JP2002047309A - Method of removing metal from alicyclic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a removing method with high energy efficiency, in which metals included can be removed with high-efficiency. SOLUTION: The metal removing method in which the monomer of an alicyclic polymer to or the polymer solution is passed through a filter on which ζ-potential acts, is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an alicyclic polymer,
Alternatively, the present invention relates to a method for removing metals such as sodium and iron contained in modified products or derivatives thereof.

[0002]

2. Description of the Related Art Alicyclic polymers are very useful materials for photoresists and have many uses in the electronics field. In these devices in the field of electronics, their structures have been increasingly miniaturized in recent years, and it has been required that the content of metal impurities in materials used for improving the performance of electrical characteristics be extremely low. Therefore, even when the alicyclic polymer is used as a material in the field of electronics, it is important that the metal impurities be suppressed to an extremely small amount.

[0003] As a conventionally known method of removing and reducing metal impurities contained in an alicyclic polymer, there is a method of adsorbing metal ions to an ion exchange resin. However, this method is difficult to handle because the ion-exchange resin is often granular, and after adsorbing metal ions,
There are problems such as reverse regeneration treatment with an alkaline (or acidic) solution, washing with water, and regeneration treatment with an acidic (or alkaline) solution, and the need for many processes.

[0004]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for removing metal which has high energy efficiency and can reduce metal with high efficiency.

[0005]

Means for Solving the Problems The present inventors have conducted research to solve the problems of the conventional technology as described above, and as a result,
The above object can be achieved by passing an alicyclic polymer in a state of being dissolved in a raw material monomer or a solvent of the alicyclic polymer through a specific filter medium, thereby completing the present invention. . That is, the present invention firstly allows a monomer (hereinafter, also referred to as a “specific monomer”) to pass through a filter medium on which zeta potential acts (hereinafter, referred to as a “functional filter medium”), and then uses the monomer to remove fat. It is characterized by synthesizing a cyclic polymer. Secondly, the present invention is characterized in that, as a metal removal method, an organic solvent solution of an alicyclic polymer is passed through a filter medium on which zeta potential acts.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

[Specific Monomer] The specific monomer to be treated by the method of the present invention is a raw material of an alicyclic polymer useful as a material for a photoresist. The alicyclic polymer mentioned here is not particularly limited as long as it is a polymer having an alicyclic skeleton. In particular, a polymer useful as a material for a photoresist and preferably used in the treatment method of the present invention is an alkali-insoluble or alkali-insoluble acid-dissociable group-containing resin having an alicyclic skeleton. A resin that becomes alkali-soluble when the acid-dissociable group is dissociated (hereinafter, also referred to as “specific resin”) may be mentioned. As the resin, for example, an alkali-insoluble or hardly alkali-soluble resin obtained by converting a part or all of the acidic functional groups in an alkali-soluble resin having an acidic functional group such as a carboxyl group and a phenolic hydroxyl group into an acid-dissociable group. A cyclic resin can be mentioned. As the specific monomer used as a starting material of the specific resin, for example, a norbornene-based compound represented by the following formula (1) (hereinafter, also referred to as “norbornene-based compound (α)”) and / or a compound represented by the following formula (2) Acrylic compound (hereinafter, also referred to as “acrylic compound (β)”) may be used.

[0008]

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[In the formula (1), A and B each independently represent a monovalent acid dissociable group having 20 or less carbon atoms which dissociates in the presence of a hydrogen atom or an acid to form an acidic functional group; At least one of A and B is the acid-dissociable group, or A and B each constitute an alicyclic skeleton of the formula (1).
X and Y form a heterocyclic acid-dissociable group represented by the following formula (a), and X and Y are each independently a hydrogen atom or a monovalent having 1 to 4 carbon atoms. And n is an integer of 0 to 2. ]

[0010]

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[0011]

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[In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or dissociation in the presence of an acid. A monovalent group having 20 or less carbon atoms which produces an acidic functional group (excluding a 1-branched alkyl group having 3 to 4 carbon atoms)
Is shown. ]

Norbornene Compound (α) In the above formula (1), the monovalent acid dissociable group of A and B having 20 or less carbon atoms (hereinafter referred to as “acid dissociable group (i)”) is as follows. For example, a group represented by the following formula (3) can be exemplified.

-(CH ₂ ) x COOR ³ (3)

[In the formula (3), R ³ has 1 to 1 carbon atoms.
0 hydrocarbon group, halogenated hydrocarbon group having 1 to 10 carbon atoms, alkoxycarbonylmethyl group (however, the alkoxyl group has 1 to 10 carbon atoms), tetrahydrofuranyl group, tetrahydropyranyl group, carbbutoxy It represents a methyl group, a carboxyloxyethyl group, a carboxyloxypropyl group or a trialkylylsilyl group (however, the alkyl group has 1 to 4 carbon atoms), and x is an integer of 0 to 4. ]

Among the acid dissociable groups (i), the group represented by the above formula (3) includes, for example, a methoxycarbonyl group,
An ethoxycarbonyl group, an n-propoxycarbonyl group,
i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n
-Pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 4-t-butylcyclohexyl An oxycarbonyl group, a cycloheptyloxycarbonyl group, a linear group such as a cyclooctyloxycarbonyl group,
Branched or cyclic alkoxycarbonyl group; aryloxycarbonyl group such as phenoxycarbonyl group, 4-t-butylphenoxycarbonyl group, 1-naphthylcarbonyl group; benzyloxycarbonyl group, 4-t-butylbenzyloxycarbonyl group and the like An aralkyloxycarbonyl group;

Methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group, n-propoxycarbonylmethoxycarbonyl group, i-propoxycarbonylmethoxycarbonyl group, n-butoxycarbonylmethoxycarbonyl group, 2-methylpropoxycarbonylmethoxycarbonyl group, 1- A linear, branched or cyclic alkoxycarbonylmethoxycarbonyl group such as a methylpropoxycarbonylmethoxycarbonyl group or a t-butoxycarbonylmethoxycarbonyl group;
Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, 2-methylpropoxycarbonylmethyl group, 1-
A linear, branched or cyclic alkoxycarbonylmethyl group such as a methylpropoxycarbonylmethyl group, a t-butoxycarbonylmethyl group, a cyclohexyloxycarbonylmethyl group, a 4-t-butylcyclohexyloxycarbonylmethyl group;

Aryloxycarbonylmethyl groups such as phenoxycarbonylmethyl group and 1-naphthyloxycarbonylmethyl group; benzyloxycarbonylmethyl group;
An aralkyloxycarbonylmethyl group such as -t-butylbenzyloxycarbonylmethyl group; a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group,
-N-propoxycarbonylethyl group, 2-i-propoxycarbonylethyl group, 2-n-butoxycarbonylethyl group, 2- (2-methylpropoxy) carbonylethyl group, 2- (1-methylpropoxy) carbonylethyl group, Linear, branched or cyclic 2-alkoxycarbonylethyl groups such as 2-t-butoxycarbonylethyl group, 2-cyclohexyloxycarbonylethyl group, 2- (4-butylcyclohexyloxycarbonyl) ethyl group; 2-phenoxy Carbonylethyl group, 2- (1
A 2-aryloxycarbonylethyl group such as -naphthyloxycarbonyl) ethyl group; a 2-aralkyloxycarbonylethyl group such as a 2-benzyloxycarbonylethyl group or a 2- (4-t-butylbenzyloxycarbonyl) ethyl group; Examples thereof include a tetrahydrofuranyloxycarbonyl group and a tetrahydropyranyloxycarbonyl group.

Of these acid dissociable groups (i), those of the formula (3) wherein x is 0 are preferred, and more preferred are methoxycarbonyl, ethoxycarbonyl and n
-Propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t
-Butoxycarbonyl group, n-pentyloxycarbonyl group, n-octyloxycarbonyl group, n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, t-butoxycarbonylmethoxycarbonyl group and the like.

In the above formula (1), X and Y
Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, Examples thereof include a methylpropyl group and a t-butyl group, and a hydrogen atom and a methyl group are particularly preferable. Further, in the formula (1), n is preferably 0 or 1.

Among the norbornene monomers (α), a specific example of the compound of the formula (1) wherein n is 0 is 5-methoxycarbonylbicyclo [2.2.1] hept-2-.
Ene, 5-ethoxycarbonylbicyclo [2.2.1]
Hept-2-ene, 5-n-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-i-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-n- Butoxycarbonylbicyclo [2.2.
1] Hept-2-ene, 5- (2'-methylpropoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5- (1'-methylpropoxy) carbonylbicyclo [2.2.1] Hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyclohexyloxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5- (4'-t-butylcyclohexyloxy) carbonylbicyclo [2.2.
1] Hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylmethoxycarbonylbicyclo [2.2.
1] Hept-2-ene, 5-tetrahydrofuranyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-tetrahydropyranyloxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5
-Ethoxycarbonylbicyclo [2.2.1] hept-
2-ene, 5-methyl-5-n-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-i-propoxycarbonylbicyclo [2.2.
1] hept-2-ene, 5-methyl-5-n-butoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5- (2'-methylpropoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5- (1'-methylpropoxy) carbonylbicyclo [2.2.1] Hept-2-ene, 5-methyl-5
t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5
-Methyl-5- (4'-t-butylcyclohexyloxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-phenoxycarbonylbicyclo [2.2.1] hept-2- Ene, 5-methyl-5-t
-Butoxycarbonylmethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-tetrahydrofuranyloxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-methyl-5-tetrahydropyranyloxycarbonylbicyclo [2.2.1]
Hept-2-ene,

5,6-di (methoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (ethoxycarbonyl) bicyclo [2.2.1] hept-2-
Ene, 5,6-di (n-propoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (i-
Propoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (n-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (t- (Butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (phenoxycarbonyl)
Bicyclo [2.2.1] hept-2-ene, 5,6-di (tetrahydrofuranyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (tetrahydropyranyloxycarbonyl ) Bicyclo [2.2.
1] Hept-2-ene, 5,6-dicarboxyanhydride bicyclo [2.2.1] hept-2-ene and the like.

Further, among the norbornene-based monomers (α), specific examples of the compound in which n in the formula (1) is 1 include:
8-methoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-i-propoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-n-
Butoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2'-methylpropoxy) carbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (1'-methylpropoxy) carbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8-cyclohexyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (4'-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodec-3-ene, 8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8-t-butoxycarbonylmethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene, 8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene,

8-methyl-8-methoxycarbonyltet
Lacyclo [4.4.0.1^2,5 . 1^{7, Ten}] Dodeca-3-
Ene, 8-methyl-8-ethoxycarbonyltetracycline
B [4.4.0.1^2,5 . 1^7,10] Dodeca-3-ene,
8-methyl-8-n-propoxycarbonyltetracyclic
B [4.4.0.1^2,5 . 1^7,10] Dodeca-3-ene,
8-methyl-8-i-propoxycarbonyltetracyclic
B [4.4.0.1^2,5. 1^7,10] Dodeca-3-ene,
8-methyl-8-n-butoxycarbonyltetracyclo
[4.4.0.1^2,5 . 1^7,10] Dodeca-3-ene, 8
-Methyl-8- (2'-methylpropoxy) carbonyl
Tetracyclo [4.4.0.1^2,5 . 1^{7, Ten}] Dodeca
3-ene, 8-methyl-8- (1'-methylpropoxy)
B) carbonyltetracyclo [4.4.0.1^2,5 . 1
^7,10] Dodeca-3-ene, 8-methyl-8-t-butoki
Cycarbonyltetracyclo [4.4.0.1^2,5 . 1
^7,10] Dodeca-3-ene, 8-methyl-8-cyclohexyl
Siloxycarbonyltetracyclo [4.4.0.1
^2,5 . 1^7,10] Dodeca-3-ene, 8-methyl-8-
(4'-t-butylcyclohexyloxy) carbonyl
Tetracyclo [4.4.0.1 ^2,5 . 1^7,10] Dodeca
3-ene, 8-methyl-8-phenoxycarbonyltet
Lacyclo [4.4.0.1^2,5 . 1^7,10] Dodeca-3-
Ene, 8-methyl-8-t-butoxycarbonyl methoxy
Cycarbonyltetracyclo [4.4.0.1^2,5. 1
^7,10] Dodeca-3-ene, 8-methyl-8-tetrahydride
Lofuranyloxycarbonyltetracyclo [4.4.
0.1^2,5 . 1^7,10] -3-dodecene, 8-methyl-8
-Tetrahydropyranyloxycarbonyltetracyclo
[4.4.0.1^2,5 . 1^7,10-3-dodecene,

8,9-di (methoxycarbonyl) tetra
Cyclo [4.4.0.1^2,5 . 1^7,10] Dodeca-3-D
, 8,9-di (ethoxycarbonyl) tetracyclo
[4.4.0.1^2,5 . 1^7,10 ] Dodeca-3-ene,
8,9-di (n-propoxycarbonyl) tetracyclo
[4.4.0.1^2,5 . 1^7,10] Dodeca-3-ene,
8,9-di (i-propoxycarbonyl) tetracyclo
[4.4.0.1^2,5 . 1 ^7,10] Dodeca-3-ene,
8,9-di (n-butoxycarbonyl) tetracyclo
[4.4.0.1^2,5 . 1^7,10] Dodeca-3-ene,
8,9-di (t-butoxycarbonyl) tetracyclo
[4.4.0.1^2,5 . 1^7,10] Dodeca-3-ene,
8,9-di (cyclohexyloxycarbonyl) tetra
Cyclo [4.4.0.1^2,5 . 1^7,10] Dodeca-3-D
, 8,9-di (phenoxycarbonyl) tetracyclo
[4.4.0.1^2,5 . 1^7,10] Dodeca-3-ene,
8,9-di (tetrahydrofuranyloxycarbonyl)
Tetracyclo [4.4.0.1^2,5 . 1^{7, Ten}] -3-do
Decene, 8,9-di (tetrahydropyranyloxycal
Bonyl) tetracyclo [4.4.0.1^2,5 . 1^7,10]
-3-Dodecene, 8,9-dicarboxyanhydride
Dotetracyclo [4.4.0.1^2,5 . 1^7,10] Dodeca
-3-ene and the like.

Among these norbornene-based monomers (α), 5-t-butoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-t-butoxycarbonylmethoxycarbonylbicyclo [2.2.1] hept-
2-ene, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8
-T- butoxycarbonyl methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.} [ ^1,7,10 ] dodec-3-ene and the like are preferred.

Acrylic Compound (β) Next, in the above formula (2), examples of the linear or branched alkyl group of R ² having 1 to 4 carbon atoms include a methyl group, an ethyl group and an n- Propyl group, i-propyl group,
Examples thereof include an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group.

Examples of the monovalent group having 20 or less carbon atoms which dissociates in the presence of the acid of R ² to generate an acidic functional group include, for example, the following substituted methyl group, 1-substituted ethyl group, 1-branch Examples thereof include an alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a cyclic acid-dissociable group. Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxyphenacyl Group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group,
Triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group,
Ethoxybenzyl group, ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-
Examples thereof include a propoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, and a t-butoxycarbonylmethyl group.

The 1-substituted ethyl group includes, for example, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group A 1-phenylethyl group, a 1,1-diphenylethyl group, a 1-methoxycarbonylethyl group,
1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl group, 1-n-butoxycarbonylethyl group, 1-t
-Butoxycarbonylethyl group and the like. Further, as the 1-branched alkyl group, for example,
1,1-dimethylpropyl group, 1-methylbutyl group,
Examples thereof include a 1,1-dimethylbutyl group.

The silyl group includes, for example, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propyl group. Examples thereof include a silyl group, a t-butyldimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. Examples of the germyl group include a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an i-propyldimethylgermyl group, a methyldi-i-propylgermyl group, and a trimethylgermyl group. -I-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group and the like. be able to. Further, as the alkoxycarbonyl group, for example, a methoxycarbonyl group,
An ethoxycarbonyl group, an i-propoxycarbonyl group,
and a t-butoxycarbonyl group.

Examples of the acyl group include acetyl, propionyl, butyryl, heptanoyl, hexanoyl, valeryl, pivaloyl, isovaleryl, laurylyl, myristoyl, palmitoyl, stearoyl, oxalyl. Group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoil group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group,
Fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, tenoyl group, nicotinoyl group, isonicotinoyl group , P-toluenesulfonyl group, mesyl group and the like.

The cyclic acid dissociable group includes, for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, 3-norbornyl, 2-isobornyl,
3-tricyclodecanyl group, 8-tricyclodecanyl group, 2-tetracyclodecanyl group, 1-adamantyl group, 1- (3-hydroxyadamantyl) group, 3-carboxytricyclodecanyl group, 8- Carboxytetracyclodecanyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiofuranyl, 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl Group, 3-tetrahydrothiophene-1,1-dioxide group, the following formulas (2-1) to
Examples include the group represented by (2-45) and substituted derivatives of these groups. Examples of the substituent in the cyclic acid dissociable group include a methyl group, an ethyl group, a hydroxyl group, and a cyano group.

[0034]

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[0035]

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R ² in the above formula (2) represents a hydrogen atom, a 1-methylpropyl group, a t-butyl group, a t-butoxycarbonylmethyl group, a 1-methoxyethyl group,
Ethoxyethyl group, 1-n-butoxyethyl group, t-butoxycarbonyl group, 1-adamantyl group, 1- (3-
Hydroxyadamantyl) group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, 4-methoxytetrahydrofuranyl group, and the above formulas (2-1), (2-5), (2-6) ),
Groups represented by the formulas (2-10), (2-19), and (2-20) are preferable, and particularly, a hydrogen atom, a t-butyl group, a 1-
A (3-hydroxyadamantyl) group represented by the above formula (2-
Preferred are groups represented by 1), Formula (2-5), Formula (2-6), Formula (2-10), Formula (2-19), Formula (2-20), and the like.

In the above formula (2), R ² is an i-propyl group, 1
-In the case of a monovalent group having 20 or less carbon atoms which dissociates in the presence of a methylpropyl group, a t-butyl group or an acid to form an acidic functional group, R ² is bonded to the carbonyloxy group in the unit; COOR ² forms an acid dissociable group that dissociates in the presence of an acid. Below, -C in these cases
OOR ^{2 is referred} to as “acid-labile group (ii)”.

The acrylic compound (β) is (meth) acrylic acid or a compound in which a hydrogen atom of a carboxyl group in (meth) acrylic acid is substituted with R ² (however, excluding a hydrogen atom).

Other Specific Monomers Other specific monomers suitably used as a starting material for the specific resin include norbornene-based compounds (α) and / or
Alternatively, other monomers used by copolymerizing with the acrylic compound (β) can be used. In particular, maleic anhydride and itaconic anhydride are preferred as copolymerization components of the norbornene-based compound (α). In particular,
Maleic anhydride has good copolymerizability with norbornene-based compounds, and by copolymerizing maleic anhydride, the molecular weight of the specific resin can be increased to a desired value.

Further, among other specific monomers, acid dissociation
Examples of the compound having a functional group include 5-hydroxy-
6-t-butoxycarbonylbicyclo [2.2.1]
Put-2-ene, 5-hydroxymethyl-6-t-buto
Xycarbonylbicyclo [2.2.1] hept-2-e
, 5-carboxy-6-t-butoxycarbonylbis
Clo [2.2.1] hept-2-ene, 8-hydroxy
-9-t-butoxycarbonyltetracyclo [4.4.
0.1^2,5 . 1^7,10 ] Dodeca-3-ene, 8-hydro
Xymethyl-9-t-butoxycarbonyltetracyclo
[4.4.0.1 ^2,5 . 1^7,10 ] Dodeca-3-ene,
8-carboxy-9-t-butoxycarbonyltetracy
Black [4.4.0.1^2,5 . 1^7,10 ] Dodeca-3-D
And other norbornene compounds; (meth) acrylonitrile
, Α-chloroacrylonitrile, crotonitrile,
Maleinnitrile, Humaronitrile, Mesaconitrile
, Citraconitrile, itaconitrile, etc.
Nitrile compound; maleimide, N-cyclohexylmale
Unsaturated imide compounds such as imide and N-phenylmaleimide
Objects and the like.

Other norbornene compounds having no acid-dissociable group include, for example, bicyclo [2.2.1] hept-2-ene (norbornene) and 5-methylbicyclo [2.2.1] hept- 2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] Hept-2-ene, 5-
Carboxybicyclo [2.2.1] hept-2-ene,
5,6-dicarboxybicyclo [2.2.1] hept-
2-ene,

Tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-methyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene,
8-ethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene,
8-fluoromethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene, 8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8
-Pentafluoroethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodeca-3-ene,

8-Hydroxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodec-3-ene, 8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene,
8,9-dicarboxytetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodeca-3-ene,

8,8-difluorotetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8, 9
-Difluorotetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodec-3-ene, 8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene,
8,8,9-Tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene,
8,8,9,9-Tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8,9-difluoro-8,
9-bis (trifluoromethyl) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8,
8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-
Ene, 8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-fluoro-8
- pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodec-3-ene, 8,9-difluoro-8-
Heptafluoroisopropyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodeca-3-ene,

8-chloro-8,9,9-trifluorote
Toracyclo [4.4.0.1^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8,9-dichloro-8,9-bis (trifur
(Oromethyl) tetracyclo [4.4.0.1^2,5 . 1
^7,10 ] Dodeca-3-ene, 8- (2,2,2-trif)
Fluorocarboxyethyl) tetracyclo [4.4.0.
1 ^2,5 . 1^7,10 Dodeca-3-ene, 8-methyl-8
-(2,2,2-trifluorocarboxyethyl) tetra
Lacyclo [4.4.0.1^2,5 . 1^7,10 ] Dodeca-3
-Ene and the like.

Other specific monomers having no acid dissociable group include, for example, cyclobutene, cyclopentene, cyclooctene, 1,5-cyclooctadiene, 1,5,9
-Cyclododecatriene, 5-ethylidene norbornene, dicyclopentadiene, tricyclo [5.2.
1.0 ^2,6 ] deca-8-ene, tricyclo [5.2.
1.0 ^2,6 ] deca-3-ene, tricyclo [4.4.
0.1 ^2,5 ] undec-3-ene, tricyclo [6.
2.1.0 ^1,8 ] undec-9-ene, tricyclo [
6.2.1.0 ^1,8 ] undec-4-ene, tetracyclo [4.4.0.1 ^2,5 . ^17,10 . 0 ^1,6 ] dodeca-3-ene, 8-methyltetracyclo [4.4.0.1
^2,5 . ^17,10 . 0 ^1,6 ] dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,12 ]
Dodeca-3-ene, 8-ethylidenetetracyclo [4.
4.0.1 ^2,5 . ^17,10 . 0 ^1,6 ] dodeca-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^{9, 13]} pentadeca-4-ene, pentacyclo [7.
4.0.1 ^2,5 . ^19,12 . 0 ^8,13] pentadeca-3
Compounds having an alicyclic skeleton such as ene; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and n-butyl (meth) acrylate Linear alkyl esters; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- (meth) acrylate
Hydroxyalkyl (meth) acrylates such as hydroxypropyl; methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, α-
Α-hydroxymethyl acrylates such as n-propyl hydroxymethyl acrylate and n-butyl α-hydroxymethyl acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesacone Aliphatic unsaturated carboxylic acids such as acids; 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3- (meth) acrylate
Free carboxyl group-containing esters of aliphatic unsaturated carboxylic acids such as carboxypropyl and 4-carboxybutyl (meth) acrylate; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; (meth) acrylamide, N, N -Dimethyl (meth) acrylamide,
Unsaturated amide compounds such as crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide; N-vinyl-ε-caprolactam;
Other nitrogen-containing vinyl compounds such as N-vinylpyrrolidone, vinylpyridine and vinylimidazole; and ethylene.

Further, among other specific monomers, examples of polyfunctional monomers include methylene glycol di (meth) acrylate and ethylene glycol di (meth) acrylate.
Acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzenedi (meth) acrylate, 1,3-bis (2-hydroxypropyl) benzenedi (meth) acrylate, 1, 2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth)
Acrylate, tricyclodecanyl dimethylol di (meth) acrylate and the like can be mentioned.

Among these other specific monomers, bicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene and 5-carboxybicyclo [2. 2.1] Hept-2-ene, 5-hydroxy-6-t-butoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-carboxy-6-t-
Butoxycarbonylbicyclo [2.2.1] hept-2
-Ene, tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene,
8-carboxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-hydroxy-9-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodec-3-ene, 8-carboxy-9-t
-Butoxycarbonyltetracyclo [4.4.0.1
^2,5 . [ ^1,7,10 ] dodec-3-ene and the like are preferred.

[Alicyclic Resin] As the alicyclic resin to be treated by the method of the present invention, the above-mentioned specific resin is preferable, and a film having a thickness of 0.4 μm is 100 to 300 μm.
60% / μ transmittance for radiation in the wavelength range of nm
m or more, preferably 65% or more, particularly preferably 70%
The above resins are desirable. In the present invention, preferred specific resins include, for example, a copolymer having a repeating unit (I) represented by the following formula (1 ′) and / or a repeating unit (II) represented by the following formula (2 ′) (hereinafter, referred to as “ Copolymer (A
1) ". ).

[0050]

Embedded image

[In the formula (1 '), A, B, X, Y and n represent A, B, X and
It is synonymous with Y and n. ]

[0052]

Embedded image

[In the formula (2 '), R ¹ and R ²
Has the same meaning as R ¹ and R ² in the above formula (2), respectively. ]

The repeating unit (I) is a repeating unit derived from the above-mentioned norbornene compound (α), and the repeating unit (II) is a repeating unit derived from the above-mentioned acrylic compound (β). When the copolymer (A1) does not have the repeating unit (I) and the repeating unit (II) does not have the acid dissociable group (ii), the copolymer (A1) has the above-mentioned acid. It is necessary to have a repeating unit derived from another specific monomer having a dissociable group.

In the present invention, preferred examples of the resin (A1) include a resin having a repeating unit (I) and a repeating unit derived from maleic anhydride, a repeating unit (I), and a repeating unit derived from maleic anhydride. And a resin having a repeating unit (II), a repeating unit derived from a norbornene-based compound other than the repeating unit (I), a repeating unit derived from maleic anhydride, and a repeating unit (II)
And the like.

Specific resins include, for example, the following (a) to (e)
And the like. (A) A method in which a norbornene-based compound (α) is subjected to radical polymerization, preferably together with maleic anhydride in the presence of another monomer, if necessary. (B) ring-opening (co) of the norbornene-based compound (α) together with another unsaturated alicyclic compound capable of ring-opening copolymerization in some cases;
Method of polymerizing (c) A method of radically polymerizing an acrylic compound (β) in the presence of another monomer, if necessary. (D) A method in which a norbornene-based compound (α) and an acrylic compound (β) are subjected to radical polymerization, preferably together with maleic anhydride, in the presence of another monomer, if necessary. (E) The acid dissociable groups in the resin obtained by the methods (a) to (d) are partially hydrolyzed and / or
Or a method of introducing a carboxyl group by solvolysis.

The weight average molecular weight (hereinafter also referred to as “Mw”) of the specific resin in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 3,000.
0 to 300,000, preferably 3,000 to 20
000. Also, Mw and GP in a specific resin
C, the number average molecular weight in terms of polystyrene (hereinafter referred to as “M
n) is usually 1 to 1 (Mw / Mn).
0, preferably 1 to 5.

[Organic Solvent] In the method of the present invention, the alicyclic polymer is passed through a functional filter medium in the form of an organic solvent solution. When passing the monomer through the functional filter medium,
It may be used as it is, or may be used after being diluted with an organic solvent. The organic solvent used for preparing the solution is not particularly limited as long as it can dissolve the alicyclic polymer. For example, n-pentane, isopentane, n-hexane, isohexane, n-heptane , Isoheptane,
Aliphatic hydrocarbon solvents such as 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, propylbenzene, isopropylbenzene, diethylbenzene, Aromatic hydrocarbon solvents such as isobutylbenzene, triethylbenzene, diisopropylbenzene, and amylnaphthalene;

Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, s
ec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, s
ec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec- Monoalcohol solvents such as tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol; ethylene Glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2-methyl-2,4
-Pentanediol, pentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2
Polyhydric alcohol solvents such as -ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin;

Acetone, methyl ethyl ketone, methyl
n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, ethyl butyl ketone, methyl hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methyl cyclohexanone, 2,4-pentane Ketone solvents such as dione, acetonylacetone, acetophenone, and pention; ethyl ether, isopropyl ether, n-butyl ether, hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolan, 4-
Methyl dioxolane, dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl Butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol mono-n-
Ether solvents such as hexyl ether, ethoxytriglycol, tetraethylene glycol dibutyl ether, monopropylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol monopropyl ether, tetrahydrofuran and 2-methyltetrahydrofuran;

Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate;
I-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate,
Methylpentyl acetate, 2-ethylbutyl acetate, 2-acetic acid
Ethylhexyl, benzyl acetate, cyclohexyl acetate,
Methyl cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol monobutyl ether, Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-pentyl propionate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, Ethyl lactate, n-butyl lactate, n-lactic acid
Ester solvents such as pentyl, diethyl malonate, dimethyl phthalate and diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N- Nitrogen compound solvents such as dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene,
Sulfur compound solvents such as tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone; 2-heptanone, 3-heptanone, 4-heptanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate , Ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate,
Examples thereof include ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, N-methylformanilide, ethyl benzoate, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.

The concentration of the alicyclic polymer in the organic solvent solution is usually adjusted to 70% by weight or less, preferably 20% by weight.
５０50% by weight. If the concentration is too low and the viscosity is high, a very high pressure is required to pass the solution, which is not suitable.

[Functional Filter Material] As the filter material used in the method of the present invention, a material which exerts a zeta potential on an organic solvent solution to be filtered is selected. Examples of such a functional filter medium include a conventional filter medium such as cotton, pulp, cellulose, polyester, diatomaceous earth, perlite, activated carbon, and zeolite to which a cationic charge control agent is added. Preferred among these are cotton, cellulose,
Polyester, activated carbon and zeolite.

A cationic charge is imparted to the filter medium by the cationic charge control agent, and a zeta potential is generated between a charged substance of the organic solvent solution, that is, a metal component, which passes through the filter medium during the filtration process. Examples of the cationic charge control agent include a reaction product of dicyandiamide, monoethanolamine and formaldehyde described in US Pat. No. 2,802,820, an aminotriazine resin described in US Pat. No. 2,839,506, and US Pat.
No. 007113, a melamine-formaldehyde cationic resin, a resin obtained by reacting N, N'-diethanolpiperazine, melamine, formalin and glycerin phthalate described in JP-B-36-20045, And polyamidopolyamine epichlorohydrin cation resin described in JP-A-63-17486. Among them, polyamide polyamine epichlorohydrin cation resin is preferable because it gives a stable cation charge.

The above-mentioned JP-B-63-17486 discloses that a polyamide polyamine epichlorohydrin cation resin is used as a cationic charge controlling agent, and cellulose,
A method for producing a filter comprising a filter material obtained by converting diatomaceous earth and perlite into a functional filter material is described. The thickness of the above-mentioned functional filter medium is preferably 10 cm or less, particularly preferably 0.1 to 5 cm. The thickness of this functional media is
It may be obtained by laminating a commercially available functional filter medium.

One preferred form of the functional filter medium used in the present invention is one that is used together with an ion exchanger and / or a chelate former. Here, the ion exchanger and / or the chelate former may be a polymer,
For example, styrene-based polymers, acrylic-based polymers, methacryl-based polymers, vinyl alcohol-based polymers, polyesters, cellulose and other polymers into which a functional group having an ion exchange function or a chelate-forming function is introduced. . The form of these ion exchangers or chelate formers is not particularly limited, and may be any form such as a granular form, a fibrous form, a porous film form or a porous film form.
In the following description, these porous films and porous films are simply referred to as films and films.
Usually, the ion exchange resin and the chelate resin are used in a granular form.

More specifically, as the ion exchanger,
Granular, fibrous, film-like or film-like materials composed of a strongly acidic cation exchanger, a weakly acidic cation exchanger, a strongly basic anion exchanger, or a weakly basic anion exchanger are used. Here, examples of the strongly acidic cation exchanger include those obtained by sulfonating a styrene polymer cross-linked with divinylbenzene and those obtained by carboxylating a methacrylic polymer. Examples of the weakly acidic cation exchanger include divinylbenzene. And a copolymer of acrylic acid and methacrylic acid. Examples of the strongly basic anion exchanger include, for example, those obtained by aminomethylating a styrene polymer cross-linked with divinylbenzene and then quaternizing the styrene polymer. Examples of the weakly basic anion exchanger include:
For example, aminomethylated styrene polymer cross-linked with divinylbenzene, or acrylamide polymer having an aminomethyl group cross-linked with divinylbenzene is exemplified.

Examples of the chelate former include a resin in which a group having an iminodiacetic acid structure is introduced into a styrene polymer crosslinked with divinylbenzene, or a group having a polyamine structure is introduced into a styrene polymer crosslinked with divinylbenzene. Examples thereof include granular, fibrous, film-like or film-like materials such as resin. These various ion exchangers or chelate formers are not only one kind,
Two or more types may be included in the same filter.

The above-mentioned ion exchanger and / or chelate former together form a filter. At this time, the ion exchanger and / or chelate former may be uniformly mixed with the above-mentioned functional filter medium. Layer and the functional filter medium layer may be arranged or joined adjacently, or two layers arranged or joined in this way may be partially mixed at the boundary. .

The pore size of the above-mentioned functional filter medium or formed by the functional filter medium is usually 0.05 to 10.0 μm.
m, and preferably 0.1 to 1.0 μm. In a functional filter medium, charged particles present in the liquid are adsorbed by the functional filter medium due to a potential difference generated when the functional filter medium is passed through, so metal impurities smaller than the pore size of the functional filter medium are also included in the functional filter medium. Be captured. Some of the trace metal is present in the form of microparticles, such as microgels, which are captured by filters that generate zeta potential. On the other hand, ion exchangers and chelate formers mainly capture free ions in the liquid. As a result, various metals having different forms can be widely removed by the method of the present invention. Therefore, the metal component contained in the alicyclic polymer can be reduced more efficiently by using the ion exchanger and / or the chelate-forming agent together.

As the functional filter used in the method of the present invention, commercially available filters can be widely used. For example, as a filter containing an ion exchange resin or a chelate resin and generating a zeta potential, a filter manufactured by Cuno Corporation As the zetaplus SH series (trade name) and a filter that does not contain an ion exchange resin or a chelate resin and generates a zeta potential, zetaplus, GN series, and LA series of the company are preferably used.

The rate at which the alicyclic polymer solution is passed through the filter medium has almost no effect on the metal separation efficiency, and may be in the range of 0.0001 to 1000 kg / (m ² · min).

If the temperature at which the liquid is passed through the filter is too high, there is a possibility that elution, deterioration, decomposition of the solvent, etc. of the filter medium may occur. On the other hand, if the temperature is too low, the viscosity of the resin in the solution increases, making it very difficult to pass the solution. Therefore, the temperature range is 0 to 80 ° C, preferably 10 to 50 ° C.
C is a suitable range.

[0074]

EXAMPLES In order to explain the present invention in more detail, examples and comparative examples are shown below, but the present invention is not particularly limited by these examples and comparative examples.

Example 1 As the alicyclic polymer, the following formulas (i-1) and (i-2)
And each of the repeating units represented by (i-3) is 3
A resin solution having a concentration of 10% by weight obtained by dissolving a copolymer having 0 mol%, 30 mol%, and 40 mol% in tetrahydrofuran was treated. As a filter medium, a zeta-plus GN filter manufactured by Cuno Inc. (material: cellulose, diatomaceous earth, perlite, cationic charge control agent; polyamide polyamine epichlorohydrin, on which zeta potential acts but does not contain an ion exchanger and / or a chelate former) Resin, 47 mm diameter, 3 mm thick circular shape)
One loaded in a stainless steel column having a length of 30 mm and a length of 30 mm was used. 500 ml of the resin solution was passed through the filter medium at room temperature at a flow rate of 9.63 × 10 ⁻³ m / s. When the metal concentrations of the solution after the treatment and the solution before the treatment were measured by an atomic absorption spectrometer, sodium was 140 ppb before the treatment,
Iron was 71 ppb, but after the treatment, sodium was 40 ppb and iron was 45 ppb, and the metal had been removed to a level suitable for use as a resist.

[0076]

Embedded image

Example 2 The functional filter medium (diameter 47 mm, thickness 3) used in Example 1
mm circular shape) were stacked in series, and processed under the same conditions as in Example 1 except that they were used in the same column as used in Example 1. The metal concentrations after the treatment were 20 ppb for sodium and 25 ppb for iron.

Example 3 A functional filter medium containing a powdery strongly acidic cation exchange resin as an ion exchanger and / or a chelate-forming agent in a cationic charge control agent as a filter medium on which zeta potential acts, a Zeta Plus SH filter manufactured by Kuno (Material: cellulose, diatomaceous earth, perlite, cationic charge control agent; polyamide polyamine epichlorohydrin resin, cation exchange resin; made of sulfonated polystyrene cross-linked with divinylbenzene, 47 mm in diameter, 3 mm thick circular shape) A solution of an alicyclic polymer in methyl isoamyl ketone was treated in the same manner as in Example 1 except that 47 mm and a circular shape having a thickness of 3 mm were used. The metal concentration after treatment is
Sodium was 11 ppb and iron was 23 ppb.

Example 4 A solution of an alicyclic polymer in methyl isoamyl ketone was treated in the same manner as in Example 1 except that the two functional filter media used in Example 3 were used in tandem. The metal concentrations after the treatment were 8 ppb for sodium and 11 ppb for iron.

Example 5 Instead of an alicyclic polymer, 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene (62.1 g), methyl adamantyl acrylate (103.4 g) as an acrylic compound, and maleic anhydride (34.5 g) as another monomer.
Was dissolved in 200 g of tetrahydrofuran, and a mixed solution of monomers was treated in the same manner as in Example 1. Using the monomer after the treatment, an alicyclic polymer having the same composition as that used in Example 1 was synthesized using 2,2′-dimethylazobis (2-methylpropionate) as a polymerization initiator, and a metal was synthesized. When the concentration was measured, sodium was 15p
pb and iron were 20 ppb.

Comparative Example 1 A 100 ml plastic bottle containing 5 ml of a commercially available strongly acidic cation exchange resin (Amberlyst 15 from Organo: styrene sulfonic acid-divinylbenzene copolymer, shape: granular) was used. 10 g of a solution of the same alicyclic polymer in methyl isoamyl ketone as the treated one was added, and the bottle was shaken for 1 hour. The metal concentrations in the solution after shaking were 80 ppb for sodium and 60 ppb for iron.

Comparative Example 2 The amount of the strongly acidic cation exchange resin in Comparative Example 1 was changed to 10 m
The norbornene-based polymer was treated in the same manner as in Comparative Example 1 except that the amount was changed to 1. The metal concentration in the solution after the treatment was 60 ppb for sodium and 55 ppb for iron.

Comparative Example 3 A metal removal treatment was carried out in the same manner as in Comparative Example 1 except that a mixture of monomers used in Example 5 was used, and an alicyclic group was produced in the same manner as in Example 5 using the monomer. Polymerization of the base polymer was carried out. When the metal concentration of the obtained alicyclic polymer was measured, sodium was 45 ppb and iron was 50 ppb.

[0084]

According to the method of the present invention, metals such as alkali metals and heavy metals are efficiently removed from an alicyclic polymer and a monomer used in the synthesis of the polymer by a simple operation of filtration. can do. In particular, in a form in which an ion exchanger and / or a chelate-forming agent are used in combination with a functional filter medium on which zeta potential acts, the metal removal life of the filter medium is long and more efficient and economical use is effective. Since the norbornene-based polymer treated by the method of the present invention has an extremely low metal content, it is suitable as a raw material of a radiation-sensitive resin composition used as a photoresist in the field of electronics such as semiconductor devices.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08F 32/00 C08F 32/00 F term (reference) 4D017 AA03 BA11 CA03 CA05 CA13 CA17 CB05 DA01 EA03 4D019 AA03 BA03 BA06 BA12 BA13 BB03 BB08 BB12 BC03 BC04 BD01 CB06 4J011 AC05 4J100 AK32Q AL08R AR09P AR11P BA03P BA03R BA04P BA15P BA40R BA72P BC08R BC09R BC12R GA17 GC35 JA37

Claims (3)

[Claims] 1. A method for removing a metal from an alicyclic polymer, comprising: passing a monomer through a filter medium on which zeta potential acts; and synthesizing an alicyclic polymer using the monomer. Method. 2. A method for removing metals from an alicyclic polymer, which comprises passing a solution of an alicyclic polymer in an organic solvent through a filter medium on which zeta potential acts. 3. The metal removing method according to claim 1, wherein the filter medium on which the zeta potential acts is used together with an ion exchanger and / or a chelate former.