.5} or more ^3MPa less than ^0.5 (preferably ^{0 MPa 0.5} ultra ^3MPa less than ^0.5), or , 20 MPa over ^0.5 (preferably over 20 MPa over ^{0.5 and over} 50 MPa ^0.5 or less).

In the present specification, the Hansen solubility parameter is intended as the Hansen solubility parameter described in "Hansen Solubility Parameter: A Users Handbook, Second Edition" (page 1-310, CRC Press, 2007) and the like. That is, the Hansen solubility parameter expresses the solubility as a multidimensional vector (dispersion term (δd), dipole internode term (δp), and hydrogen bond term (δh)), and these three parameters are Hansen space. It is considered to be the coordinates of a point in a three-dimensional space called.
The distance of the Hansen solubility parameter is the distance of the two compounds in the Hansen space, and the distance of the Hansen solubility parameter is calculated by the following formula.
(Ra) ² = 4 (δd2-δd1) ² + (δp2-δp1) ² + (δh2-δh1) ²
Ra: Distance of Hansen solubility parameter between the first compound and the second compound (unit: MPa ^0.5 )
δd1: Dispersion term of the first compound (unit: MPa ^0.5 )
δd2: Dispersion term of the second compound (unit: MPa ^0.5 )
δp1: The dipole term of the first compound (unit: MPa ^0.5 )
δp2: Interdipole term of the second compound (unit: MPa ^0.5 )
δh1: Hydrogen bond term of the first compound (unit: MPa ^0.5 )
δh2: Hydrogen bond term of the second compound (unit: MPa ^0.5 )
In the present specification, the Hansen solubility parameter of a compound is specifically calculated using HSPiP (Hansen Solubility Parameter in Practice).

-Other components The liquid to be purified may contain components other than the above. Examples of other components include inorganic substances (metal ions, metal particles, metal oxide particles, etc.), resins, organic substances other than resins, water, and the like.

-Inorganic substance The liquid to be purified may contain an inorganic substance. The inorganic substance is not particularly limited, and examples thereof include metal ions and metal-containing particles.

The metal-containing particles may contain metal atoms, and their morphology is not particularly limited. For example, a simple substance of a metal atom, a compound containing a metal atom (hereinafter, also referred to as “metal compound”), a complex thereof, and the like can be mentioned. Further, the metal-containing particles may contain a plurality of metal atoms.

The composite is not particularly limited, and includes so-called core-shell type particles containing a simple substance of a metal atom and a metal compound covering at least a part of the simple substance of the metal atom, a metal atom and another atom. Solid solution particles, eutectic particles containing metal atoms and other atoms, aggregate particles of simple substances of metal atoms and metal compounds, aggregate particles of different types of metal compounds, and continuous from the particle surface toward the center. Alternatively, a metal compound or the like whose composition changes intermittently can be mentioned.

The atom other than the metal atom contained in the metal compound is not particularly limited, and examples thereof include a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a phosphorus atom.

The metal atom is not particularly limited, but Al (aluminum), B (boron), Ba (barium), Ca (calcium), Cd (cadmium), Co (cobalt), Cr (chromium), Cu (copper), Fe. (Iron), K (potassium), Li (lithium), Mg (magnesium), Mn (manganese), Mo (molybdenum), Na (sodium), Ni (nickel), P (phosphorus), Pb (lead), Sb (Antimon), Si (silicon), Ti (titanium), V (vanadium), Zn (zinc) and the like can be mentioned. The metal-containing particles may contain the above-mentioned metal atom alone or in combination of two or more.

The particle size of the metal-containing particles is not particularly limited, but is generally 1 to 100 nm in many cases.

Inorganic substances may be added to the liquid to be purified, or may be unintentionally mixed with the liquid to be purified in the manufacturing process. Examples of cases where the chemical solution is unintentionally mixed in the manufacturing process of the chemical solution include, for example, when an inorganic substance is contained in a raw material (for example, an organic solvent) used for producing the chemical solution, and when the mixture is mixed in the manufacturing process of the chemical solution (for example). , Contamination), etc., but are not limited to the above.

・ ・ Resin The liquid to be purified may contain a resin.
The chemical solution may further contain a resin. As the resin, a resin P containing a group that is decomposed by the action of an acid to generate a polar group is more preferable.

As the resin P, a resin containing a repeating unit represented by the formula (AI) described later, which is a resin whose solubility in a developing solution containing an organic solvent as a main component is reduced by the action of an acid, is more preferable. The resin containing the repeating unit represented by the formula (AI) described later contains a group (hereinafter, also referred to as “acid-degradable group”) which is decomposed by the action of an acid to form an alkali-soluble group.
Examples of the polar group include an alkali-soluble group. Examples of the alkali-soluble group include a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a phenolic hydroxyl group, and a sulfo group.

In the acid-degradable group, the polar group is protected by an acid-eliminating group (acid-eliminating group). Examples of the acid-eliminating group include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and -C (R ₀₁ ) (R). ₀₂ ) (OR ₃₉ ) and the like.

In the formula, R _{36 to} R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be combined with each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

Hereinafter, the resin P whose solubility in a developing solution containing an organic solvent as a main component is reduced by the action of an acid will be described in detail.

Formula (AI): Repeating unit containing an acid-degradable group The resin P preferably contains a repeating unit represented by the formula (AI).

In formula (AI)
Xa ₁ represents an alkyl group which may contain a hydrogen atom or a substituent.
T represents a single bond or a divalent linking group.
Ra _{1 to Ra 3} independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic).
Two of Ra _{1 to Ra 3} may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Represented by xa _1, as the alkyl group which may contain a substituent include groups represented by methyl and _-CH 2 _{-R 11,.} R ₁₁ represents a halogen atom (fluorine atom or the like), a hydroxyl group, or a monovalent organic group.
Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

Examples of the divalent linking group of T include an alkylene group, an -COO-Rt- group, an -O-Rt- group and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a −CH ₂ − group, a − (CH ₂ ) ₂ − group, or a − (CH ₂ ) ₃ − group.

As _{the alkyl group of Ra 1 to Ra 3} , an alkyl group having 1 to 4 carbon atoms is preferable.

Examples of the cycloalkyl group of Ra _{1 to Ra 3} include a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polyboronyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like. A cycloalkyl group of the ring is preferred.
The _{cycloalkyl group formed by combining Ra 1 to Ra 3} is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododecanyl. A polycyclic cycloalkyl group such as a group or an adamantyl group is preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

The cycloalkyl group formed by bonding two Ra _{1 to Ra 3} is, for example, a group in which one of the methylene groups constituting the ring contains a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced with.

As the repeating unit represented by the formula (AI), for example, it is preferable that Ra ₁ is a methyl group or an ethyl group, and Ra ₂ and Ra ₃ are bonded to form the above-mentioned cycloalkyl group.

Each of the above groups may contain a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), and a carboxy group. , Alkoxycarbonyl group (2 to 6 carbon atoms) and the like, and 8 or less carbon atoms are preferable.

The content of the repeating unit represented by the formula (AI) is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, and further 30 to 80 mol% with respect to all the repeating units in the resin P. preferable.

... Repeating unit containing a lactone structure The resin P preferably contains a repeating unit Q containing a lactone structure.

The repeating unit Q containing a lactone structure preferably contains a lactone structure in a side chain, and more preferably a repeating unit derived from a (meth) acrylic acid derivative monomer.
The repeating unit Q containing a lactone structure may be used alone or in combination of two or more, but it is preferably used alone.
The content of the repeating unit Q containing the lactone structure is preferably 3 to 80 mol%, more preferably 3 to 60 mol%, based on all the repeating units in the resin P.

As the lactone structure, a 5- to 7-membered lactone structure is preferable, and a structure in which another ring structure is condensed in a form of forming a bicyclo structure or a spiro structure in the 5- to 7-membered lactone structure is more preferable.
The lactone structure preferably contains a repeating unit containing a lactone structure represented by any of the following formulas (LC1-1) to (LC1-17). As the lactone structure, a lactone structure represented by the formula (LC1-1), the formula (LC1-4), the formula (LC1-5), or the formula (LC1-8) is preferable, and the lactone structure is represented by the formula (LC1-4). The lactone structure is more preferable.

The lactone structural moiety may contain a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. , Halogen atom, hydroxyl group, cyano group, acid-degradable group and the like. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different, or the plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring. ..

... Repeating unit containing a phenolic hydroxyl group Further, the resin P may contain a repeating unit containing a phenolic hydroxyl group.
Examples of the repeating unit containing a phenolic hydroxyl group include a repeating unit represented by the following general formula (I).

During the ceremony
R ₄₁ , R ₄₂ and R ₄₃ independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may _{be bonded to Ar 4} to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.

X ₄ represents a single bond, -COO-, or -CONR _64- , and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or an alkylene group.
Ar ₄ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when combined with _{R 42 to form a ring.}
n represents an integer of 1 to 5.

_{The alkyl group of R 41} , R ₄₂ and R ₄₃ in the general formula (I) may contain a substituent, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and sec-butyl. An alkyl group having 20 or less carbon atoms such as a group, a hexyl group, a 2-ethylhexyl group, an octyl group and a dodecyl group is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is further preferable.

_{The cycloalkyl groups of R 41} , R ₄₂ and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. As the cycloalkyl group, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group, which may contain a substituent, is preferable.

_{Examples of the halogen atom of R 41} , R ₄₂ and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

As the alkyl group contained in the alkoxycarbonyl group _{of R 41} , R ₄₂ and R ₄₃ in the general formula (I), the same _{group as the alkyl group in R 41} , R ₄₂ and R ₄₃ is preferable.

Examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group, a thioether group and an acyl group. , Achilloxy group, alkoxycarbonyl group, cyano group, nitro group and the like, and the substituent has preferably 8 or less carbon atoms.

Ar ₄ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group when n is 1 may contain a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylen group, a naphthylene group and an anthracenylene group, and an arylene group having 6 to 18 carbon atoms. , Thiophen, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazol, thiazole and other heterocyclic ring groups.

As a specific example of the (n + 1) -valent aromatic ring group when n is an integer of 2 or more, (n-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent aromatic ring group. There is a group that is made up of.
The (n + 1) -valent aromatic ring group may further contain a substituent.

Examples of the substituent that can be contained in the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and (n + 1) -valent aromatic ring group include R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I). The above-mentioned alkyl groups; alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; aryl groups such as phenyl group can be mentioned.

_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom or an alkyl group) The alkyl group for _{R 64} in may contain a substituent, a methyl group, an ethyl group, a propyl group , Isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and other alkyl groups having 20 or less carbon atoms, and alkyl groups having 8 or less carbon atoms are more preferable.

As X ₄ , a single bond, -COO- or -CONH- is preferable, and a single bond or -COO- is more preferable.

The alkylene group for L _4, may contain a substituent, a methylene group, an ethylene group, a propylene group, a butylene group, an alkylene group having 1 to 8 carbon atoms such as hexylene group and octylene group.

As Ar ₄ , an aromatic ring group having 6 to 18 carbon atoms which may contain a substituent is preferable, and a benzene ring group, a naphthalene ring group or a biphenylene ring group is more preferable.

The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar ₄ is preferably a benzene ring group.

The content of the repeating unit containing a phenolic hydroxyl group is preferably 0 to 50 mol%, more preferably 0 to 45 mol%, still more preferably 0 to 40 mol%, based on all the repeating units in the resin P.

... Repeating unit containing an organic group containing a polar group Resin P is a repeating unit containing an organic group containing a polar group, particularly a repeating unit containing an alicyclic hydrocarbon structure substituted with a polar group. May be further contained. This improves substrate adhesion and developer affinity.
As the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with the polar group, an adamantyl group, a diamantyl group or a norbornane group is preferable. As the polar group, a hydroxyl group or a cyano group is preferable.

When the resin P contains a repeating unit containing an organic group containing a polar group, the content thereof is preferably 1 to 50 mol%, preferably 1 to 30 mol%, based on all the repeating units in the resin P. Is more preferable, 5 to 25 mol% is further preferable, and 5 to 20 mol% is particularly preferable.

... Repeat unit represented by the general formula (VI) The resin P may contain a repeating unit represented by the following general formula (VI).

In the general formula (VI),
R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may _{be bonded to Ar 6} to form a ring, in which case R ₆₂ represents a single bond or an alkylene group.
X ₆ represents a single bond, -COO-, or -CONR _64- . R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when combined with _{R 62 to form a ring.}
Y ₂ represents a group desorbed by the action of a hydrogen atom or an acid independently when n ≧ 2. However, _{at least one of Y 2} represents a group that is eliminated by the action of an acid.
n represents an integer of 1 to 4.

_{As the group Y 2} desorbed by the action of an acid, a structure represented by the following general formula (VI-A) is preferable.

L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
Q, M, of at least two members to the ring (preferably, 5-membered or 6-membered ring) L ₁ may be formed.

The repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (3).

In the general formula (3)
Ar ₃ represents an aromatic ring group.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group.
M ₃ represents a single bond or a divalent linking group.
Q ₃ are an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
At _{least two of Q 3} , M ₃ and R ₃ may be combined to form a ring.

The _{aromatic ring group represented by Ar 3 is the same as that of Ar 6} in the general formula (VI) when n in the general formula (VI) is 1, preferably a phenylene group or a naphthylene group, and a phenylene group is more preferable. preferable.

The repeating unit containing a silicon atom in the side chain The resin P may further contain a repeating unit containing a silicon atom in the side chain. Examples of the repeating unit containing a silicon atom in the side chain include a (meth) acrylate-based repeating unit containing a silicon atom and a vinyl-based repeating unit containing a silicon atom. The repeating unit containing a silicon atom in the side chain is typically a repeating unit containing a group containing a silicon atom in the side chain, and examples of the group containing a silicon atom include a trimethylsilyl group and a triethylsilyl group. Group, triphenylsilyl group, tricyclohexylsilyl group, tristrimethylsiloxysilyl group, tristrimethylsilylsilyl group, methylbistrimethylsilylsilyl group, methylbistrimethylsiloxysilyl group, dimethyltrimethylsilylsilyl group, dimethyltrimethylsiloxysilyl group, and the following Cyclic or linear polysiloxanes such as, or cage-type, ladder-type, or random-type silsesquioxane structures and the like can be mentioned. In the formula, R and R ¹ each independently represent a monovalent substituent. * Represents a bond.

As the repeating unit containing the above group, for example, a repeating unit derived from an acrylate compound or a methacrylate compound containing the above group, or a repeating unit derived from a compound containing the above group and a vinyl group is preferable. ..

When the resin P contains a repeating unit containing a silicon atom in the side chain, the content thereof is preferably 1 to 30 mol%, preferably 5 to 25 mol%, based on all the repeating units in the resin P. More preferably, 5 to 20 mol% is further preferable.

The weight average molecular weight of the resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and 5,000 to 15,000 as a polystyrene conversion value by the GPC (Gel permeation chromatography) method. More preferred. When the weight average molecular weight is set to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability deteriorates, viscosity becomes high, and film forming property deteriorates. Can be prevented.

The degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0.

As for other components (for example, acid generator, basic compound, quencher, hydrophobic resin, surfactant, solvent, etc.) contained in the chemical solution, known components can be used.

(Aqueous liquid to be purified)
The aqueous purification liquid contains more than 50% by mass of water with respect to the total mass of the solvent contained in the water-based purification liquid, and is preferably 51 to 95% by mass.
The water is not particularly limited, but it is preferable to use ultrapure water used for semiconductor production, and water obtained by further purifying the ultrapure water to reduce inorganic anions, metal ions and the like is used. Is more preferable. The purification method is not particularly limited, but purification using a filtration membrane or an ion exchange membrane and purification by distillation are preferable. Further, for example, it is preferable to purify by the method described in JP-A-2007-254168.

-Oxidizing agent The aqueous purification liquid may contain an oxidizing agent, and the oxidizing agent is not particularly limited, and a known oxidizing agent can be used. Examples of the oxidizing agent include hydrogen peroxide, peroxide, nitric acid, nitrate, iodate, permanganate, hypochlorite, chlorate, chlorate, permanganate, and persulfate. Examples thereof include salts, hypochlorites, permanganates, ozone water, silver (II) salts, iron (III) salts and the like.

The content of the oxidizing agent is not particularly limited, but is preferably 0.1% by mass or more, and preferably 99.0% by mass or less, based on the total mass of the aqueous purification liquid. The oxidizing agent may be used alone or in combination of two or more. When two or more kinds of oxidizing agents are used in combination, the total content is preferably within the above range.

-Inorganic acid The aqueous purification liquid may contain an inorganic acid. The inorganic acid is not particularly limited, and a known inorganic acid can be used. Examples of the inorganic acid include sulfuric acid, phosphoric acid, hydrochloric acid and the like. The inorganic acid is not included in the above-mentioned oxidizing agent.
The content of the inorganic acid in the aqueous purification liquid is not particularly limited, but is preferably 0.01% by mass or more, and preferably 99.0% by mass or less, based on the total mass of the water-based purification liquid.
As the inorganic acid, one type may be used alone, or two or more types may be used in combination. When two or more kinds of inorganic acids are used in combination, the total content is preferably within the above range.

-Corrosion inhibitor The water-based purified liquid may contain an anticorrosive agent. The anticorrosive agent is not particularly limited, and a known anticorrosive agent can be used. Examples of the anticorrosive agent include 1,2,4-triazole (TAZ), 5-aminotetrazole (ATA), 5-amino-1,3,4-thiadiazol-2-thiol, 3-amino-1H-1,2. , 4 triazole, 3,5-diamino-1,2,4-triazole, triltriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 1 -Amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole , Nafttriazole, 1H-tetrazole-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazoline-5-thione, 2-mercaptobenzoimidazole (2-MBI), 4-methyl- 2-Phenylimidazole, 2-mercaptothiazolin, 2,4-diamino-6-methyl-1,3,5-triazole, thiazole, imidazole, benzoimidazole, triazole, methyltetrazole, bismuthiol I, 1,3-dimethyl-2 -Imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazole, imidazolinthione, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino -1,3,4-Thiasiazol-2-thiol, benzothiazole, tritol phosphate, indazole, adenine, citocin, guanine, timine, phosphate inhibitors, amines, pyrazoles, propanethiol, silanes, secondary amines , Benzohydroxamic acids, heterocyclic nitrogen inhibitors, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, potassium ethylxanthogenate, glycine, dodecylphosphonic acid, Imino diacetic acid, boric acid, malonic acid, succinic acid, nitrilotriacetic acid, sulfolane, 2,3,5-trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, quinoxalin, acetylpyrrole, pyridazine, histadine , Pyrazine, glutathione (reduced form), cysteine, cystine, thiophene, mercaptopyridine N-oxide, thiamine HCl, tetraethylthiuram disulfide, 2,5-dimercapto-1,3-thiadiazol ascorbic acid, ascorbi Acids, catechols, t-butylcatechols, phenols, and pyrogallols can be mentioned.

Examples of the anticorrosive agent include aliphatic carboxylic acids such as dodecanoic acid, palmitic acid, 2-ethylhexanoic acid, and cyclohexanoic acid; citric acid, malic acid, oxalic acid, malonic acid, succinic acid, itaconic acid, maleic acid, and glycol. Acids, mercaptoacetic acid, thioglycolic acid, salicylic acid, sulfosaricylic acid, anthranyl acid, N-methylanthranyl acid, 3-amino-2-naphthoic acid, 1-amino-2-naphthoic acid, 2-amino-1-naphthoic acid , 1-Aminoanthraquinone-2-carboxylic acid, tannic acid, carboxylic acid containing chelating ability such as gallic acid; etc. may be used.

Examples of the anticorrosive agent include palm fatty acid salt, castor sulfate oil salt, lauryl sulfate salt, polyoxyalkylene allylphenyl ether sulfate salt, alkylbenzene sulfonic acid, alkylbenzene sulfonate, alkyldiphenyl ether disulfonate, and alkylnaphthalene sulfant. Anionic surfactants such as acid salts, dialkyl sulfosuccinate salts, isopropyl phosphate, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene allylphenyl ether phosphate salts; oleylamine acetate, lauryl pyridinium chloride, cetyl pyridinium chloride, lauryl trimethyl ammonium Cationic surfactants such as chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, didecyldimethylammonium chloride; palm alkyldimethylamine oxide, fatty acid amidepropyldimethylamine oxide, alkylpolyaminoethylglycine hydrochloride, amide betaine type activator, Amphoteric surfactants such as alanine-type activators and lauryliminodipropionic acid; polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene laurylamine, polyoxyethylene oleylamine, polyoxyethylene poly Nonionic surfactants of polyoxyalkylene primary alkyl ethers or polyoxyalkylene secondary alkyl ethers such as styrylphenyl ethers and polyoxyalkylene polystyrylphenyl ethers, polyoxyethylene dilaurate, polyoxyethylene laurate, and polyoxyethylene acidified castor oil. , Polyoxyethylene hardened castor oil, sorbitan lauric acid ester, polyoxyethylene sorbitan lauric acid ester, other polyoxyalkylene-based nonionic surfactants such as fatty acid diethanolamide; octyl stearate, trimethylol propanthridecanoate, etc. Fatty acid alkyl ester; Polyether polyol such as polyoxyalkylene butyl ether, polyoxyalkylene oleyl ether, and trimethylolpropanthris (polyoxyalkylene) ether may be used.
Examples of the above-mentioned commercially available products include New Calgen FS-3PG (manufactured by Takemoto Oil & Fat Co., Ltd.) and Hosten HLP-1 (manufactured by Nikko Chemicals Co., Ltd.).

Moreover, you may use a hydrophilic polymer as an anticorrosive agent.
Examples of the hydrophilic polymer include polyglycols such as polyethylene glycol, alkyl ethers of polyglycols, polyvinyl alcohol, polyvinylpyrrolidone, polysaccharides such as alginic acid, and carboxylic acid-containing polymers such as polymethacrylic acid and polyacrylic acid. Examples thereof include polyacrylamide, polymethacrylamide, and polyethyleneimine. Specific examples of such hydrophilic polymers include water-soluble polymers described in Japanese Patent Application Laid-Open No. 2009-88243, paragraphs 0042 to 0044 and JP-A-2007-194261, paragraph 0026.

Moreover, you may use cerium salt as an anticorrosive agent.
The cerium salt is not particularly limited, and known cerium salts can be used.
Examples of the cerium salt include cerium acetate, cerium nitrate, cerium chloride, cerium carbonate, cerium oxalate, and cerium sulfate as trivalent cerium salts. Examples of the tetravalent cerium salt include cerium sulfate, cerium ammonium sulfate, cerium ammonium nitrate, diammonium cerium nitrate, and cerium hydroxide.

The anticorrosive agent may contain a substituted or unsubstituted benzotriazole. Suitable substituted benzotriazoles include, but are not limited to, benzotriazoles substituted with an alkyl group, an aryl group, a halogen group, an amino group, a nitro group, an alkoxy group, or a hydroxyl group. Substituted benzotriazoles also include compounds fused with one or more aryl (eg, phenyl) or heteroaryl groups.

The content of the anticorrosive agent in the aqueous purification solution is preferably adjusted to be 0.01 to 5% by mass with respect to the total mass of the chemical solution. One type of anticorrosive agent may be used alone, or two or more types may be used in combination. When two or more kinds of anticorrosive agents are used in combination, the total content is preferably within the above range.

-Organic solvent The water-based purified liquid may contain an organic solvent. The organic solvent is not particularly limited, but is as described above as the organic solvent contained in the organic solvent-based purified liquid. When an organic solvent is contained, the content of the organic solvent is preferably 5 to 35% by mass with respect to the total mass of the solvent contained in the aqueous purification liquid.

<Filtration process>
The method for producing a chemical solution according to the present embodiment is a filtration step of filtering the liquid to be purified using the filter of the present invention (typically, a filtration device equipped with the filter of the present invention) to obtain the chemical solution. contains.
The supply pressure of the liquid to be purified to each filter in the above filtration device is not particularly limited, but is generally preferably 0.00010 to 1.0 MPa.
Among them, in terms of chemical solution containing better defect suppression is obtained, the supply pressure _{P 2} is preferably 0.00050~0.090MPa, 0.0010~0.050MPa more preferably, from 0.0050 to 0 .040 MPa is more preferable.
Further, since the filtration pressure affects the filtration accuracy, it is preferable that the pressure pulsation during filtration is as small as possible.

Although the filtration rate is not particularly limited, in that more excellent defective inhibitory easy chemical liquid containing obtain a preferably 1.0 L / min / m ² or more, 0.75 L / min / m ² or more, and More preferably, 0.6 L / min / m ^{2 or more.}
The filter has a differential pressure resistance that guarantees filter performance (the filter does not break), and if this value is large, the filtration pressure can be increased to increase the filtration rate. That is, the upper limit of the filtration rate usually depends on the differential pressure resistance of the filter, but is usually ^{preferably 10.0 L / min / m 2} or less.

The temperature at which the liquid to be purified is passed through the filter is not particularly limited, but is generally preferably below room temperature.

The filtration step is preferably carried out in a clean environment. Specifically, it is preferable to carry out the operation in a clean room satisfying Class 1000 (Class 6 in ISO 14644-1: 2015) of the US federal standard (Fed. Std. 209E), and a clean room satisfying Class 100 (Class 5 in ISO 14644-1: 2015). Is more preferable, and a clean room satisfying Class 10 (Class 4 in ISO 14644-1: 2015) is more preferable, and contains Class 1 (Class 3 in ISO 14644: 1: 2015) or higher cleanliness (Class 2 or Class 1). A clean room is particularly preferred.
It is preferable that each step described later is also carried out in the above-mentioned clean environment.

Further, when the filtration device includes a return flow passage, the filtration step may be a circulation filtration step. The circulation filtration step is a step of filtering the liquid to be purified by at least the filter A, returning the liquid to be purified after being filtered by the filter A to the upstream of the filter A to the flow passage, and filtering the liquid again by the filter A. ..
The number of circulation filtrations is not particularly limited, but is generally preferably 2 to 10 times. In the circulation filtration, the liquid to be purified may be returned to the upstream of the filter A so as to repeat the filtration by the filter A, but at this time, it is returned so as to repeat the filtration by a filter other than the filter A in addition to the filter A. The flow path may be adjusted.

<Other processes>
The method for producing a chemical solution according to this embodiment may include steps other than the above. Examples of the steps other than the above include an apparatus cleaning step, a static elimination step, and the like. In the following, each step will be described in detail.

(Equipment cleaning process)
The device cleaning step is a step of cleaning the wetted portion of the filtration device before the filtration step. The method of cleaning the wetted portion of the filtration device before the filtration step is not particularly limited, but in the following, the filter is contained in the cartridge with a filter, and the cartridge with the filter is contained in the housing arranged on the flow path. The filtration device housed in the housing will be described as an example.

The device cleaning step is a step A of cleaning the wetted portion of the filtration device with a cleaning liquid in a state where the cartridge with a filter is removed from the housing, and after the step A, the cartridge with a filter is stored in the housing and the cleaning liquid is further cleaned. It is preferable to include the step B of cleaning the wetted portion of the filtration device using the above.

・ Process A
Step A is a step of cleaning the wetted portion of the filtration device with a cleaning liquid in a state where the cartridge with a filter is removed from the housing. With the filter removed from the housing, means cleaning the wetted parts of the filtration device with a cleaning solution before removing the filter cartridge from the housing or housing the filter cartridge in the housing.
The method of cleaning the wetted portion of the filtration device with the filter removed from the housing (hereinafter, also referred to as “filter not stored”) with the cleaning liquid is not particularly limited. An example is a method in which a cleaning liquid is introduced from the inflow portion and collected from the outflow portion.

Among them, in terms of obtaining a more excellent effect of the present invention, as a method of cleaning the wetted portion of the filtration device not stored in the filter with a cleaning liquid, a method of filling the inside of the filtration device not stored in the filter with the cleaning liquid is used. Can be mentioned. The inside of the filtration device not stored in the filter is filled with the cleaning liquid, and the wetted portion of the filtration device not stored in the filter comes into contact with the cleaning liquid. As a result, impurities adhering to the wetted portion of the filtration device are transferred (typically eluted) to the cleaning liquid. Then, the cleaning liquid after cleaning may be discharged to the outside of the filtration device (typically, it may be discharged from the outflow portion).

-Cleaning liquid The cleaning liquid is not particularly limited, and a known cleaning liquid can be used. Among them, the cleaning liquid preferably contains water or an organic solvent as a main component, and more preferably contains an organic solvent as a main component, in that a more excellent effect of the present invention can be obtained. In the present specification, the main component means a component contained in an amount of 99.9% by mass or more based on the total mass of the cleaning liquid, and more preferably 99.99% by mass or more.

The organic solvent is not particularly limited, and for example, water and the organic solvent already described as the organic solvent contained in the chemical solution can be used. As an organic solvent, PGMEA, cyclohexanone, ethyl lactate, butyl acetate, MIBC (4-methyl-2-pentanol), MMP (3-methylmethoxypropionate) can be obtained in that the effect of the present invention is more excellent. , MAK (2-heptanone), n-pentyl acetate, ethylene glycol, isoamyl acetate, PGME (propylene glycol monoethyl ether), MEK (methyl ethyl ketone), 1-hexanol, and at least one selected from the group consisting of decane. Is preferable.

・ Process B
Step B is a method of cleaning the filtration device with a cleaning liquid in a state where the filter is housed in the housing.
As a method of cleaning the filtration device using the cleaning liquid, in addition to the cleaning method in step A already described, a method of passing the cleaning liquid through the filtration device can also be used. The method of passing the cleaning liquid through the filtration device is not particularly limited, but the cleaning liquid may be introduced from the inflow portion and discharged from the outflow portion. The cleaning liquid that can be used in this step is not particularly limited, and the cleaning liquid described in step A can be used.

(Static elimination process)
The static elimination step is a step of removing static electricity from the liquid to be purified to reduce the charging potential of the liquid to be purified. The static elimination method is not particularly limited, and a known static elimination method can be used. Examples of the static elimination method include a method of bringing the liquid to be purified into contact with the conductive material.
The contact time for bringing the liquid to be purified into contact with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, still more preferably 0.01 to 0.1 seconds. Examples of the conductive material include stainless steel, gold, platinum, diamond, glassy carbon and the like.
Examples of the method of bringing the liquid to be purified into contact with the conductive material include a method of arranging a grounded mesh made of the conductive material so as to cross the flow passage and allowing the liquid to be purified to flow there.

[Corrosion resistant material]
Next, the corrosion resistant material will be described. In the filtration device and the purification device according to the embodiment of the present invention described so far, it is preferable that at least a part of the wetted portion is made of a corrosion resistant material, and 90% or more of the wetted portion is resistant to corrosion. It is more preferably formed of a corrosive material, and it is further preferable that 99% or more of the wetted parts are made of a corrosive resistant material.

The state in which the wetted portion is made of a corrosion-resistant material is not particularly limited, but typically, each member (for example, the tank described above) is made of a corrosion-resistant material, and each member is made of a corrosion-resistant material. Examples thereof include a state in which the member contains a base material and a coating layer arranged on the base material, and the coating layer is formed of a corrosion-resistant material.

The corrosion resistant material is a non-metal material and an electropolished metal material. The non-metallic material is not particularly limited, and is, for example, polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, ethylene tetrafluoride resin, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, ethylene tetrafluoride-6. Propylene fluoride copolymer resin, ethylene tetrafluoride-ethylene copolymer resin, ethylene trifluoride-ethylene copolymer resin, vinylidene fluoride resin, ethylene trifluoride copolymer resin, vinyl fluoride resin, etc. However, it is not limited to this.

The metal material is not particularly limited, and examples thereof include a metal material in which the total content of Cr and Ni is more than 25% by mass with respect to the total mass of the metal material, and among them, 30% by mass or more is more preferable. .. The upper limit of the total content of Cr and Ni in the metal material is not particularly limited, but is generally preferably 90% by mass or less.
Examples of the metal material include stainless steel and Ni—Cr alloy.

The stainless steel is not particularly limited, and known stainless steel can be used. Among them, an alloy containing 8% by mass or more of Ni is preferable, and an austenitic stainless steel containing 8% by mass or more of Ni is more preferable. Examples of austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), and SUS316 ( Ni content 10% by mass, Cr content 16% by mass), SUS316L (Ni content 12% by mass, Cr content 16% by mass) and the like.

The Ni—Cr alloy is not particularly limited, and a known Ni—Cr alloy can be used. Of these, a NiCr alloy having a Ni content of 40 to 75% by mass and a Cr content of 1 to 30% by mass is preferable.
Examples of Ni—Cr alloys include Hastelloy (trade name, the same shall apply hereinafter), Monel (trade name, the same shall apply hereinafter), Inconel (trade name, the same shall apply hereinafter) and the like. More specifically, 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), Hastelloy C-22 ( Ni content 61% by mass, Cr content 22% by mass) and the like.
Further, the Ni—Cr alloy may further contain B, Si, W, Mo, Cu, Co and the like in addition to the above alloy, if necessary.

The method for electrolytically polishing a metal material is not particularly limited, and a known method can be used. For example, the methods described in paragraphs 0011 to 0014 of JP2015-227501 and paragraphs 0036 to 0042 of JP2008-264929 can be used.

It is presumed that the content of Cr in the passivation layer on the surface of the metal material is higher than the content of Cr in the parent phase by electropolishing. Therefore, it is presumed that if a purification device in which the wetted portion is formed of an electrolytically polished metal material is used, metal impurities containing metal atoms are unlikely to flow out into the liquid to be purified.
The metal material may be buffed. The method of buffing is not particularly limited, and a known method can be used. The size of the abrasive grains used for finishing the buffing is not particularly limited, but # 400 or less is preferable because the unevenness of the surface of the metal material tends to be smaller. The buffing is preferably performed before the electrolytic polishing.

[Use of chemicals]
The chemical solution produced by using the filter of the present invention (preferably a filtration device containing the filter) is preferably used for producing a semiconductor substrate. In particular, it is more preferably used for forming a fine pattern having a node of 10 nm or less (for example, a step including pattern formation using extreme ultraviolet rays).
In other words, the filtration device is preferably used for manufacturing a chemical solution for manufacturing a semiconductor substrate, and specifically, for a semiconductor device including a lithography step, an etching step, an ion injection step, a peeling step, and the like. In the manufacturing process, it is preferably used for the production of a chemical solution used for treating an inorganic substance and / or an organic substance after the completion of each step or before moving to the next step.
Specifically, the above-mentioned filtration device includes a developing liquid, a rinsing liquid, a wafer cleaning liquid, a line cleaning liquid (for example, a pipe cleaning liquid), a pre-wet liquid, a wafer rinsing liquid, a resist liquid, a lower layer film forming liquid, an upper layer film forming liquid, and It is preferably at least one selected from the group consisting of a hard coat forming liquid (a chemical solution obtained by purifying an organic-based purified liquid), and other forms include an aqueous aqueous developing solution, an aqueous rinsing solution, and the like. At least one type (aqueous purification liquid) selected from the group consisting of a stripping liquid, a remover, an etching liquid, an acidic cleaning liquid, and a phosphoric acid, a phosphoric acid-hydrogenated water mixture (SPM: Sulfric acid-Hydrogen Peroxide Mixture). It is preferable to use it for the production of a chemical solution obtained by purifying.

Further, the filter of the present invention (preferably a filter device containing a filter) can also be used for producing a chemical solution used for rinsing the edge erase of a semiconductor substrate before and after resist coating.
Further, the filter of the present invention (preferably a filtration device containing a filter) can also be used for producing a diluted solution of a resin contained in a resist solution and a solvent contained in the resist solution.

Further, the filter of the present invention (preferably a filtration device containing a filter) can be used for manufacturing a chemical solution used for other purposes other than manufacturing a semiconductor substrate, and can be used for polyimide, a resist for a sensor, a resist for a lens, etc. It can also be used for manufacturing a developer, a rinse solution, and the like.
The filter of the present invention (preferably a filter device containing the filter) can also be used for producing a solvent for medical use or cleaning use. In particular, it can be used for producing a chemical solution used for cleaning containers, pipes, substrates (for example, wafers, glass, etc.) and the like.
Among them, the filter of the present invention (preferably a filter device containing a filter) is composed of a group consisting of a pre-wet liquid, a developing liquid, a rinsing liquid, and a pipe cleaning liquid for cleaning a device for transferring these liquids in pattern formation. It is preferably used in the production of at least one selected.

When the manufactured chemical solution contains an organic solvent as a main component (for example, the content of the organic solvent is 80% by mass or more (preferably 99% by mass or more, more preferably 99.9% by mass or more) with respect to the total mass of the chemical solution. When the upper limit is, for example, 100% by mass or less), the chemical solution ^{preferably contains a Hansen solubility parameter distance of 3 to 20 MPa 0.5} (more preferably 5 to 20 MPa ^0.5 ) with respect to Eikosen.
When two or more kinds of organic solvents are used, it is preferable that at least one kind satisfies the range of the Hansen solubility parameter.
When two or more kinds of organic solvents are used, it is preferable that the weighted average value of the Hansen solubility parameter based on the molar ratio of the content of each organic solvent satisfies the range of the Hansen solubility parameter.
As the organic solvent, for example, the organic solvent mentioned as the organic solvent as the liquid to be purified can be similarly mentioned.

For example, it is also preferable that the chemical solution is only an organic solvent that substantially satisfies the range of the Hansen solubility parameter from the viewpoint of being more excellent in defect suppression. The chemical solution is only an organic solvent that substantially satisfies the range of the Hansen solubility parameter, that is, the content of the organic solvent that satisfies the range of the Hansen solubility parameter is 99% by mass or more based on the total mass of the organic solvent ( It is preferably 99.9% by mass or more).

Further, for example, it is also preferable that the chemical solution is a mixed solvent containing both an organic solvent satisfying the range of the Hansen solubility parameter and an organic solvent not satisfying the range of the Hansen solubility parameter.
In this case, the chemical solution (mixed solvent) contains 20 to 80% by mass (preferably 30) of an organic solvent satisfying the above range of the Hansen solubility parameter with respect to the total mass of the chemical solution, from the viewpoint of more excellent defect suppression property of the obtained chemical solution. It is preferable to contain 20 to 80% by mass (preferably 30 to 70% by mass) of an organic solvent containing (~ 70% by mass) and not satisfying the above range of the Hansen solubility parameter with respect to the total mass of the chemical solution.
When the content of the organic solvent satisfying the range of the Hansen solubility parameter and the content of the organic solvent not satisfying the range of the Hansen solubility parameter are equal to or higher than a certain level, the organic solvent not satisfying the range of the Hansen solubility parameter is specified. Compared with the case where the amount is out of the range (for example, 1% by mass or more and less than 20% by mass or more than 80% by mass with respect to the total mass of the mixed solvent), the affinity of the chemical solution for the metal-based material and the organic-based material is improved. It can be adjusted to an appropriate range, and it is considered that the effect of the present invention is more excellent.
In this case, the total content of the organic solvent satisfying the Hansen solubility parameter range and the organic solvent not satisfying the Hansen solubility parameter range is preferably 99.0% by mass or more with respect to the total mass of the chemical solution. .. The upper limit value is not particularly limited, but is generally preferably 99.999999% by mass or less.
Incidentally, in an organic solvent which does not satisfy the range of the Hansen solubility parameter, the distance of Hansen parameters for eicosene is, ^{0 MPa 0.5} or more ^3MPa less than ^0.5 (preferably ^{0 MPa 0.5} ultra ^3MPa less than ^0.5), or , 20 MPa over ^0.5 (preferably over 20 MPa over ^{0.5 and over} 50 MPa ^0.5 or less).

[Chemical solution container]
The chemical solution produced by the filtration device may be contained in a container and stored until use. Such a container and the chemical solution contained in the container are collectively referred to as a chemical solution container. The chemical solution is taken out from the stored chemical solution container and used.

As the container for storing the chemical solution, a container having a high degree of cleanliness in the container for manufacturing a semiconductor substrate and in which impurities are less likely to elute from the chemical solution during storage is preferable.
The containers that can be used are not particularly limited, and examples thereof include, but are not limited to, the "clean bottle" series manufactured by Aicello Chemical Corporation and the "pure bottle" manufactured by Kodama Resin Industry.

As the container, a multi-layer bottle having a 6-layer structure with 6 types of resin or a multi-layer bottle with a 7-layer structure with 6 types of resin is used for the purpose of preventing impurities from being mixed in the chemical solution. Is also preferable. Examples of these containers include the containers described in Japanese Patent Application Laid-Open No. 2015-123351.

It is preferable that at least a part of the wetted portion of this container is made of the corrosion-resistant material described above. It is preferable that 90% or more of the area of the wetted portion is made of the above material from the viewpoint of obtaining more excellent effects of the present invention.

Hereinafter, the present invention will be described in more detail based on Examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the invention should not be construed as limiting by the examples shown below.

In addition, in the preparation of the chemicals of Examples and Comparative Examples, the handling of the container, the preparation, filling, storage and analytical measurement of the chemicals were all carried out in a clean room at a level satisfying ISO class 2 or 1. In order to improve the measurement accuracy, in the measurement of the content of organic compounds and the measurement of the content of metal components, when measuring the components below the detection limit by normal measurement, the chemical solution is concentrated and measured. Then, the content was calculated by converting to the concentration of the solution before concentration.
Unless otherwise specified, the equipment and the like used for the test have been sufficiently cleaned in advance.

[Making a filter]
[Packing material for filters]
We obtained a filter to be processed packed with the following packing materials.
The abbreviations for the packaging material of the filter to be processed are as follows.

-HDPE: HDPE bag whose contact part with the filter to be treated is HDPE (high density polyethylene) -Fluororesin: Fluororesin bag whose contact part with the filter to be treated is fluororesin-EP-SUS: Processed Stainless steel capsule in which the contact area with the filter is electrolytically polished stainless steel

[Filter to be processed]
A filter containing a filtration layer containing the following materials and a filter body containing a support layer was subjected to pretreatment as a filter to be treated.
The abbreviations for the material of the filter body of each filter (filter to be processed) are as follows.

-PP: Polypropylene-IEX (PTFE): PTFE with a cation exchange group introduced
-PTFE: Polytetrafluoroethylene-Nylon: Nylon-UPE: Ultra-high molecular weight polyethylene-PFA: Perfluoroalkoxyalkane-Polyester: Polyester-Graft Nylon: Nylon grafted with a nylon-based polymer

・ A1:
_{First, the bis-olefin of formula CH 2} CH-C ₆ F _12- CHCH ₂ as a pre-crosslinker, IC ₄ F _8- I as a chain transfer agent, and potassium persulfate as a radical initiator. It was used to emulsion polymerization and a vinyl ether of TFE and formula _{CF 2 = CF-O-CF} 2 CF 2 -SO 2 F.
As for the conditions of emulsion polymerization, the copolymer C1 of Table 2 above was synthesized according to the conditions of Table 2 of paragraph 0121 of JP2012-522882A.
Next, the fluorocarbon composition of S1 described in paragraphs 0123 to 0125 (particularly Table 3 of paragraph 0123) of JP2012-522882A was prepared.
Next, the fluorocarbon composition was adjusted so that the ionomer content was 1.3% by mass. The prepared fluorocarbon composition contains a cross-linking agent and a radical initiator. A film in which a coating layer is formed on the surface of a porous substrate made of PTFE using the prepared fluorocarbon composition.

A2: A film prepared by preparing hollow fibers of a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer with reference to paragraph 0058 of JP-A-2015-61727 and using the fibers.

-A3: A first layer containing a porous base material made of polytetrafluoroethylene and a sulfonic acid group bonded to the surface of the porous base material, and polytetrafluoroethylene arranged on the first layer. A film containing a porous base material made of the above-mentioned product and a second layer containing an amide group bonded to the surface of the porous base material.

-Anion exchange group: A grafted ultra-high molecular weight polyethylene film (containing a quaternary ammonium group as an anion exchange group) with reference to the description in paragraph 09999 of JP-A-2017-536232.
This membrane is an asymmetric porous membrane.

-Cation exchange group: An ultra-high molecular weight polyethylene film grafted with reference to the description in paragraphs 0130 to 0132 of JP-A-2017-536232 (containing a sulfonic acid group as a cation exchange group).
This membrane is an asymmetric porous membrane.

Neutral Graft UPE1: Refer to the description in paragraphs 0058 to 0059 of JP-A-2017-536232, and grafted ultra-high molecular weight polyethylene membrane (containing a hydroxy group derived from hydroxymethylacrylamide as a neutral group). doing).
This membrane is an asymmetric porous membrane.

Neutral Graft UPE2: Ultra-high molecular weight polyethylene film (as a neutral group, as a neutral group) in the same manner as above except that vinyl chloridebenzyltrimethylammonium monomer was not used in paragraphs 0058 to 0059 of JP-A-2017-536232. Contains a hydroxy group derived from hydroxymethylacrylamide).
This membrane is an asymmetric porous membrane.

-PFSA / PTFE: Commercially available Entegris, inc. The Fluroguard AT manufactured in Japan was dipped in a 0.25% PFSA solution (Aquivion PFSA 24: D83-24B Solvay Plastics) in a polymer solution prepared in an aqueous methanol solvent until sufficiently wet, drained, and then dried. Washed with ultrapure water for 24 hours.

-PTFE-a1:
A film in which a poly (M8-b-NPF6) coating layer is formed on the surface of a PTFE porous film with reference to the description in paragraphs 0124 and 0125 of JP-A-2016-194038.
The pore diameter was adjusted by the coating amount of poly (M8-b-NPF6).
The resin forming the coating layer of PTFE-1 contains a polyoxyalkylene group as a hydrophilic group.

-PTFE-a2:
Poly (M8-b-NPF6) -S (CH ₂ ) SO ₃ Na described in paragraph 0023 of JP-A-2016-194038 was synthesized. Specifically, the above copolymer was synthesized with reference to the description in paragraphs 0103 to 0109 of JP-A-2016-194038. A porous PTFE membrane containing a coating layer produced by the same method as PTFEa-1 using the synthesized copolymer.
The resin forming the coating layer of PTFE-2 contains a polyoxyalkylene group and a sulfonic acid (salt) group as hydrophilic groups.

-PTFE-a3:
Poly (M8-b-NPF6) -S-CH ₂ COOH described in paragraph 0023 of JP-A-2016-194038 was synthesized. Specifically, the above copolymer was synthesized with reference to the description in paragraphs 0103 to 0109 of JP-A-2016-194038. A porous PTFE film containing a coating layer produced by the same method as PTFE-a1 using the synthesized copolymer.
The resin forming the coating layer of PTFE-a3 contains a polyoxyalkylene group and a carboxylic acid (salt) group as hydrophilic groups.

-PTFE-a4:
Poly (NTEG-b-NPF6) / thioglycerol described in paragraph 0014 of JP-A-2016-199733 was synthesized. Specifically, the above copolymer was synthesized with reference to the description in paragraphs 0106 to 0108 of JP2016-199733. A porous PTFE film containing a coating layer produced by the same method as PTFE-a1 using the synthesized copolymer.
The resin forming the coating layer of PTFE-a4 contains a polyoxyalkylene group as a hydrophilic group and a group containing a thioether group and a hydroxyl group.

-PTFE-b1:
Second generation Grubbs catalyst (3.0 mg, 0.004 mmol), 2-butene-1,4-diol (10.0 mg, 0.12 mmol), and 1,5- in a 50 ml round bottom flask equipped with a stir bar. Cyclooctadiene (490 mg, 4.54 mmol) was mixed, degassed with argon for 5 minutes and transferred to an oil bath at 40 ° C. Heating was continued for 1 hour, the remaining 1,5-cyclooctadiene (4.5 mg, 4.2 mmol) in 5 ml DCM was added to the mixture and heating was continued for an additional 6 hours. Hydroxy terminal polymers (PCOD) were isolated by precipitation in methanol. ^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 5.3 to 5.5 (s, wide, 1H), 1.75 to 2.5 (s, wide).

The above PCOD homopolymer was post-functionalized with 1H, 1H, 2H, 2H-perfluorodecanethiol in the presence of a photoinitiator under UV irradiation to give fluorinated PCOD.
The porous PTFE film is composed of a fluorinated PCOD (1-10% by mass) THF solution, a photoinitiator (Irgacure, 1 to 15% by mass), and a sodium 3-mercaptoethanesulfonic acid salt (1 to 15% by mass, uniform). The film is immersed in a solution containing (neutralized with an aqueous solution of THF and dilute hydrochloric acid (1)) until a THF solution is obtained, and coated with a fluorinated PCOD modified via a thiolene reaction. The membrane is crosslinked with this mixture using UV irradiation (300-480 nm, 150-250 milliwatts, 60-180 seconds). Then, the membrane obtained by washing with water and drying at 100 ° C. for 10 minutes.

The PTFE-b1 obtained by the above method is a group which is arranged on a porous substrate made of PTFE so as to cover the porous substrate and contains a thioether group as an adsorptive group with PCOD as the main chain. It contained a coating layer with a copolymer containing (-SCH ₂ CH ₂ (CF ₂ ) ₇ CF _3).

-PTFE-b2:
With reference to the description in paragraphs 0018 to 0032 of JP-A-2017-002273, a coating resin in which a carboxylic acid group was introduced into a side chain was obtained by a thiolene reaction between mercaptoacetic acid and an allyl group. Further, a film obtained by forming a coating layer with the above resin on a PTFE porous film with reference to the description in paragraphs 0070 to 0071 of JP-A-2017-002273.

The PTFE-b2 obtained by the above method is a copolymer of the formula (I) arranged on a porous substrate made of PTFE so as to cover the porous substrate, and has a thioether group as an adsorptive group. , And a coating layer with a copolymer containing a group containing a carboxylic acid group (-SCH _{2 COOH).}

The copolymer of formula (I) is a random copolymer or a block copolymer, Rf is a perfluoro substituent, Rh is an adsorptive group, Ra is a methyl or ethyl group, and m and n are 10 independently. ~ 1000, X is an alkyl group and Y is a reactive functional group.

-PTFE-b3:
With reference to the description in paragraphs 0018 to 0032 of JP-A-2017-002273, an aminoethyl group is introduced by a thiolene reaction between mercaptoethyldiethylamine and an allyl group, and then a quaternary ammonium group is subjected to a quaternization reaction with ethyl bromide. Was introduced into the side chain to obtain a coating resin. Further, a film obtained by forming a coating layer with the above resin on a PTFE porous film with reference to the description in paragraphs 0070 to 0071 of JP-A-2017-002273.

The PTFE-b3 obtained by the above method is a copolymer of the formula (I) arranged on a porous substrate made of PTFE so as to cover the porous substrate, and has a thioether group as an adsorptive group. , And a coating layer with a copolymer containing a group containing a quaternary ammonium group.

-PTFE-b4:
A coating resin into which a thioether group was introduced was obtained by a thiolene reaction between 2 ethylhexylthiopropyl mercaptan and an allyl group with reference to the description in paragraphs 0018 to 0032 of JP-A-2017-002273. A film obtained by forming a coating layer with the above resin on a PTFE porous film with reference to the description in paragraphs 0070 to 0071 of JP-A-2017-002273.

The PTFE-b4 obtained by the above method is a copolymer of the formula (I) arranged on a porous substrate made of PTFE so as to cover the porous substrate, and has a thioether group as an adsorptive group. It contained a coating layer made of a copolymer containing a group containing.

-PTFE-b5:
With reference to the description in paragraphs 0018 to 0032 of JP-A-2017-002273, a coating resin into which a phosphoric oxy group was introduced was obtained by a thiol-ene reaction between tripropyloxyphosphoric oxypropyl mercaptan and an allyl group. A film obtained by forming a coating layer with the above resin on a PTFE porous film with reference to the description in paragraphs 0070 to 0071 of JP-A-2017-002273.

The PTFE-b5 obtained by the above method is a copolymer of the formula (I) arranged on a porous substrate made of PTFE so as to cover the porous substrate, and has a thioether group as an adsorptive group. , And a coating layer made of a copolymer containing a group containing a phosphoric acid group.

-PTFE-b6:
A PTFE porous membrane coated with PFDT-PG-AGE to which perfluorodecanethiol is bound, with reference to the description in paragraphs 0068 to 028 of JP2016-29146A.

The PTFE-b6 obtained by the above method is a fluorinated polymer containing a structure of "PFDT-PG-AGE" arranged on a porous substrate made of PTFE so as to cover the porous substrate. It contained a coating layer made of a copolymer containing a group containing a thioether group as an adsorptive group.

-PTFE-b7:
A PTFE porous membrane coated with poly (SZNB-b-NPF6) -2 with reference to the description in paragraphs 0085-0088 of JP2016-194040.
The PTFE-7 obtained by the above method has a "poly (SZNB-b-NPF6) -2" structure arranged on a porous substrate made of PTFE so as to cover the porous substrate. It was a fluorinated polymer containing, and contained a coating layer made of a copolymer containing a sulfonic acid group as an adsorptive group and a group containing a quaternary ammonium group.

-PTFE-b8
Poly (C2 diacid-r-NPF6) was synthesized with reference to the description in paragraphs 0110 to 0112 of JP-A-2016-196625, and coated on the PTFE porous membrane with reference to the description in paragraph 0109 of the same. A film obtained by forming a layer.

The PTFE-b8 obtained by the above method has a "poly (C2dioic acid-r-NPF6)" structure arranged on a porous substrate made of PTFE so as to cover the porous substrate. A coating layer made of a copolymer containing a carboxylic acid group and an oxyalkylene group as an adsorptive group was contained.

-PTFE-b9:
Poly (C4-r-NPF6-r-NHS) was synthesized with reference to the description in paragraphs 0120 to 0124 of JP-A-2016-196625, and on the PTFE porous membrane with reference to the description in paragraph 0109. A film obtained by forming a coating layer on the surface.
^{1 1} H-NMR (300 MHz, CDCl3): δ (ppm) 6 (s wide), 5.9 to 5.0 (m wide), 5.1 to 4.6 (m wide), 4.6 to 4. 1 (m wide), 4.0 to 3.0 (m wide), 3.0 to 2.4 (m wide), 2.3 to 1.4 (m wide), 1.25 (s wide).

The PTFE-9 obtained by the above method is "poly (C4-r-NPF6-r-NHS)" arranged on a porous substrate made of PTFE so as to cover the porous substrate. A coating layer made of a copolymer containing a thioether group as an adsorptive group and a group containing a diester group was contained.

・ Filter Y1:
A porous film containing a polyimide resin produced by referring to the description in paragraphs 0223, 0234 to 0239 of JP-A-2017-68262.
The imidization rate was controlled by adjusting the particle size and the like of the fine particles to be used to control the pore diameter, and adjusting the firing temperature and / or the re-baking temperature and the like. The imidization rate was 1.85. The pore diameter is shown in the table described later.

-Filters Y2 to Y6:
A film produced by the same method as the filter Y1 except that the particle size of the fine particles to be used and the firing temperature and / or the re-baking temperature were adjusted so that the pore diameter and the imidization rate became desired values. ..
The imidization ratio is 1.82, 1.60, 1.93, 1.68, 0.88 in order from the filter Y2. The pore diameter is shown in the table described later.

・ R:
A porous film containing a polyimide resin, which is produced by referring to the description in paragraphs 0019 to 0027 of Japanese Patent Application Laid-Open No. 2016-538122.
The imidization rate was 1.45. Although the porous film contained a structure in which the imidization rate was different in the film thickness direction, it was determined as the average value of the entire porous film.

・ S:
A porous film containing a polyimide resin produced by referring to the description in paragraphs 202 to 203 of JP-A-2018-20301.
The produced porous membrane is the membrane described as Example 1 of JP-A-2018-20301. The B value and the imidization rate were 8 nm and 1.43, respectively.

・ T:
A porous film containing a polyimide resin produced by referring to the description in paragraphs 202 to 203 of JP-A-2018-20301.
The produced porous membrane is the membrane described as Example 2 of JP-A-2018-20301. The B value and the imidization rate were 10 nm and 1.54, respectively.

[Organic cleaning solution]
The organic cleaning solution used for the pretreatment is shown below. High-purity grade was used for all organic cleaning solutions.
-PGMEA: Propylene glycol monomethyl ether acetate-IPA: Isopropanol-CyHe: Cyclohexane-nBA: Butyl acetate

〔Preprocessing〕
The filter to be treated was pretreated by the cleaning method shown below.
The filter to be processed was subjected to pretreatment in a state of being contained in a cartridge with a filter having a filter cylinder length of 1 inch, and then subjected to a test described later.

<Immersion treatment>
The filter to be treated was immersed in 20 liters of organic cleaning solution. The type of organic cleaning liquid, liquid temperature, and immersion period are shown in the table below.

<Sonication>
The filter to be treated was subjected to ultrasonic treatment in a state of being immersed in 20 liters of organic cleaning liquid (PGMEA). Sonication continued for 1 hour. The ultrasonic output is shown in the table below.

<Liquid flow treatment>
The organic cleaning liquid was passed through a filter unit in which a cartridge with a filter containing a filter to be treated was housed and installed. The types and volume of organic cleaning liquids are shown in the table below.

When the pretreatment contained two or more treatments, the next treatment was carried out immediately after one treatment was completed in the order of immersion treatment, ultrasonic treatment, and liquid passing treatment.
After the pretreatment, the filter (cartridge with filter) was housed in the housing used in the [Manufacturing of chemicals] test described in the subsequent stage.
If the organic cleaning solution that was last contacted was different from the purified solution used in [Production of chemical solution], 400 kg of the purified solution was passed through the solution before being subjected to the test of [Production of chemical solution].

〔analysis〕
The preprocessed filter was analyzed.
In the analysis, in order to prevent the content of the specific organic compound or the like in the filter from being affected by the analysis treatment (elution treatment, etc.), each filter is used for manufacturing a chemical solution described later. In addition to the above, two filters were prepared and used for the analysis before the pretreatment and the analysis after the pretreatment, respectively.
Specifically, when the filter 1 shown in the latter table is manufactured, it is obtained and obtained at the same opportunity with the same configuration as the filter to be treated, which is used for pretreating and subjecting to the production test of the chemical solution. Two more filters (filters to be processed) that were distributed and stored under the conditions were prepared. One of the above two filters was analyzed before the pretreatment, and the content of the analyzed specific organic compound and the like were contained in the specific organic compound before the filter 1 was pretreated. It was determined to be the content of the compound and the like. Further, the other of the above two filters is analyzed after being subjected to the same pretreatment as the filter 1, and the content of the analyzed specific organic compound and the like are pretreated on the filter to be treated. It was determined that the content of the specific organic compound contained in the obtained filter 1 and the like.

<Specific organic compound>
The content of the specific organic compound in the various filters was measured by the method described above in the specification.
The compounds detected as specific organic compounds are as follows.

-Compound represented by the general formula (I)

-Compound represented by the general formula (II)

-Compound represented by the general formula (III)

-Compound represented by the general formula (IV)

-Compound represented by the general formula (V)

-Compound represented by the general formula (VI)

-Compound represented by the general formula (VII)

-Compound represented by the general formula (VIII)

-Compounds represented by the general formula (X) When applied to the general formula (X), compounds having j of 12 to 50 were detected, respectively.

-Compounds represented by the general formula (XI) When applied to the general formula (XI), compounds having k of 12 to 50 were detected, respectively.

-The compound squalene represented by the general formula (XII) was detected.

<Specific metal component>
The contents of the specific metal components (specific metal ions and specific metal particles) in the various filters were measured using the Aguilent 8900 by the method described above in the specification.

Table 1 below shows the conditions of the pretreatment and the contents of the specific organic compound and the specific metal component in the filter after the treatment.

[Manufacturing of chemicals]
Four filters that had undergone pretreatment were selected and used as the first filter to the fourth filter. A filtration device was produced in which the first filter to the fourth filter were arranged in series in this order between the inflow portion and the outflow portion. Each filter was housed in a housing while being contained in a cartridge with a filter to form a filter unit.
The liquid to be purified was purified using the above filtration device. The names of the chemicals referred to below correspond to the numbers of each example. For example, the chemical solution produced in Example A001 described in the latter part and used for the test is referred to as chemical solution A001.

[Liquid to be purified]
The liquid to be purified used for purification is shown below. All the liquids to be purified are high-purity grades. ^{The value in parentheses is the distance (MPa 0.5} ) of the Hansen solubility parameter of each liquid to be purified (organic solvent) with respect to Eikosen.
-PGMEA: Propylene glycol monomethyl ether acetate (9.5)
PGME: Propylene glycol monoethyl ether (11.0)
PGMEA / PGME (v / v = 7/3): 7: 3 (volume-based) mixture of PGMEA and PGME (10.2)
-PGMP: Propylene glycol monopropyl ether (10.6)
-MPM: Methyl methoxypropionate (8.8)
-CHN: Cyclohexanone (5.1)
NBA: Butyl acetate (4.6)
-ΓBL: γ-Butyrolactone (8.5)
MIBC: 4-methyl-2-pentanol (12.1)
-IAA: Isoamyl acetate (6.0)
Butyl butyrate (4.6)
-Isobutyl isobutyrate (3.6)
・ Isoamyl ether (2.1)
・ Undecane (1.8)
Dimethyl malonate / isoamyl ether = 9/1 (9: 1 (mass-based) mixture of dimethyl malonate and isoamyl ether) (9.4)
Dimethyl malonate / isoamyl ether = 5/5 (5: 5 (mass-based) mixture of dimethyl malonate and isoamyl ether) (5.9)
-Dimethyl malonate / isoamyl ether = 1/9 (mixture of dimethyl malonate and isoamyl ether 1: 9 (mass basis)) (2.7)
The distance of the Hansen solubility parameter for Eikosen when dimethyl malonate is used alone is 10.3 MPa ^0.5 .

[test]
[Pre-wet liquid, rinse liquid]
The defect suppression property of the produced chemical solution when used as a pre-wet solution and a rinse solution was evaluated by the method shown below.
First, a chemical solution was spin-discharged onto a silicon substrate having a diameter of 300 mm, and 0.5 cc of each chemical solution was discharged onto the surface of the substrate while rotating the substrate. Then, the substrate was spin-dried. Next, the number of defects existing on the substrate after the chemical solution was applied was measured using a wafer inspection device “SP-5” manufactured by KLA-Tencor.
Next, using EDAX (energy-dispersive X-ray spectroscopy), among the defects of this wafer, "metal residue defects" containing particulate foreign matter as the main component of metal and "particles" containing organic matter as the main component are used. It was classified into "state organic residue defects" and measured respectively. Further, non-particle-like stain-like defects were counted as "stain-like defects".
If the evaluation of the metal residue defect, the particulate organic residue defect, and the stain-like residue defect is C or higher, it can be suitably used as a pre-wet liquid and a rinse liquid.

<Metal residue defects, particulate organic residue defects, stain-like residue defects>
A: The corresponding number of defects was 20 / wafer or less.
B: The corresponding number of defects exceeded 20 / wafer and was 50 / wafer or less.
C: The corresponding number of defects exceeded 50 / wafer and was 100 / wafer or less.
D: The number of corresponding defects exceeds 100 / wafer.

[Piping cleaning liquid]
The defect performance suppression property of the manufactured chemical solution when used as a pipe cleaning solution was evaluated by the method shown below.
The pipe was cleaned by passing 5000 ml of the chemical solution to be evaluated at 500 ml / min through the pipe (wetted part: made of PTFE, φ: 50 mm, length: 5 m) immediately after purchase.
Next, the same test as the evaluation of the performance as the pre-wet solution or the rinse solution described above except that the chemical solution A021 (the chemical solution obtained by the purification treatment of Example A021) was discharged onto the wafer through this pipe. Was performed and evaluated according to the same criteria. If the chemical solution A021 that has passed through the pipe after cleaning can be suitably used as a pre-wet liquid or a rinse liquid, defects may occur when the equipment is cleaned by applying such a pipe cleaning liquid to the resist process. It can be judged that it can be suppressed.

[Developer / rinse solution]
The defect performance inhibitory property when the produced chemical solution was used as a developing solution or a rinsing solution was evaluated by the method shown below.

≪Test 1 (ArF exposure) ≫
First, a resist pattern was formed by the following operations.
The organic antireflection film forming composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon substrate having a diameter of 300 mm and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 78 nm.
In order to improve the coatability, a pre-wet solution (chemical solution A021 was used) was dropped on the surface of the silicon wafer on which the antireflection film was formed on the antireflection film side, and spin coating was performed.
Next, a sensitive light-sensitive or radiation-sensitive resin composition (the following sensitive light-sensitive or radiation-sensitive resin composition 1) is applied onto the antireflection film after the pre-wet step, and the temperature is 100 ° C. for 60 seconds. Prebaking (PB) was carried out over the course to form a resist film having a film thickness of 150 nm.

(Actinic cheilitis or radiation-sensitive resin composition 1)
Acid-degradable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the numerical value described in each repeating unit means mol%): 100 parts by mass.

Photoacid generator shown below: 8 parts by mass

Quencher shown below: 5 parts by mass (mass ratio was 0.1: 0.3: 0.3: 0.2 in order from the left). Among the following citrates, the polymer type citrate has a weight average molecular weight (Mw) of 5,000. In addition, the numerical value described in each repeating unit means a molar ratio.

Hydrophobic resin shown below: 4 parts by mass (Mass ratio was 0.5: 0.5 in order from the left.) Of the following hydrophobic resins, the hydrophobic resin on the left has a weight average molecular weight. (Mw) is 7000, and the weight average molecular weight (Mw) of the hydrophobic resin on the right side is 8000. In each hydrophobic resin, the numerical value described in each repeating unit means the molar ratio.

solvent:
PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass Cyclohexanone: 600 parts by mass γ-BL (γ-butyrolactone): 100 parts by mass

The wafer on which the resist film was formed was subjected to pattern exposure at ^{25 mJ / cm 2} using an ArF excimer laser scanner (Numerical aperture: 0.75). Then, it was heated at 120 ° C. for 60 seconds. Then, it was developed by paddling with a developer for 30 seconds, and then paddled with a rinse solution for 30 seconds for development. Then, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds to form a negative resist pattern. Then, the obtained negative pattern was heated at 200 ° C. for 300 seconds. Through the above steps, an L / S pattern (average pattern width: 45 nm) having a line / space of 1: 1 was obtained. For each pattern, the developability and defect suppression property were evaluated.
Here, when evaluating the developing solution, the developing solution to be evaluated was used as the developing solution, and the chemical solution B049 (the chemical solution obtained by the purification treatment of Example B049) was used as the rinsing solution.
When evaluating the rinse solution, a chemical solution B018 was used as the developer, and the rinse solution to be evaluated was used as the rinse solution.

<Defect suppression>
The pattern of the formed wafer was observed using a pattern defect device (Multipurpose SEM (Scanning Electron Microscope) "Inspago" RS6000 series manufactured by Hitachi High-Technology Co., Ltd.), and the number of the following defects was measured.
-Development defect: Defect in which no space is formed to the bottom of the pattern-Residue defect: Defect in which foreign matter exists on the pattern-Uniformity defect: Defect in which the pattern width is 3 nm or more larger than the target (45 nm) , Development defect, residue defect, and uniformity defect can be suitably used as a pre-wet solution and a rinse solution as long as the evaluation is C or higher.

<Development defect, residue defect, uniformity defect>
A: The corresponding number of defects was 5 / wafer or less.
B: The number of corresponding defects exceeded 5 / wafer and was 10 / wafer or less.
C: The number of corresponding defects exceeded 10 / wafer and was 30 / wafer or less.
D: The corresponding number of defects exceeded 30 / wafer.

≪Test 2 (EUV exposure) ≫
(Actinic cheilitis or radiation-sensitive resin composition (resist composition 1))
First, the resist composition 1 was obtained by mixing each component with the following composition.
-Resin (A-1): 0.77 g
-Photoacid generator (B-1): 0.03 g
-Basic compound (E-3): 0.03 g
-PGMEA (commercially available, high-purity grade): 67.5 g
-Ethyl lactate (commercially available, high-purity grade): 75 g

-Resin As the resin, the following resins were used.

-Photoacid generator The following compounds were used as the photoacid generator.

-Basic compounds The following compounds were used as the basic compounds.

(Pattern formation and evaluation)
The residual defect suppressing performance, the bridge defect suppressing performance, and the stain-like defect suppressing performance of the chemical solution were evaluated by the following methods. ^{A coater developer "RF 3S} " manufactured by SOKUDO was used for the test.
First, AL412 (manufactured by Brewer Science) was applied onto a silicon wafer having a direct line of 300 mm and baked at 200 ° C. for 60 seconds to form a resist underlayer film having a film thickness of 20 nm. A pre-wet solution (chemical solution A021) was applied thereto, a resist composition was applied thereto, and baking (PB: Prebake) was performed at 100 ° C. for 60 seconds to form a resist film having a film thickness of 30 nm.

This resist film was exposed through a reflective mask using an EUV exposure machine (manufactured by ASML; NXE3350, NA0.33, Dipole 90 °, outer sigma 0.87, inner sigma 0.35). Then, it was heated at 85 ° C. for 60 seconds (PEB: Post Exposure Bake). Then, the developing solution was sprayed for 30 seconds by the spray method for development, and the rinse solution was discharged onto the silicon wafer for 20 seconds by the rotary coating method for rinsing. Subsequently, the silicon wafer was rotated at a rotation speed of 2000 rpm for 40 seconds to form a line-and-space pattern having a space width of 20 nm and a pattern line width of 15 nm.
Here, when evaluating the developing solution, the developing solution to be evaluated was used as the developing solution, and the chemical solution B049 (the chemical solution obtained by the purification treatment of Example B049) was used as the rinsing solution.
When evaluating the rinse solution, a chemical solution B018 was used as the developer, and the rinse solution to be evaluated was used as the rinse solution.

The above pattern was observed with a pattern defect device (Hitachi High-Technology Multipurpose SEM (Scanning Electron Microscope) "Inspago" RS6000 series), and "PLOT defect", which is a protrusion-like defect, and a cross-linking-like defect between patterns were observed. The numbers of "BRIDGE defects" and "GEL defects", which are defects of the film-like residue, were measured and evaluated according to the following criteria.

(PLOT defect evaluation criteria)
A: The number of defects was 20 / wafer or less.
B: The number of defects was 21 / wafer or more and 50 / wafer or less.
C: The number of defects was 51 / wafer or more and 100 / wafer or less.
D: The number of defects was 101 / wafer or more.

(BRIDGE defect evaluation criteria)
A: The number of defects was 20 / wafer or less.
B: The number of defects was 21 / wafer or more and 50 / wafer or less.
C: The number of defects was 51 / wafer or more and 100 / wafer or less.
D: The number of defects was 101 / wafer wafer or more.

(Evaluation criteria for GEL defects)
A: The number of defects was 20 / wafer or less.
B: The number of defects was 21 / wafer or more and 50 / wafer or less.
C: The number of defects was 51 / wafer or more and 100 / wafer or less.
D: The number of defects was 101 / wafer wafer or more

[result]
Tables 2 and 3 below show the types of liquids to be purified and filters used in the purification treatment, and the results of evaluating the obtained chemicals.
In Table 2, "P / R" described in the column of use is an evaluation of defect inhibitory property when the chemical solution is used as the pre-wet solution and the rinse solution by the method shown in the item of [Pre-wet solution, rinse solution]. Indicates that “Piping” indicates that the defect suppression property was evaluated when used as a piping cleaning solution by the method shown in the item of [Piping cleaning solution].
Table 3 shows the results of evaluating the defect suppressivity when the chemical solution is used as a developer or a rinse solution by the method shown in the item of [Developer / Rinse solution]. Tables 3a1 and 3a2 show the treatment conditions of the liquid to be purified (the liquid to be purified and the filter used) and the test results using the manufactured chemicals, respectively, in the same example. The relationship between Table 3a2 and Table 3a2 is also the same.

From the results shown in the table, it was confirmed that the filter of the present invention can be used to produce a chemical solution having excellent defect suppressing properties.

Further, it was confirmed that when the pore diameter of the filter is 10 nm or less, the defect suppressing property of the produced chemical solution tends to be more excellent (comparison between Examples A003 and A019, etc.).

A filter having a content of the first organic compound of less than 5.0 mass ppt easily adsorbed the second organic compound in the washing process and in the environment. Therefore, the chemical solution produced by using a filter having a content of the first organic compound of 5.0 mass ppt or more has a stain-like defect inhibitory property when the chemical solution is used as a pre-wet solution or a rinse solution, and a chemical solution. It was confirmed that the uniformity defect suppression property was more excellent when the above was used as a developing solution (comparison between Example A013 and Examples A003, A012, A018. Example B008 and Examples B001, B007, B013. Comparison with etc.).

The total content of the first organic compound is 5.0 mass ppt or more with respect to the mass of the filter, and the compounds represented by the general formulas (I) to (VIII) are represented by the general formula (X). Using a filter in which the total content of the alkane and the compound selected from the group consisting of the alkenes represented by the general formulas (XI) and (XII) is 6500 mass ppt or less with respect to the mass of the filter. It was confirmed that the produced chemical solution tended to have more excellent stain-like defect suppressing property when the chemical solution was used as a pre-wet solution or a rinsing solution, and more uniform defect suppressing property when the chemical solution was used as a developing solution (implementation). Comparison of Example A013 with Examples A003, A012, A018. Comparison of Examples A014, A015, A017 with Examples A012, A018. Comparison of Example B008 with Examples B001, B007, B013 and the like. Comparison of Examples B009, B010, B012 with Examples B007, B013, etc.).

For the chemical solution produced using the filter in which the total content of the compounds selected from Group A was 0.10 to 3200 mass ppt with respect to the mass of the filter, the chemical solution was used as a pre-wet solution or a rinse solution. It was confirmed that the stain-like defect suppressing property in the case and the uniformity defect suppressing property when the chemical solution was used as the developing solution tended to be more excellent (comparison between Example A013 and Examples A003, A012, A018. Comparison of Examples A014, A015, A017 with Examples A012, A018. Comparison of Example B008 with Examples B001, B007, B013, etc. Examples B009, B010, B012 and Examples B007, B013 Comparison etc.).

For the chemical solution produced using the filter in which the total content of the compounds selected from Group B was 1.0 to 1200 mass ppt with respect to the mass of the filter, the chemical solution was used as a pre-wet solution or a rinse solution. It was confirmed that the stain-like defect suppressing property in the case and the uniformity defect suppressing property when the chemical solution was used as the developing solution tended to be more excellent (comparison between Example A013 and Examples A003, A012, A018. Comparison of Examples A014, A015, A017 with Examples A012, A018. Comparison of Example B008 with Examples B001, B007, B013, etc. Examples B009, B010, B012 and Examples B007, B013 Comparison etc.).

It was confirmed that the chemical solution produced by using the filter containing 0.10 to 5000 mass ppt of the specific metal component with respect to the mass of the filter tends to have more excellent defect suppressing property (results of Example A016, etc.). ..

It was confirmed that when the filter body contains an ion exchange group, the defect-suppressing property of the produced chemical solution tends to be more excellent (comparison of Examples A023 to A027, etc.).

It was confirmed that when the filter body is made of a material other than the fluorine-based material, the defect-suppressing property of the produced chemical solution tends to be more excellent (results of Examples B018 and 019, etc.).

When the chemical solution produced is an organic solvent and the distance of the Hansen solubility parameter to Eikosen is 3 to 20 MPa ^0.5 , the effect of the present invention (particularly, a pattern is formed by EUV exposure and the chemical solution is rinsed. It was confirmed that the defect suppressivity when used as is more excellent (comparison of Examples B048, B051, B054, B057, etc.).

Moreover, if the drug solution to be produced, including an organic solvent distance Hansen parameter is 3 to 20 mPa ^0.5 for eicosene, and an organic solvent distance Hansen parameters for eicosene is not a 3 to 20 mPa ^0.5, the mixing ratio It was confirmed that when the (mass ratio) is 20/80 to 80/20, the effect of the present invention (particularly, defect suppression property when a pattern is formed by EUV exposure and the chemical solution is used as a rinse solution) is more excellent. (Results of Examples B060, B063, B066, etc.).

Further, in the filters to be treated used for manufacturing the "filter 79, filter 80, filter 81, filter 82", the same filters to be treated are prepared except that the packing material is a fluororesin, and "filters" are prepared. The same pretreatment as "79, filter 80, filter 81, filter 82" was performed to obtain "filter 79b, filter 80b, filter 81b, filter 82b".
The analysis results of the contents of the specific organic compound and the specific metal compound in "filter 79b, filter 80b, filter 81b, filter 82b" were equivalent to those of "filter 79, filter 80, filter 81, filter 82", respectively.
Using the obtained "filter 79b, filter 80b, filter 81b, filter 82b", the same test as the test performed using "filter 79, filter 80, filter 81, filter 82" was performed. The same results as the test performed using "filter 79, filter 80, filter 81, filter 82" were obtained.
By comparing such results with the results of Examples B045 and B046, pretreatment is performed on the filter to be treated, in which the contact portion with the filter to be treated is packed with a packing material of fluororesin or stainless steel. When the filter of the present invention was obtained, it was confirmed that the effect of the present invention was more excellent.

100 Filtration device 101 Inflow part 102 Outflow part 103, 104 Filter 105 Piping

Claims (29)

It is a filter for filtration
With the filter body
Selected from the group consisting of compounds represented by the general formulas (I) to (V), alkanes represented by the general formula (X), and alkenes represented by the general formulas (XI) and (XII). Contains one or more first organic compounds,
A filter in which the total content of the first organic compound is 0.10 to 10000 mass ppt with respect to the mass of the filter.

In the general formula (I), R ^1a and R ^1c each independently represent an alkyl group which may contain a substituent.
R ^1b represents an alkylene group which may contain a substituent.

In the general formula (II), X contains a benzene ring group which may contain a substituent, a cyclohexane ring group which may contain a substituent, or a cycloalkyloxy group as a substituent. Represents a cyclohexane ring group. The cyclohexane ring group may contain yet another substituent.

In the general formula (III), R ^{3a to} R ^3h each independently represent an alkyl group which may contain a substituent.
R ^3b and R ^3e may be combined with each other to form a ring.
The ^{group formed by bonding R 3b} and R ^3e to each other is −O− (−Si ( ^R3i ) ₂₋ O−) _a− .
a represents an integer of 1 or more.
R ³ⁱ represents an alkyl group which may contain a substituent.
The plurality of R ³ⁱ existing may be the same or different from each other.

In the general formula (IV), R ^4a represents -N (R ^4c ) R ^4d or -SR ^4e .
R ^4c , R ^4d , and R ^4e independently represent a hydrogen atom or a substituent.
R ^4b represents -NH- or -S-.

In the general formula (V), Y represents a benzene ring group in which the alkyl group may be substituted, or a group represented by the formula (A).

When Y represents a benzene ring group, s represents 1 and L represents a single bond and R ^5a represents an alkyl group which may contain a substituent. The alkyl group may contain a hetero atom. When the alkyl group is substituted on the benzene ring group, the alkyl group and R ^5a may be bonded to each other to form a ring. When a plurality of alkyl groups are substituted on the benzene ring group, the alkyl groups may be bonded to each other to form a ring.
When Y represents a group represented by the formula (A), s represents 3, L represents a methylene group, and R ^5a independently represents an alkyl group.

In the general formula (X), j represents an integer of 12 to 50. Two j are the same value

In the general formula (XI), k represents an integer of 12 to 50. The two k are the same value.

n represents an integer of 30 to 50.
m represents an integer of 20 to 90 and 2n-2 or less. The filter according to claim 1, wherein the filter further contains one or more of a second organic compound selected from the group consisting of compounds represented by the general formulas (VI) to (VIII).

R ^6a represents an alkyl group or a hydrogen atom which may contain a substituent.
R ^6b and R ^6c independently represent a hydrogen atom, -AL-O-R ^6d , -CO-R ^6e , or -C (OH) -R ^6f , respectively.
AL represents an alkylene group which may contain a substituent.
R ^6d , R ^6e , or R ^6f each independently represent a substituent.
When there are a plurality of ^{R 6d , the plurality of R 6d} may be the same or different. When there are a plurality of ^{R 6e , the plurality of R 6e} may be the same or different. When there are a plurality of ^{R 6fs , the plurality of R 6fs} may be the same or different.
Two combinations selected from the group consisting of ^{substituents R 6d} , R ^6e , and R ^6f which may be contained in the alkyl group represented by R ^{6a , two R 6d} each other, two R ^6e each other. Or, the two R ^6fs may be bonded to each other to form a ring.
At ^{least one of R 6a} , R ^6b , or R ^6c is a non-hydrogen atom.

In the general formula (VII), R ^7a and R ^7b each independently represent an alkyl group which may contain a substituent.

In the general formula (VIII), R ^{8a to} R ^8c independently represent a hydrogen atom, an alkyl group which may contain a substituent, or a benzene ring group which may contain a substituent. The total content of the first organic compound is 5.0 mass ppt or more with respect to the mass of the filter, and
Compounds selected from the group consisting of compounds represented by the general formulas (I) to (VIII), alkanes represented by the general formula (X), and alkenes represented by the general formulas (XI) and (XII). The filter according to claim 2, wherein the total content of the above is 6500 mass ppt or less with respect to the mass of the filter. The filter
One or more of the compounds selected from the group A consisting of the compounds represented by the general formulas (I) to (VIII), and
2 or claim 2, which contains an alkane represented by the general formula (X) and one or more compounds selected from the group B consisting of alkanes represented by the general formulas (XI) and (XII). The filter according to 3. The filter according to claim 4, wherein the total content of the compounds selected from the group A is 0.10 to 3200 mass ppt with respect to the mass of the filter. The filter according to claim 4 or 5, wherein the total content of the compounds selected from the group B is 1.0 to 1200 mass ppt with respect to the mass of the filter. Further, a metal component containing a metal element selected from the group consisting of Al, Ca, Cr, Cu, Fe, K, Mg, Na, Ni, Zn, and Pb is added to 0 with respect to the mass of the filter. The filter according to any one of claims 1 to 6, which contains 10 to 5000 mass ppt. The filter body contains nylon
The filter according to any one of claims 4 to 7, which contains one or more compounds selected from the group A and two or more compounds selected from the group B. It contains an alkane represented by the general formula (X) and an alkene represented by the general formula (XI).
The alkane content A represented by the general formula (X), the alkene content B represented by the general formula (XI), and the alkene content C represented by the general formula (XII) are based on mass. The filter according to claim 8, wherein C <A and C <B. The filter body contains polyethylene or polytetrafluoroethylene, and the filter body contains polyethylene or polytetrafluoroethylene.
The filter according to any one of claims 4 to 7, which contains one or more compounds selected from the group A and an alkane represented by the general formula (X). The filter according to any one of claims 1 to 10, wherein the pore diameter of the filter is 10 nm or less. The filter according to any one of claims 1 to 11, wherein the filter body contains an ion exchange group. The filter according to any one of claims 1 to 12, wherein the filter body contains two or more layers made of different materials. The filter according to any one of claims 1 to 13, wherein the filter body contains an asymmetric porous membrane. The filter according to any one of claims 1 to 14, wherein the filter body is made of a material other than a fluorine-based material. The method for manufacturing a filter according to any one of claims 1 to 15.
Selected from the group consisting of compounds represented by the general formulas (I) to (VIII), alkanes represented by the general formula (X), and alkenes represented by the general formulas (XI) and (XII) 1 A method for producing a filter, which comprises a step of subjecting an untreated filter containing seeds or more to a pretreatment using an organic cleaning solution.

In the general formula (I), R ^1a and R ^1c each independently represent an alkyl group which may contain a substituent.
R ^1b represents an alkylene group which may contain a substituent.

In the general formula (II), X contains a benzene ring group which may contain a substituent, a cyclohexane ring group which may contain a substituent, or a cycloalkyloxy group as a substituent. Represents a cyclohexane ring group. The cyclohexane ring group may contain yet another substituent.

In the general formula (III), R ^{3a to} R ^3h each independently represent an alkyl group which may contain a substituent.
R ^3b and R ^3e may be combined with each other to form a ring.
The ^{group formed by bonding R 3b} and R ^3e to each other is −O− (−Si ( ^R3i ) ₂₋ O−) _a− .
a represents an integer of 1 or more.
R ³ⁱ represents an alkyl group which may contain a substituent.
The plurality of R ³ⁱ existing may be the same or different from each other.

In the general formula (IV), R ^4a represents -N (R ^4c ) R ^4d or -SR ^4e .
R ^4c , R ^4d , and R ^4e independently represent a hydrogen atom or a substituent.
R ^4b represents -NH- or -S-.

In the general formula (V), Y represents a benzene ring group in which the alkyl group may be substituted, or a group represented by the formula (A).

When Y represents a benzene ring group, s represents 1 and L represents a single bond and R ^5a represents an alkyl group which may contain a substituent. The alkyl group may contain a hetero atom. When the alkyl group is substituted on the benzene ring group, the alkyl group and R ^5a may be bonded to each other to form a ring. When a plurality of alkyl groups are substituted on the benzene ring group, the alkyl groups may be bonded to each other to form a ring.
When Y represents a group represented by the formula (A), s represents 3, L represents a methylene group, and R ^5a independently represents an alkyl group.

In the general formula (X), j represents an integer of 12 to 50. Two j are the same value

In the general formula (XI), k represents an integer of 12 to 50. The two k are the same value.

n represents an integer of 30 to 50.
m represents an integer of 20 to 90 and 2n-2 or less.

R ^6a represents an alkyl group or a hydrogen atom which may contain a substituent.
R ^6b and R ^6c independently represent a hydrogen atom, -AL-O-R ^6d , -CO-R ^6e , or -C (OH) -R ^6f , respectively.
AL represents an alkylene group which may contain a substituent.
R ^6d , R ^6e , or R ^6f each independently represent a substituent.
When there are a plurality of ^{R 6d , the plurality of R 6d} may be the same or different. When there are a plurality of ^{R 6e , the plurality of R 6e} may be the same or different. When there are a plurality of ^{R 6fs , the plurality of R 6fs} may be the same or different.
Two combinations selected from the group consisting of ^{substituents R 6d} , R ^6e , and R ^6f which may be contained in the alkyl group represented by R ^{6a , two R 6d} each other, two R ^6e each other. Or, the two R ^6fs may be bonded to each other to form a ring.
At ^{least one of R 6a} , R ^6b , or R ^6c is a non-hydrogen atom.

In the general formula (VII), R ^7a and R ^7b each independently represent an alkyl group which may contain a substituent.

In the general formula (VIII), R ^{8a to} R ^8c independently represent a hydrogen atom, an alkyl group which may contain a substituent, or a benzene ring group which may contain a substituent. The organic cleaning solution is propylene glycol monomethyl ether acetate, isopropanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, γ-butyrolactone, diisoamyl. Ether, butyl acetate, isoamyl acetate, 4-methyl-2-pentanol, dimethylsulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone, 2 -Heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, mesitylene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2 -The method for producing a filter according to claim 16, which contains at least one selected from the group consisting of octanol, ethyl acetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate. The method for producing a filter according to claim 16 or 17, wherein the pretreatment includes a step of immersing the untreated filter in the organic cleaning solution for 3 days or more. The method for producing a filter according to any one of claims 16 to 18, which comprises a step of ultrasonically treating the untreated filter immersed in the organic cleaning liquid to perform the pretreatment. The pretreatment includes a step of passing the organic cleaning liquid through the untreated filter having a hollow cylindrical shape.
The method for manufacturing a filter according to any one of claims 16 to 19, wherein the organic cleaning liquid through which the liquid is passed is 10 kg or more with respect to 1 inch of the cylinder length of the untreated filter. Compounds represented by the general formulas (I) to (VIII), alkanes represented by the general formula (X), and alkenes represented by the general formulas (XI) and (XII) in the untreated filter. For the total content of compounds selected from the group consisting of
In the filter after the pretreatment, the compounds represented by the general formulas (I) to (VIII), the alkane represented by the general formula (X), and the general formulas (XI) and (XII) are used. The method for producing a filter according to any one of claims 16 to 20, wherein the mass ratio of the total content of the compounds selected from the group consisting of the represented alkanes is 0.5000 or less. Claims 16 to 21 wherein the untreated filter before being pretreated is packed with a packing material in which at least a part of the contact portion with the untreated filter is a fluororesin or stainless steel. The method for manufacturing a filter according to any one of the above items. Inflow part, outflow part,
2. The filter according to any one of claims 1 to 15 and the like.
Two or more of the filters are arranged in series between the inflow and outflow.
A filtration device for purifying a liquid to be purified to obtain a chemical liquid, which contains a flow passage from the inflow portion to the outflow portion. The filtration according to claim 23, wherein among the two or more filters, the filter having the largest pore diameter has a pore diameter of 10 to 200 nm, and the filter having the smallest pore diameter has a pore diameter of 1 to 10 nm. apparatus. The filtration device according to claim 23 or 24, which comprises the filter according to claim 12. The filtration device according to any one of claims 23 to 25, which comprises the filter according to claim 9. The filtration device according to any one of claims 23 to 26, which comprises the filter according to claim 10. A method for producing a chemical solution by purifying the solution to be purified to obtain a chemical solution.
A method for producing a chemical solution, which comprises a step of filtering the liquid to be purified using the filter according to any one of claims 1 to 15 to obtain a chemical solution. The liquid to be purified is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, cyclohexanone, methyl methoxypropionate, butyl acetate, γ-butyrolactone, 4-methyl-2-pentanol, propylene glycol monoethyl. Ether, ethyl lactate, cyclopentanone, diisoamyl ether, isoamyl acetate, isopropanol, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone, 2-Heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, mesitylene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, The method for producing a drug solution according to claim 28, which comprises one or more selected from the group consisting of 2-octanol, ethyl acetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate.

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