JP2003342319A - Method of removing metal contained in alicyclic hydrocarbon polymer, and radiation-sensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a purification process by which a metal contained in alicyclic hydrocarbon polymers as an impurity is removed and to provide a radiation-sensitive resin composition of a high performance photoresist which is composed of the purified polymer. <P>SOLUTION: 1. The method of removing a metal contained in the alicyclic hydrocarbon polymer comprises the following processes: a process of coagulating the alicyclic hydrocarbon polymer by mixing an acid-added organic solvent solution of the polymer with its poor solvent, and a process of dissolving the coagulated polymer into a water-insoluble organic solvent, followed by bringing the solution into contact with an acidic hot water solution, extracting the metal contained therein. 2. The radiation-sensitive composition contains the alicyclic hydrocarbon polymer purified by the above-mentioned processes to remove the contained metal, and a radiation-sensitive acid generator. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for removing a metal contained in alicyclic hydrocarbon polymers and a radiation-sensitive composition.

[0002]

2. Description of the Related Art Alicyclic hydrocarbon polymers are very useful substances as photoresist materials and have many applications in the electronics field. In recent years, the structures of these devices in the electronics field have become finer and finer, and it has become necessary to suppress the content of metal impurities in the materials used to improve the electrical characteristics to a significantly low level. Is coming. Therefore, even when the alicyclic hydrocarbon polymer is used as a material in the electronics field, it is important that the metal impurities are suppressed to a very small amount. As a method for removing and reducing metal impurities contained in conventionally known alicyclic hydrocarbon-based polymers,
There is a method of adsorbing metal ions on an ion exchange resin.
However, this method is difficult to handle because many ion exchange resins are granular, and after adsorbing metal ions, reverse regeneration treatment with an alkaline (or acidic) solution, washing with water, and acid (or There are problems that regeneration treatment with an (alkaline) solution and many processes are required, and that the metal removing ability is not sufficient.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for highly efficiently reducing metal impurities contained in an alicyclic hydrocarbon polymer, and to provide a metal by the method. It is intended to provide a radiation-sensitive composition using a purified alicyclic hydrocarbon-based polymer in which impurities are reduced.

[0004]

Means for Solving the Problems As a result of research to solve the above-mentioned problems of the conventional techniques, the present inventors have found that the alicyclic hydrocarbon-based polymer is purified and extracted by coagulation. The present invention has been completed by finding that the above problems can be solved by carrying out purification. That is, the present invention is a step of mixing an alicyclic hydrocarbon-based polymer in an organic solvent solution with a poor solvent for the alicyclic hydrocarbon-based polymer and an acid to coagulate the alicyclic hydrocarbon-based polymer. (Hereinafter, also referred to as “step I”) and a step of mixing the solidified alicyclic hydrocarbon-based polymer, a water-insoluble organic solvent, an acid and water to extract a contained metal (hereinafter, also referred to as “step II”) The present invention relates to a method for removing a metal contained in an alicyclic hydrocarbon-based polymer, which comprises:

The alicyclic hydrocarbon polymer used in the present invention has a repeating unit represented by the following formula (2), the following formula (3) or the following formula (4). preferable. Among these polymers, a polymer having a repeating unit represented by the following formula (2) is usually represented by the following formula (1)
Obtained by polymerizing or copolymerizing the monomer represented by the formula (I) with a metal compound such as Ni or Pd as a catalyst, and having at least one repeating unit represented by the following formula (3) and the following formula (4) The polymer is usually obtained by copolymerizing a monomer represented by the following formula (1) and carbon monoxide with a metal compound such as Ni or Pd as a catalyst.

[0006]

[Chemical 5] (In the formula (2), A and B are the same or different and each is a hydrogen atom,
A monovalent acid having 20 or less carbon atoms which dissociates in the presence of a monovalent linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group or an acid to produce an acidic functional group. Represents a dissociable group, wherein at least one of A and B is a monovalent acid dissociable group having 20 or less carbon atoms, or A and B are carboxylic acid anhydrides bonded to each other to form an integral unit. Represents a ring, X and Y are the same or different and represent a hydrogen atom or a monovalent linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. )

[0007]

[Chemical 6] (In the formula (3), A, B, X, Y, and n are as defined in relation to the formula (2).)

[0008]

[Chemical 7] (In the formula (4), A, B, X, Y, and n are as defined in relation to the formula (2).)

[0009]

[Chemical 8] (In the formula (1), A, B, X, Y, and n are as defined in relation to the formula (2).) The present invention also provides an alicyclic hydrocarbon purified by the method for removing a contained metal. The present invention relates to a radiation-sensitive composition comprising a polymer and a radiation-sensitive acid generator.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. 1. About the method for removing the metal contained in the alicyclic hydrocarbon-based polymer <Alicyclic hydrocarbon-based polymer> The alicyclic hydrocarbon-based polymer used in the present invention is, for example, represented by the above formula (1). A polymer having a repeating unit represented by the above formula (2) obtained by polymerizing or copolymerizing a monomer represented by the above formula, or the above formula (copolymerization of the monomer represented by the above formula (1) and carbon monoxide ( Examples thereof include polymers having the repeating units represented by 3) and (4). These alicyclic hydrocarbon-based polymers are usually polymers polymerized by using a metal compound such as Ni or Pd as a catalyst, and the metal derived from these catalysts is contained in the alicyclic hydrocarbon-based polymer. Remains in. In addition, Fe and N not derived from the catalyst
Even metals such as a, K, and Cu are contained as impurities in the alicyclic hydrocarbon-based polymer.

The monomer represented by the above formula (1) and having an acid dissociable group is, for example, one having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group, It is converted into a dissociative group, and as a result, the polymer or copolymer of the monomer can be made insoluble in alkali or hardly soluble in alkali. In the above formula, A and / or B is a monovalent acid dissociable group having 20 or less carbon atoms (hereinafter referred to as "acid dissociable group (i)").
And A and / or B are, for example,
Examples thereof include a group represented by the following formula (5).

[0012]

Embedded image ^{_{- (CH 2) X COOR 1}} (5) ( In the formula, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group having 1 to 10 carbon atoms, alkoxycarbonylmethyl Group, alkoxycarbonylethyl group, alkoxycarbonylpropyl group (however, the number of carbon atoms of the alkoxy group is 1 to 10), tetrahydrofuranyl group, tetrahydropyranyl group or triacylsilyl group
(However, the number of carbon atoms of the alkyl group is 1 to 4), and x is an integer of 0 to 4. )

Of the acid dissociable groups (i), the group represented by the formula (5) is, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxy group, when x = 0. Carbonyl 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-butylcyclohexyloxy A linear, branched or cyclic alkoxycarbonyl group such as a carbonyl group, a cycloheptyloxycarbonyl group or a cyclooctyloxycarbonyl group;

Aryloxycarbonyl group such as phenoxycarbonyl group, 4-t-butylphenoxycarbonyl group, 1-naphthylcarbonyl group; aralkyloxycarbonyl group such as benzyloxycarbonyl group, 4-t-butylbenzyloxycarbonyl group; methoxy Carbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group, n-propoxycarbonylmethoxycarbonyl group, i-propoxycarbonylmethoxycarbonyl group,
a linear, branched or cyclic alkoxycarbonylmethoxycarbonyl group such as an n-butoxycarbonylmethoxycarbonyl group, a 2-methylpropoxycarbonylmethoxycarbonyl group, a 1-methylpropoxycarbonylmethoxycarbonyl group, a t-butoxycarbonylmethoxycarbonyl group; Etc. can be mentioned.

Similarly, when n = 1, for example, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-
Propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, 2-methylpropoxycarbonylmethyl group, 1-methylpropoxycarbonylmethyl group, t-butoxycarbonylmethyl group, cyclohexyloxycarbonylmethyl group, 4- t-
Linear, branched or cyclic alkoxycarbonylmethyl group such as butylcyclohexyloxycarbonylmethyl group; aryloxycarbonylmethyl group such as phenoxycarbonylmethyl group, 1-naphthyloxycarbonylmethyl group; benzyloxycarbonylmethyl group, 4- aralkyloxycarbonylmethyl group such as t-butylbenzyloxycarbonylmethyl group; and the like.

Similarly, when n = 2, for example, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group,
2-n-propoxycarbonylethyl group, 2-i-propoxycarbonylethyl group, 2-n-butoxycarbonylethyl group, 2- (2-methylpropoxy) carbonylethyl group, 2- (1
-Methylpropoxy) carbonylethyl group, 2-t-butoxycarbonylethyl group, 2-cyclohexyloxycarbonylethyl group, 2- (4-butylcyclohexyloxycarbonyl) ethyl group, or other linear, branched or cyclic 2-
Alkoxycarbonylethyl group; 2-aryloxycarbonylethyl group such as 2-phenoxycarbonylethyl group, 2- (1-naphthyloxycarbonyl) ethyl group, 2-benzyloxycarbonylethyl group, 2- (4-t-butylbenzyl) 2-aralkyloxycarbonylethyl group such as (oxycarbonyl) ethyl group; and the like.

In the acid dissociable group (i), the group represented by the formula (5) is, in addition to the above, 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, and 2-hydroxy- group. 2,2-di (trifluoromethyl) ethoxycarbonyl group and the like can be mentioned. Of these acid-dissociable groups (i), groups of the general formula (5) in which x = 0 are preferable, and more preferable are methoxycarbonyl group, ethoxycarbonyl group, 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, cyclopentyloxy Carbonyl group, cyclohexyloxycarbonyl group, 1-methylcyclopentyloxycarbonyl group,
Examples include t-butoxycarbonylmethoxycarbonyl group.

In the formula (1), the linear or branched alkyl group having 1 to 4 carbon atoms of X or Y is, for example, methyl group, ethyl group, n-propyl group,
i-propyl group, n-butyl group, 2-methylpropyl group, 1-
Methylpropyl group, and a t- butyl group, especially, a hydrogen atom, methyl group is preferred. further,
In the formula (1), n is preferably 0 or 1.

Specific examples of the compound of the formula (1) in which n is 0 include 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-en, 5
-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonyl-5-trifluoromethylbicyclo [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- (2-tetrahydrofuranyl) oxycarbonylbicyclo [2.2.1] hept-2-ene, 5- (2-tetrahydropyranyl) oxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyanobicyclo [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- (2-
Tetrahydrofuranyl) oxycarbonylbicyclo [2.2.
1] hept-2-ene, 5-methyl-5- (2-tetrahydropyranyl) oxycarbonylbicyclo [2.2.1] hept-2-ene, 5
-Methyl-5-cyanobicyclo [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 [(2-tetrahydrofuranyl) oxycarbonyl] bicyclo [2.2.1] Hept-2-
Ene, 5,6-di [(2-tetrahydropyranyl) oxycarbonyl] bicyclo [2.2.1] hept-2-ene, 5,6-dicarboxyanhydride bicyclo [2.2.1] hept-2-ene, Five-
Hydroxy-6-t-butoxycarbonylbicyclo [2.2.1]
Hept-2-ene, 5-hydroxymethyl-6-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-carboxy
Examples include -6-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene.

Among norbornene type monomers, general
Specific examples of the compound of the formula (1) in which n is 1 include 8-meth
Xycarbonyltetracyclo [4.4.0.1^2,5.1^7,10] Dodeca
-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1
^2,5.1^7,10] Dodeca-3-ene, 8-n-propoxycarbonyl
Tetracyclo [4.4.0.1^2,5.1^7,10] Dodeca-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] Dodeca-3-ene, 8- (2'-methylpro
(Poxy) carbonyltetracyclo [4.4.0.1^2,5.1^7,10] Do
Deca-3-ene, 8- (1'-methylpropoxy) carbonyl tet
Racyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-ene, 8-t-but
Xycarbonyltetracyclo [4.4.0.1^2,5.1^7,10] Dodeca
-3-ene, 8-cyclohexyloxycarbonyltetrasi
Black [4.4.0.1^2,5.1^7,10] Dodeca-3-ene, 8- (4'-t-butyl
Cyclohexyloxy) carbonyltetracyclo [4.4.
0.1^2,5.1^7,10] Dodeca-3-ene, 8-phenoxycarbonyl
Tetracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-ene, 8-t-
Butoxycarbonyl methoxycarbonyl tetracyclo
[4.4.0.1 ^2,5.1^7,10] Dodeca-3-ene, 8- (2-tetrahydro
Furanyl) oxycarbonyltetracyclo [4.4.0.1^2,5.1
^7,10] -3-Dodecene, 8- (2-tetrahydropyranyl) oxy
Carbonyl tetracyclo [4.4.0.1^2,5.1^7,10] -3-Dodese
8-cyanotetracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3
-En,

8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .8] 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-methyl-
8-i-propoxycarbonyl tetracyclo [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'-methyl-propoxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl-8- (1'
Methylpropoxy) carbonyltetracyclo [4.4.0.
1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl -8-t-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl -8-Cyclohexyloxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] Dodeca-3-ene, 8-methyl-
8- (4'-t-butyl cyclohexyloxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methyl -
8 phenoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1
^7,10 ] Dodeca-3-ene, 8-methyl-8-t-butoxycarbonylmethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1, ^7,10 ]
Dodeca-3-ene, 8-methyl-8- (2-tetrahydrofuranyl)
Oxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] Dodeca-3-ene, 8-methyl-8- (2-tetrahydropyranyl) oxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] dodeca-3
- ene, 8-methyl-8-cyano-tetracyclo [4.4.0.1 ^{2, 5} .1
^7,10 ] dodeca-3-en,

8,9-di (methoxycarbonyl) tetracyclo
[4.4.0.1 ^2,5 .1 ^7,10 ] Dodeca-3-ene, 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) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] Dodeca-3-ene, 8,9-di (phenoxycarbonyl) tetracyclo [4.4.0.1 ^{2, 5} .1 ^{7, 10} ] Dodeca-3-ene, 8,9-di [(2-tetrahydrofuranyl) oxycarbonyl] tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] Dodeca-3-ene, 8,9-di [( 2-Tetrahydropyranyl) oxycarbonyl] tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8,
9-dicarboxyanhydride tetracyclo [4.4.0.1
^2,5 .1 ^7,10 ] dodeca-3-ene, 8-hydroxy-9-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3
- ene, 8-hydroxymethyl -9-t-butoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] dodeca-3-ene, 8-carboxy -9-t-butoxycarbonyl tetracyclo [4.4.
0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene and the like.

Of these norbornene-based monomers, the special
And 5-t-butoxycarbonylbicyclo [2.2.1] hept-2
-Ene, 5-t-butoxycarbonylmethoxycarbonylbi
Cyclo [2.2.1] hept-2-ene, 5-hydroxy-6-t-but
Xycarbonylbicyclo [2.2.1] hept-2-ene, 5-cal
Boxy-6-t-butoxycarbonylbicyclo [2.2.1] hep
To-2-ene, 8-t-butoxycarbonyltetracyclo [4.
4.0.1^2,5.1^7,10] Dodeca-3-ene, 8-t-butoxycarbo
Nylmethoxycarbonyltetracyclo [4.4.0.1 ^2,5.1
^7,10] Dodeca-3-ene, 8-hydroxy-9-t-butoxycal
Bonyl tetracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-d
8-carboxy-9-t-butoxycarbonyltetracycline
B [4.4.0.1^2,5.1^7,10] Dodeca-3-enetcIs preferred.

<Other Monomers> The alicyclic hydrocarbon-based polymer in the present invention includes not only the homopolymer of the monomer represented by the above formula (1) but also the one represented by the formula (1). Among these monomers, a copolymer of two or more different monomers, or a copolymer of another monomer different from the monomer represented by the formula (1) is the above formula ( 3) and (4) are included together with the copolymer with carbon monoxide. Here, the following can be mentioned as other monomers for obtaining a copolymer from two or more monomers including the monomer represented by the formula (1).

Among the monomers to be copolymerized, examples of the monofunctional monomer having no acid-labile group include bicyclo [2.
2.1] Hept-2-ene (norbornene), 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- [2-hydroxy-2- 2-di (trifluoromethyl)] bicyclo [2.2.1] hept-2-ene, 5- [2-t-butoxy-2,2-
Di (trifluoromethyl) ethyl carbonoxy] bicyclo [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] Dodeca-3
-Ene, 8-methyltetracyclo [4.4.0.1^2,5.1^7,10] Dode
Ca-3-ene, 8-ethyltetracyclo [4.4.0.1^2,5.1^7,10]
Dodeca-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] Dodeca-3-ene, 8-difluoromethyi
Rutetracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-en, 8-
Trifluoromethyl tetracyclo [4.4.0.1^2,5.1^7,10] Do
Deca-3-ene, 8-pentafluoroethyl tetracyclo [4.
4.0.1^2,5.1^7,10] Dodeca-3-ene, 8-hydroxytetrasi
Black [4.4.0.1^2,5.1^{7,1 0}] Dodeca-3-ene, 8-hydroxy
Methyl tetracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-d
8-carboxytetracyclo [4.4.0.1^2,5.1^7,10] Dode
Ca-3-ene, 8,9-dicarboxytetracyclo [4.4.0.
1^2,5.1^7,10] Dodeca-3-ene, 8,8-difluorotetrasic
B [4.4.0.1^2,5.1^7,10] Dodeca-3-ene, 8,9-difluoro
Tetracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-ene, 8,8-
Bis (trifluoromethyl) tetracyclo [4.4.0.1^2,5.1
^7,10] Dodeca-3-ene, 8,9-bis (trifluoromethyl) te
Tracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-ene, 8-meth
Le-8-trifluoromethyltetracyclo [4.4.0.1^2,5.1
^7,10] Dodeca-3-ene, 8,8,9-trifluorotetracyclo
[4.4.0.1^2,5.1^7,10] Dodeca-3-ene, 8,8,9-tris (tri
Fluoromethyl) tetracyclo [4.4.0.1^2,5.1^7,10] Dode
Ca-3-ene, 8,8,9,9-tetrafluorotetracyclo [4.4.
0.1^2,5.1^7,10] Dodeca-3-ene, 8,8,9,9-tetrakis (to
Lifluoromethyl) tetracyclo [4.4.0.1^2,5.1^7,10] Do
Deca-3-ene, 8,8-difluoro-9,9-bis (trifluoro
Methyl) tetracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-d
, 8,9-difluoro-8,9-bis (trifluoromethyl) thene
Tracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-en, 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-pentafluoro
Propoxytetracyclo [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]
Dodeca-3-ene, 8,9-difluoro-8-heptafluoroiso
Propyl-9-trifluoromethyltetracyclo [4.4.0.1
^2,5.1^7,10]] Dodeca-3-ene, 8-chloro-8,9,9-triflu
Orotetracyclo [4.4.0.1^2,5.1^7,10] Dodeca-3-en,
8,9-Dichloro-8,9-bis (trifluoromethyl) tetracy
Black [4.4.0.1^2,5.1^7,10] Dodeca-3-ene, 8- (1'-carbo
Xy-2 ', 2', 2'-trifluoroethyl) tetracyclo [4.4.
0.1^2,5.1^7,10] Dodeca-3-ene, 8-methyl-8- (1'-carbo
Xy-2 ', 2', 2'-trifluoroethyl) tetracyclo [4.4.
0.1^2,5.1^7,10] Norbornene (derivative) such as dodeca-3-ene
Kind of

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 .1 ^{7, 10} .0 ^1,6 ] dodeca-3-ene,
8-Methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] Dodeca-
3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,12]
Dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0.
1 ^{2,5 1,7} 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 .1 ^9,12 .0 ^{8,1 3]} pentadeca-3 compound having an alicyclic skeleton such as ene;

Linear alkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate and n-butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate,
Hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxypropyl (meth) acrylic acid and 3-hydroxypropyl (meth) acrylic acid; α-hydroxymethyl methyl acrylate, α-hydroxymethyl ethyl acrylate,
α-Hydroxymethyl acrylic acid esters such as n-propyl α-hydroxymethyl acrylic acid n-butyl; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid , Unsaturated carboxylic acids such as mesaconic acid; (meth)
Free carboxyl group-containing ester of aliphatic unsaturated carboxylic acid such as 2-carboxyethyl acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate and 4-carboxybutyl (meth) acrylate Kind;

Vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; (meth) acrylamide-n-
n-dimethyl (meth) acrylamide, crotonamide,
Unsaturated amide compounds such as maleamide, fumaramide, mesacone amide, citracone amide and itacone amide
-n-vinyl-ε-caprolactam-n-vinylpyrrolidone,
Other nitrogen-containing vinyl compounds such as vinyl pyridine and vinyl imidazole; ethylene and the like can be mentioned.

Examples of the monofunctional monomer having an acid dissociable group other than the monomer represented by the above formula (1) include (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile and malein. Unsaturated nitrile compounds such as nitrile, fumaronitrile, mesacone nitrile, citracon nitrile and itacone nitrile; maleimide-
Examples thereof include unsaturated imide compounds such as n-cyclohexylmaleimide-n-phenylmaleimide. Further, among other monomers, examples of polyfunctional monomers include, for example, methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexane. The Olde
(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-adamantanedioldi
Examples thereof include (meth) acrylate and tricyclodecanyl dimethylol di (meth) acrylate.

Among these other monomers, bicyclo [2.
2.1] hept-2-ene, 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 5-carboxy bicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^{2, 5} .1 ^{7, 10} ] Dodeca-3-en, 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 ] dodeca-3-ene and the like are preferable.

<Metal Component Contained> Examples of impurities contained in the alicyclic hydrocarbon-based polymer include L
i, Ti, W, Al, Sn, Pd, Ni, Pt, Mo,
Oxides of metals such as Rh, Zr, B and V, and Fe,
Metal ions of metals such as Na, K, and Cu. Among these, Ni, Pd, etc., in particular, contain impurities derived from the catalyst at the time of polymerization. <Step I> In the metal removal method of the present invention, first, a solution of an alicyclic hydrocarbon-based polymer in an organic solvent is mixed with a poor solvent of the alicyclic hydrocarbon-based polymer and an acid to form an alicyclic compound. Solidify the hydrocarbon polymer. When the alicyclic hydrocarbon-based polymer is dissolved in an organic solvent, the concentration of the alicyclic hydrocarbon-based polymer relative to the organic solvent is 1 to 30 wt%, preferably 5 to 25 w
t%, more preferably 10 to 20 wt%, most preferably 10
It is prepared so as to be in the range of ˜15 wt%. If it is 1 wt% or less, the amount of the organic solvent used becomes large, which is economically unsuitable and the production efficiency becomes poor. If the amount used exceeds 30% by weight, the viscosity of the solution will increase depending on the molecular weight of the polymer, making handling difficult. Further, it may not be dissolved depending on the kind of the polymer. Examples of the organic solvent that dissolves the alicyclic hydrocarbon-based polymer include aromatic hydrocarbon compounds such as toluene and xylene.

The poor solvent used for coagulating the alicyclic hydrocarbon-based polymer is an organic solvent that does not substantially dissolve the alicyclic hydrocarbon-based polymer, and specific examples include formic acid. Lower alcohol esters of lower carboxylic acids such as methyl, ethyl formate, methyl acetate and ethyl acetate, lower alkyl ketones such as acetone and methyl ethyl ketone, lower alcohols such as methanol, ethanol, propanol, butanol, pentanol and hexanol, or One selected from these mixed solvents can be used. Further, aliphatic hydrocarbon compounds such as hexane, heptane, octane, nonane, decane, undecane and dodecane can also be used. Among these, those selected from lower alcohols such as methanol, ethanol and propanol are particularly preferable. Also,
Depending on the type of alicyclic hydrocarbon-based polymer, there are some that do not serve as poor solvents, so it is necessary to select an appropriate solvent. Further, when the poor solvent used contains impurities, it is preferable to remove the impurities by distillation or the like.

The amount of these poor solvents added is such that the weight ratio of the organic solvent solution of the alicyclic hydrocarbon polymer to the poor solvent (a water-insoluble organic solvent solution of the alicyclic hydrocarbon polymer / a poor solvent). Is 1
The amount is in the range of / 1 to 1/10, preferably 1/3 to 1/6. If the ratio of the poor solvent is less than 1/1, coagulation tends to be insufficient, or the effect of removing the metallic impurities tends to decrease. If it is more than 1/10, a large amount of poor solvent is used, which is uneconomical in industry.

Examples of the acid added in this step include formic acid, acetic acid, lactic acid, butyric acid, citric acid, oxalic acid, tartaric acid,
Benzoic acid, toluenesulfonic acid-n-propionic acid, valeric acid, maleic acid, maleic anhydride, fumaric acid, malonic acid, adipic acid, phthalic acid, terephthalic acid, salicylic acid, benzenesulfonic acid, camphorsulfonic acid,
And the like, or inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. Of these, oxalic acid is preferably used. In addition, the acid is in the form of powder, aqueous solution,
It may be in any gas state, and there is no limitation on the state. The addition amount of these organic acids or inorganic acids is 0.01 to 10 wt% with respect to the organic solvent solution of the alicyclic hydrocarbon-based polymer,
It is preferably 0.1 to 5% by weight. 0.01
If it is less than 10% by weight, the effect of removing metal impurities tends to decrease, and if it is more than 10% by weight, problems such as deterioration of the alicyclic hydrocarbon polymer may occur. Also,
The use of excess acidic material has no effect on metal removal. By adding these acids to the organic solvent solution of the alicyclic hydrocarbon polymer and mixing them, it becomes possible to improve the metal removal efficiency.

As a specific procedure of step I, the above poor solvent and acid are added to an organic solvent solution of an alicyclic hydrocarbon polymer, and a mixing treatment is carried out by stirring or the like. After the mixing treatment, the poor solvent phase and the solidified alicyclic hydrocarbon-based polymer are separated. Here, the order of adding the poor solvent and the acid to the organic solvent solution of the alicyclic hydrocarbon polymer is not particularly limited, but it is more preferable to add the acid before the poor solvent. Alternatively, a mixture of a poor solvent and an acid may be added in advance. Further, the poor solvent may be added all at once, or may be added little by little. The temperature during the mixing treatment in step I is usually -10 to 150 ° C, preferably 0 to 80 ° C, more preferably 20 to 50 ° C. The mixing treatment time is usually 1 minute to 1 hour, preferably 5 minutes to 20 minutes. By the above operation, the metal compound component contained in the alicyclic hydrocarbon-based polymer was extracted into the poor solvent phase with high separation efficiency, and as a result, the separated alicyclic hydrocarbon-based polymer was a metal compound. The content of the components is reduced. A known method is used to isolate the solidified alicyclic hydrocarbon polymer. Known methods include methods such as separation by filtration. The alicyclic hydrocarbon-based polymer after filtration may be dried, or the step II described below may be performed without being dried, in a state where a small amount of a poor solvent is contained.

<Step II> The alicyclic hydrocarbon polymer after coagulation and isolation is mixed with a water-insoluble organic solvent, an acid and water, and the metal is extracted and removed. Preferably, the alicyclic hydrocarbon polymer is dissolved in a water-insoluble organic solvent, then mixed with an acid and water, and the metal is extracted and removed under high temperature conditions. Specific examples of the non-water-soluble organic solvent used in this step include acetic acid esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and 2-pentanone. Glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate,
Examples thereof include aromatic hydrocarbons such as toluene and xylene. Among these, methyl isobutyl ketone, ethyl acetate, butyl acetate and the like are preferable. These solvents may be used alone or in combination of two or more.

The acid and water used in this step may be added in the form of an acidic aqueous solution, preferably an acidic hot aqueous solution, or the acid and water may be added separately. The acidic hot aqueous solution is obtained by adding an acid to heated water or by adding an acid to water and then heating. It is necessary to use the water used in this step after removing impurities such as ion exchange. Specifically, it is desirable that the concentration of metallic impurities such as Fe, Na, and Ni be 5 ppb or less. The amount of water added is the weight ratio of the total amount of the alicyclic hydrocarbon-based polymer and the non-water-soluble organic solvent to water (the total amount of the alicyclic hydrocarbon-based polymer and the non-water-soluble organic solvent / water). Is 1 / 0.1 to 1/10, preferably 1 /
The range is 0.5 to 1/2. Here, if the proportion of water is too small, the efficiency of removing metal impurities tends to decrease. On the other hand, if the proportion of water is too large, it becomes difficult to separate the alicyclic hydrocarbon-based polymer from the solution of the non-water-soluble organic solvent, and the removal efficiency of the metal-based impurities decreases, which is not preferable. Further, the removal efficiency can be increased by appropriately adjusting the amount of water according to the type of alicyclic hydrocarbon-based polymer to be treated and the type of metallic impurities to be removed.

As the acid used in this step, the organic acid or inorganic acid exemplified as the acid used in the above step I can be mentioned. Of these, oxalic acid is preferably used. The acid may be in a powder state, an aqueous solution state or a gas state, and there is no limitation on the state. The amount of acid added is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on water. If it is less than 0.01% by weight, the effect of removing metal impurities tends to decrease, and if it is more than 10% by weight, problems such as deterioration of the alicyclic hydrocarbon polymer may occur. Also, the use of excess acidic material has no effect on metal removal. These acids
Addition to the above solution and mixing treatment can improve the efficiency of removing impurities such as metal compounds. Depending on the type of alicyclic hydrocarbon-based polymer to be treated, it may be deteriorated by a specific acid. Therefore, it is necessary to select a suitable type and amount of the acid.

In this step, a metal-removing efficiency can be further improved by adding a poor solvent for the alicyclic hydrocarbon polymer and a water-soluble solvent. Specific examples include acetone, propylene glycol monomethyl ether, dioxane, ethyl lactate, gamma butyl lactone, and the like. Of these, acetone is preferably used. The addition amount is preferably 10 with respect to the total amount of the alicyclic hydrocarbon-based polymer and the water-insoluble organic solvent.
% To 100% by weight, particularly preferably 20 to 50% by weight. 100
If it exceeds 5% by weight, problems such as a decrease in the yield of the alicyclic hydrocarbon-based polymer may occur. In addition, depending on the type of alicyclic hydrocarbon-based polymer to be treated, it may be deteriorated by a specific poor solvent, so it is necessary to select a suitable type and amount of the solvent. The temperature during metal extraction in this step is usually 30 to 150 ° C, preferably 50 to 90 ° C. Depending on the type of alicyclic hydrocarbon-based polymer to be treated, it may deteriorate at high temperatures, so it is necessary to select a suitable temperature. The temperature at the time of extraction is adjusted by using an acidic hot aqueous solution or by heating at the time of extraction.

The extraction time is usually 1 minute to 100 hours, preferably 1 hour to 20 hours. It is also preferable to keep the temperature constant during the extraction. The temperature is usually 30-150
C, preferably 50 to 90C. An appropriate extraction time needs to be selected because an appropriate time varies depending on the type of alicyclic hydrocarbon-based polymer to be treated and the amount of metal to be removed. In extraction, stirring or shaking is sufficient as a method for ensuring sufficient contact between the organic layer and the aqueous layer. Industrially, uniflow, countercurrent extraction and the like can be mentioned, but any method may be used as long as the contact between the organic layer and the aqueous layer is sufficient.

The order of adding the alicyclic hydrocarbon-based polymer, the non-water-soluble organic solvent, the acid and the water is not limited, but the alicyclic hydrocarbon-based polymer is dissolved in the non-water-soluble organic solvent and then the acid and the water are dissolved. The preferred order is to add water. In this case, water may be added after adding the acid, or acid may be added after adding water. Further, a water-insoluble organic solvent, an acid and water may be added to the alicyclic hydrocarbon-based polymer at the same time. The pressure during extraction may be normal pressure, reduced pressure, or increased pressure, and there is no limitation.

After the extraction, the water layer and the organic layer are separated. The separation of the organic layer and the aqueous layer after extraction may be performed by static separation, but a more efficient separation method such as a coalescer or a centrifuge may be used. By such treatment, the content of metal impurities in the alicyclic hydrocarbon-based polymer can be reduced to 100 ppb or less, respectively, but the water-insoluble organic solvent of the obtained alicyclic hydrocarbon-based polymer can be reduced. It is also possible to further reduce the metal content of the layer by repeating the operations of adding acid and water, mixing by stirring, standing, and liquid separation several times. In addition, after the above-mentioned extraction treatment, it is desirable that the acid be removed by further performing extraction treatment several times using only water. The non-water-soluble organic solvent solution of the alicyclic hydrocarbon-based polymer thus obtained is added with other solvent as necessary, and then the remaining water and the non-water-soluble organic solvent are removed by an operation such as vacuum distillation. Thus, an alicyclic hydrocarbon-based polymer having a reduced metal content can be obtained. The alicyclic hydrocarbon-based polymer treated according to the present invention has a significantly reduced content of each metal of 100 ppb or less as compared with that before treatment.

2. Radiation-sensitive composition A radiation-sensitive composition can be obtained from the alicyclic hydrocarbon-based polymer purified by the method for removing contained metal in the present invention and the radiation-sensitive acid generator. <Acid Generator> Examples of the acid generator used in the present invention include onium salts, sulfone compounds, sulfonate compounds, sulfonimide compounds, diazomethane compounds, disulfonylmethane compounds and halogen-containing compounds. Examples of these acid generators are shown below. Onium salt: Examples of the onium salt include iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, and pyridinium salt.

Specific examples of the onium salt compound include bis.
(4-t-Butylphenyl) iodonium perfluoro-n-
Octane sulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butane sulfonate, bis
(4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium pyrenesulfonate, bis (4-t-butylphenyl)
Iodonium n-dodecylbenzene sulfonate, bis
(4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium benzenesulfonate, bis (4-t-butylphenyl) ) Iodonium naphthalene sulfonate,
Bis (4-t-butylphenyl) iodonium 10-camphor sulfonate, bis (4-t-butylphenyl) iodonium octane sulfonate, bis (4-t-butylphenyl)
Iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 2,4-difluorobenzenesulfonate,

Diphenyliodonium perfluoro-n-
Octane sulfonate, diphenyl iodonium nonafluoro-n-butane sulfonate, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium pyrene sulfonate, diphenyl iodonium n
-Dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium naphthalenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium octanesulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate , Diphenyliodonium 4-trifluoromethylbenzenesulfonate, diphenyliodonium 2,4-difluorobenzenesulfonate,

Triphenylsulfonium perfluoro-
n-octane sulfonate, triphenyl sulfonium nonafluoro-n-butane sulfonate, triphenyl sulfonium trifluoro methane sulfonate, triphenyl sulfonium pyrene sulfonate, triphenyl sulfonium n-dodecyl benzene sulfonate, triphenyl sulfonium hexafluoro antimonate, triphenyl sulfonium p -Toluene sulfonate, triphenyl sulfonium benzene sulfonate, triphenyl sulfonium naphthalene sulfonate, triphenyl sulfonium 10-camphor sulfonate, triphenyl sulfonium octane sulfonate, triphenyl sulfonium 2-trifluoromethyl benzene sulfonate, triphenyl sulfonium 4-trifluoromethyl benzene Sulfonate, Triphenylsulfonium 2,4
Difluorobenzene sulfonate,

4-t-butylphenyl diphenylsulfonium nonafluorobutane sulfonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium pyrene sulfonate, 4-t-butylphenyl
Diphenylsulfonium dodecylbenzene sulfonate, 4-t-butylphenyl diphenylsulfonium p-
Toluene sulfonate, 4-t-butylphenyl diphenylsulfonium benzene sulfonate, 4-t-butylphenyl diphenylsulfonium 10-camphor sulfonate, 4-t-butylphenyl diphenylsulfonium octane sulfonate, 4-t-butylphenyl diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butylphenyl / diphenylsulfonium 4-trifluoromethylbenzenesulfonate, 4-
t-butylphenyl diphenylsulfonium 2,4-difluorobenzene sulfonate, 4-t-butoxyphenyl diphenylsulfonium nonafluorobutane sulfonate, 4-hydroxyphenyl benzyl methylsulfonium p-toluene sulfonate,

2,4,6-tristrimethylphenyl diphenylsulfonium nonafluorobutane sulfonate, 2,
4,6-Tristrimethylphenyl / diphenylsulfonium trifluoromethanesulfonate, 2,4,6-Tristrimethylphenyl / diphenylsulfonium pyrenesulfonate, 2,4,6-Tristrimethylphenyl / diphenylsulfonium dodecylbenzenesulfonate, 2,4,6 -Tristrimethylphenyl / diphenylsulfonium p-
Toluenesulfonate, 2,4,6-tristrimethylphenyl diphenylsulfonium benzenesulfonate, 2,
4,6-tristrimethylphenyl diphenylsulfonium 10-camphor sulfonate, 2,4,6-tristrimethylphenyl diphenylsulfonium octane sulfonate, 2,4,6-tristrimethylphenyl diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 2,4,6-tristrimethylphenyl / diphenylsulfonium 4-trifluoromethylbenzenesulfonate,
2,4,6-tristrimethylphenyl diphenylsulfonium 2,4-difluorobenzenesulfonate,

Cyclohexyl-2-oxocyclohexyl-methylsulfonium trifluoromethanesulfonate, cyclohexyl-2-oxocyclohexyl-methylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl-2-oxocyclohexyl-methylsulfonium perfluoro-n-octanesulfonate, Dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium nonafluoro-n-butanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium perfluoro-n-octanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate , 2-oxocyclohexyldimethylsulfonium nona Ruoro -n- butane sulfonate, 2-oxo-cyclohexyl dimethyl sulfonium perfluoro -n- octane sulfonate,

4-hydroxyphenyl phenyl methylsulfonium p-toluene sulfonate, 4-hydroxyphenyl benzyl methyl sulfonium p-toluene sulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldimethylsulfonium nonafluoro-n- Butanesulfonate, 1-naphthyldimethylsulfonium perfluoro-n-octanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 1-naphthyldiethylsulfonium perfluoro-n-octanesulfonate 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium nonafluoro- -Butanesulfonate, 4-cyano-1-naphthyldimethylsulfonium perfluoro-n-octanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate , 4-cyano-1-naphthyldiethylsulfonium perfluoro-n-oct

Tan sulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-nitro-1-naphthyldimethylsulfonium perfluoro-n- Octanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-nitro-1-naphthyldiethylsulfonium perfluoro-n-octanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldimethylsulfonium perfluoro-n-octane Sulfonates, 4-methyl-1-naphthyl diethyl sulfonium trifluoromethane sulfonate, 4-methyl-1-naphthyl diethyl sulfonium nonafluoro -n- butane sulfonate, 4-methyl-1-naphthyl diethyl sulfonium perfluoro -n- octane sulfonate,

4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy
-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium perfluoro-n-octanesulfonate,
4-hydroxy-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium perfluoro-n-octanesulfonate, 1- ( 3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3, 5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octane sulfonate,

1- (4-methoxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-methoxyphenyl)
Tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (2,4-dimethoxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1-
(2,4-dimethoxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (2,4-dimethoxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-hydroxynaphthalene- 1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxynaphthalene-1-
1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-propoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane Sulfonate, 1- (4-i-propoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate,
1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-
t-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate,

1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butane sulfonate, 1- (4-methoxy-naphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butane Sulfonate, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-propoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butane Sulfonate, 1- (4-i-propoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n -Butanesulfonate, 1- (4-t-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfo Over door,

1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate , 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4-n-propoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate , 1- (4-i-propoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n- Octane sulfonate, 1- (4-t-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-o Kutansulfonate, 1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1 -(4-Methoxymethoxynaphthalene-1
-Yl) tetrahydrothiophenium perfluoro-n-
Octane sulfonate,

1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1 -(4-Ethoxymethoxynaphthalene-1
-Yl) tetrahydrothiophenium perfluoro-n-
Octane sulfonate, 1- {4- (1-methoxyethoxy) naphthalen-1-yl} tetrahydrothiophenium trifluoromethanesulfonate, 1- {4- (1-methoxyethoxy) -naphthalen-1-yl} tetrahydrothiophenium Nonafluoro-n-butane sulfonate, 1- {4- (1-methoxyethoxy) naphthalen-1-yl} tetrahydrothiophenium perfluoro-n-octane sulfonate,

1- {4- (2-methoxyethoxy) naphthalene-1
-Yl} tetrahydrothiophenium trifluoromethanesulfonate, 1- {4- (2-methoxyethoxy) naphthalen-1-yl} tetrahydrothiophenium nonafluoro-
n-butane sulfonate, 1- {4- (2-methoxyethoxy)
Naphthalen-1-yl} tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxycarbonyloxynaphthalene- 1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-ethoxycarbonyloxy Naphthalene-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxycarbonyloxynaphthalene-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-ethoxycarbonyloxynaphthalene- 1-Il) te La hydro thiophenium bromide perfluoro -n- octane sulfonate,

1- (4-n-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro- n-butane sulfonate, 1- (4-
(n-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- ( 4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-
i-Propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- ( 4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-
Butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate,

1- (4-t-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-t-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro- n-butane sulfonate, 1- (4-t-
Butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- {4- (2-tetrahydrofuranyloxy) naphthalen-1-yl} tetrahydrothiophenium trifluoromethanesulfonate, 1- { 4- (2-Tetrahydrofuranyloxy) naphthalen-1-yl} tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- {4- (2-
Tetrahydrofuranyloxy) naphthalen-1-yl} tetrahydrothiophenium perfluoro-n-octane sulfonate,

1- {4- (2-tetrahydropyranyloxy) naphthalen-1-yl} tetrahydrothiophenium trifluoromethanesulfonate, 1- {4- (2-tetrahydropyranyloxy) naphthalen-1-yl} tetrahydro Thiophenium nonafluoro-n-butane sulfonate, 1- {4-
(2-Tetrahydropyranyloxy) naphthalen-1-yl}
Tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4-benzyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-benzyloxynaphthalen-1-yl) tetrahydrothiophenium Nonafluoro-n-butane sulfonate, 1- (4-benzyloxynaphthalene-1-
1) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium nonafluoro-n-butane Examples thereof include sulfonate and 1- (1-naphthylacetomethyl) tetrahydrothiophenium perfluoro-n-octane sulfonate.

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and these α-diazo compounds. Specific examples of the sulfone compound include phenacylphenyl sulfone, mesitylphenacyl sulfone, bis (phenylsulfonyl) methane, 4-trisphenacyl sulfone and the like. Sulfonic acid ester compound: Examples of the sulfonic acid ester compound include alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, imino sulfonate and the like.
Specific examples of the sulfonate compound, benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, pyrogallol tris nonafluorobutane sulfonate, pyrogallol methanesulfonic acid triester, nitrobenzyl-9,10-diethoxyanthracene-2
-Sulfonate, α-methylol benzoin tosylate,
α-methylol benzoin octane sulfonate, α-methylol benzoin trifluoromethane sulfonate,
Examples include α-methylol benzoindodecyl sulfonate and the like.

Sulfonimide compound: As the sulfonimide compound, for example, the following formula (6):

[0066]

[Chemical 10] (In the formula, M represents a divalent group such as an alkylene group, an arylene group or an alkoxylene group, and R ² represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group. .) Can be mentioned.

Specific examples of the sulfonimide compound include:
N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy)
Diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2-3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] ] Hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (tri Fluoromethylsulfonyloxy) naphthylimide,

N- (nonafluorobutylsulfonyloxy) succinimide, N- (nonafluorobutylsulfonyloxy) phthalimide, N- (nonafluorobutylsulfonyloxy) diphenylmaleimide, N- (nonafluorobutylsulfonyloxy) bicyclo [2.2. 1] Hept-5-
Ene-2,3-dicarboximide, N- (nonafluorobutylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (nonafluorobutylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-
Oxy-2,3-dicarboximide, N- (nonafluorobutylsulfonyloxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide ,

N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy)
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (10-camphorsulfonyloxy) bicyclo [2.
2.1] Heptane-5,6-oxy-2,3-dicarboximide, N
-(10-camphorsulfonyloxy) naphthylimide, N
-(p-toluenesulfonyloxy) succinimide, N-
(p-toluenesulfonyloxy) phthalimide, N- (p-
Toluenesulfonyloxy) diphenylmaleimide, N-
(p-Toluenesulfonyloxy) bicyclo [2.2.1] hept
-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p -Toluenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (p-toluenesulfonyloxy)
Examples thereof include naphthyl imide and compounds represented by the following formulas (7-1) to (7-6).

[0070]

[Chemical 11] (In formulas (7-1) to (7-6), C independently represents an organic group having an ester bond having 2 to 10 carbon atoms, and D independently represents an alkyl group having 1 to 10 carbon atoms or a carbon atom. Represents an alkoxyl group having 1 to 10 atoms, p is an integer of 1 to 11, q is an integer of 0 to 10, and the sum of p + q is 11 or less.) Diazomethane compound: As a diazomethane compound,
For example, a compound represented by the following formula (8) can be given.

[0071]

[Chemical 12] (In the formula, R ³ and R ⁴ are the same or different and each represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, and a halogen-substituted aryl group.) Specific examples of the diazomethane compound include bis ( Trifluoromethylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane,
Methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, a compound represented by the following formula (8-1) Etc. can be mentioned.

[0072]

[Chemical 13] Disulphonylmethane compound: Examples of the disulphonylmethane compound include compounds represented by the following formula (9).

[0073]

[Chemical 14] [Wherein R ⁵ and R ⁶ are the same or different and represent a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or another monovalent organic group having a hetero atom, E And F are the same or different and represent a hydrogen atom, a linear or branched alkyl group, an aryl group or another monovalent organic group having a hetero atom,
And at least one of E and F is an aryl group, or E and F are linked to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond,
Alternatively, E and F are linked to each other to form a group represented by the following formula (9-1).

[0074]

[Chemical 15] (In the formula, E ′ and F ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or E ′ and F ′ are connected to each other to form a carbon atom. A monocyclic structure is formed, and r is 2 to 1.
It is an integer of 0. ) Specific preferred examples of the disulfonylmethane compound include compounds represented by the following formulas (10) to (17).

[0075]

[Chemical 16]

[0076]

[Chemical 17]

[0077]

[Chemical 18]

[0078]

[Chemical 19]

[0079]

[Chemical 20]

[0080]

[Chemical 21]

[0081]

[Chemical formula 22]

[0082]

[Chemical formula 23] Halogen-containing compound: As the halogen-containing compound,
Examples thereof include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferable halogen-containing compounds include phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine-1-naphthylbis (trichloromethyl) -s-triazine and the like (trichloro Examples thereof include methyl) -s-triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.

Of these acid generators, compounds which generate an acid having a boiling point of 165 ° C. or higher under normal pressure are preferable, and particularly, bis (4-t-butylphenyl) iodonium nonafluorobutane sulfonate and bis (4 -t-butylphenyl)
Iodonium dodecylbenzene sulfonate, bis (4-
t-butylphenyl) iodonium p-toluene sulfonate, bis (4-t-butylphenyl) iodonium 10-camphor sulfonate, bis (4-t-butylphenyl) iodonium octane sulfonate, diphenyliodonium p-toluene sulfonate, diphenyliodonium benzene sulfonate , Diphenyliodonium 10-camphorsulfonate, diphenyliodonium octanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium naphthalenesulfonate,

4-t-butoxyphenyl diphenylsulfonium nonafluorobutanesulfonate, 4-hydroxyphenylbenzyl methylsulfonium p-toluenesulfonate, N- (nonafluorobutylsulfonyloxy) succinimide, N- (nonafluorobutylsulfonyloxy) ) Phthalimide, N- (nonafluorobutylsulfonyloxy) diphenylmaleimide, N- (nonafluorobutylsulfonyloxy) bicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- (nonafluorobutylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (nonafluorobutylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-
Oxy-2,3-dicarboximide, N- (nonafluorobutylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphor Sulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene
-2,3-Dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthyl Imide and the like are preferable.

In the present invention, the acid generator may be used alone or in combination of two or more. The amount of the acid generator used is usually 0.5 to 20 per 100 parts by weight of the polymer.
Parts by weight, preferably 1 to 10 parts by weight. <Other additives> The radiation-sensitive composition of the present invention has an action of controlling the diffusion phenomenon of an acid generated from an acid generator by exposure in a resist film and suppressing an unfavorable chemical reaction in a non-exposed region. It is preferable to add an acid diffusion control agent having the following (hereinafter, also referred to as “acid diffusion control agent”).

By using such an acid diffusion controlling agent, the storage stability of the composition is improved, the resolution as a resist is further improved, and the line width change of the resist pattern due to the fluctuation of PED is significantly suppressed. The process stability is extremely excellent. The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change due to exposure or heat treatment during the resist pattern forming step. As such a nitrogen-containing organic compound, for example, the following formula (18):

[0087]

[Chemical formula 24]

(In the formula, R ⁷ , R ⁸ and R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms,
Aryl group having 6 to 15 carbon atoms or 7 to carbon atoms
Shows 15 aralkyl groups. ) Compound represented by (hereinafter,
It is called "nitrogen-containing compound (I)". ), A diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound”).
(II) ”. ), A diamino polymer having three or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (III)”), an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, and the like.

Examples of the nitrogen-containing compound (I) include n-
Monoalkylamines such as hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n -Heptylamine, di
dialkylamines such as -n-octylamine, di-n-nonylamine and di-n-decylamine; triethylamine,
Tri-n-propylamine, tri-n-butylamine, tri
-n-pentylamine, tri-n-hexylamine, tri-
n-heptylamine, tri-n-octylamine, tri-n
-Trialkylamines such as nonylamine, tri-n-decylamine and tri-n-dodecylamine; aniline, N-
Methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine,
Aromatic amines such as 1-naphthylamine; trialcoholamines such as triethanolamine.

Examples of the nitrogen-containing compound (II) include ethylenediamine, tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diamino. Benzophenone, 4,4'-diaminodiphenylamine, 2,2'-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl ) -2- (3-Hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1
-Methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and the like can be mentioned. Examples of the nitrogen-containing compound (III) include polyethyleneimine and polyallylamine. Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N,
Examples thereof include N-dimethylacetamide, propionamide, benzamide, pyrrolidone and N-methylpyrrolidone. Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea and tributylthiourea. be able to.

Examples of the nitrogen-containing heterocyclic compound include imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole, 1-t-butoxycarbonyloxy-2-phenyl. Imidazoles such as benzimidazole; pyridine, 2-methylpyridine, 4-methylpyridine,
2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, benzyl nicotinate, quinoline, 8-oxyquinoline, acridine In addition to pyridines such as pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-
Examples include diazabicyclo [2.2.2] octane.

Of these nitrogen-containing organic compounds, the nitrogen-containing compounds (I), nitrogen-containing heterocyclic compounds and the like are preferable. Also,
Among the nitrogen-containing compounds (I), trialkylamines are particularly preferable, and among the nitrogen-containing heterocyclic compounds, pyridines are particularly preferable. In the present invention, the acid diffusion controller may be used alone or in combination of two or more. The amount of the acid diffusion controller used is usually 0.001 to 15 parts by weight, preferably 0.001 to 10 parts by weight, and more preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the copolymer component. In this case, if the amount of the acid diffusion control agent used is too small, the resolution and PED stability as a resist tend to be lowered, and if the amount is too high, the sensitivity as a resist and the developability of the exposed portion tend to be lowered. . Further, the radiation-sensitive composition of the present invention may contain, if necessary, a surfactant having an effect of improving the coating property and striation of the composition, the developability as a resist, and the like.

Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether,
Examples thereof include polyoxyethylene nonylphenol ether, polyethylene glycol dilaurate, polyethylene glycol distearate and the like. Examples of commercially available products include Ftop EF301, EF303,
EF352 (manufactured by Tochem Products), Megafax F171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.),
Florard FC430, FC431 (Sumitomo 3M
Co., Ltd.), Asahi Guard AG710, Surflon S-3
82, SC101, SC102, SC103, SC10
4, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), KP34
1 (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflo-no. 75-no.
95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. The content of the surfactant is usually 2 parts by weight or less per 100 parts by weight of the copolymer component.

The positive and negative radiation-sensitive compositions of the present invention have the function of absorbing the energy of radiation and transmitting the energy to the acid generator, thereby increasing the amount of acid produced. If desired, a sensitizer having the effect of improving the apparent sensitivity of the resist can be added. Examples of preferable sensitizers include benzophenones, rose bengals, anthracenes, carbazoles and the like. The compounding amount of the sensitizer is
It is usually 50 parts by weight or less per 100 parts by weight of the component (A).
Further, by blending a dye and / or a pigment,
The latent image in the exposed area can be visualized to alleviate the effect of halation during exposure, and the addition of an adhesion aid can further improve the adhesion to the substrate. Furthermore, 4-hydroxy-4′-, as another additive, if necessary.
Antihalation agent such as methyl chalcone, shape improver,
A storage stabilizer, a defoaming agent and the like can be added.

<Preparation and Use of Composition> When the radiation-sensitive composition of the present invention is used, the concentration of the total solid content is, for example, 5 to 50% by weight, preferably 10 to 40% by weight. After being uniformly dissolved in a solvent, for example, a composition solution is prepared by filtering with a filter having a pore size of about 0.2 μm. Examples of the solvent used for preparing the composition solution include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, and the like. Glycol monoalkyl ether acetates; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether,
Propylene glycol monoalkyl ethers such as propylene glycol mono-n-butyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol di-n-butyl ether;

Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate and other propylene glycol monoalkyl ether acetates; methyl lactate, ethyl lactate, Lactic acid esters such as n-propyl lactate and i-propyl lactate; n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, Aliphatic carboxylic acid esters such as n-amyl acetate, i-amyl acetate, i-propyl propionate, n-butyl propionate, i-butyl propionate; ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate , 2-hydroxy-3-methyl Methyl acid, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutylacetate, 3-methyl-3 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate,
Other esters such as methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; toluene,
Aromatic hydrocarbons such as xylene; methyl ethyl ketone,
Ketones such as methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone and lactones such as γ-butyrolactone. These solvents may be used alone or in combination of two or more.

<Formation of resist pattern> When a resist pattern is formed from the radiation-sensitive composition of the present invention,
By applying the composition solution prepared as described above, by suitable coating means such as spin coating, cast coating, and roll coating, for example, by coating on a substrate such as a silicon wafer or a wafer coated with aluminum. Then, a resist film is formed and, if necessary, a heat treatment (hereinafter referred to as “prebaking”) is performed at a temperature of about 70 ° C. to 160 ° C., and then exposure is performed through a predetermined mask pattern. The radiation used at that time is, for example, ultraviolet rays such as i-line (wavelength 365 nm) or far ultraviolet rays such as ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm), depending on the type of acid generator. X-rays such as synchrotron radiation and charged particle beams such as electron beams are appropriately selected and used. In addition, the exposure conditions such as the exposure amount are appropriately selected according to the composition of the radiation-sensitive resin composition, the type of each additive, and the like.

In the present invention, exposure is carried out in order to stably form a highly precise fine pattern which is excellent in resolution, developability and pattern shape, has no particular problem of pattern tailing, and is excellent in PED stability. Later, at a temperature of 90-160 ℃ 3
It is preferable to perform a heat treatment (hereinafter referred to as “post-exposure bake”) for 0 second or longer. In this case, if the post-exposure bake temperature is lower than 90 ° C., the effect of improving the PED stability tends to decrease, and depending on the conditions such as the resist film thickness, for example, the SiN substrate, the SiO ₂ film may be doped with boron or phosphorus. When forming a resist pattern on an ion-implanted BPSG substrate or the like, the pattern is likely to be skirted, which may not be suitable for manufacturing an actual device.

Then, the exposed resist film is alkali-developed using an alkali developer under conditions of usually 10 to 50 ° C. for 30 to 200 seconds to form a predetermined resist pattern. Examples of the alkaline developer include alkali metal hydroxide, aqueous ammonia, mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, tetraalkyl Ammonium hydroxides, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo-
[4.3.0] -5-nonene and other alkaline compounds are usually
An alkaline aqueous solution which is dissolved to have a concentration of 10% by weight, preferably 1 to 5% by weight is used.

Further, a water-soluble organic solvent such as methanol or ethanol, or a surfactant may be appropriately added to the developer containing the alkaline aqueous solution. When a developing solution composed of an alkaline aqueous solution is used, it is generally washed with water after development. In forming the resist pattern, a protective film may be provided on the resist film in order to prevent the influence of basic impurities contained in the ambient atmosphere.

[0101]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 10 equipped with a Teflon coated stir bar
Bicyclo [2.2.1] hept-5-ene-2-methylethyl carbonate (17.15 g, 0.0764 mol) and t-butyl ester of norbornene (14.85 g, 0.0764mo) in a 0 ml glass bottle.
l) and 50 ml of toluene were added. 0.3699 g (0.2049
mol) of (toluene) Ni (C ₆ F ₅ ) ₂ is dissolved in 15 ml of toluene, and a nickel catalyst [toluene complex of bisperfluorophenyl nickel: (toluene) Ni (C ₆ F ₅ ) ₂ ] is dry-boxed. Prepared in.

The prepared active catalyst solution was added at room temperature to a toluene solution of the above monomer using an injector, and the mixture was reacted at room temperature for 6 hours while stirring. The obtained reaction solution was diluted with toluene to obtain a polymer solution having a solid content concentration of 20% by weight (hereinafter, also referred to as "polymer solution (I)"). At this point, the concentration of metallic impurities in the polymer was measured by an atomic absorption spectrophotometer to find that Na: 600 ppb, K: 150 p
pb, Fe: 250 ppb, Al: 150 ppb, Ni: 7000 ppb,
Cu: It was 150 ppb. 0.8% oxalic acid was added to this polymer solution.
77 g was added, and the mixture was stirred at room temperature for 1 minute. Then, the mixture was added dropwise to 350.8 g of methanol heated to 30 ° C., and the mixture was stirred for 5 minutes while maintaining the same temperature. Then, the obtained coagulated product of the polymer was collected by filtration.

Methyl isobutyl ketone was added to the obtained polymer.
140 g, oxalic acid 0.28 g, deionized water 175 g, acetone
50 g was added, the temperature was raised to 80 ° C., the mixture was stirred in the range of 79 to 81 ° C. for 15 hours, and then allowed to stand. As a result, the polymer solution layer and the water layer were separated, so the lower water layer was removed. To the obtained polymer solution layer, 260 g of ion-exchanged water was added again, and 38 ~ 4
After stirring for 1 minute in the temperature range of 2 ° C, let stand and separate the water layer,
Removed. After that, 152 g of the polymer solution was dropped into 608 g of methanol at room temperature, and after stirring for 1 minute, the coagulated product of the produced polymer was collected by filtration. The obtained coagulated product was dried at 60 ° C. and 10 atm for 5 hours to obtain 15 g of a polymer. The concentration of metal impurities in the polymer thus purified was measured by an atomic absorption spectrophotometer to find that Na: 3 ppb, K: 5 p
pb, Fe: 3 ppb, Al: 1 pppb, Ni: 65 ppb, C
The content of u: 3 ppb and metallic impurities was significantly reduced. This polymer is referred to as "polymer (A-1)".

Example 2 5- [2-hydroxy-2,2 was added to a 300 ml eggplant-shaped flask equipped with a Teflon (registered trademark) -coated stir bar.
-Di (trifluoromethyl)] bicyclo [2.2.1] hept-2-ene (14.39 g, 52.5 mmol) and 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene (4.37 g, 22.5 mm)
ol) was added. Then, in a nitrogen stream, distilled toluene 1
00 ml was added and stirred. Furthermore, 365 mg of a nickel catalyst [toluene complex of bisperfluorophenyl nickel: (toluene) Ni (C ₆ F ₅ ) ₂ ] 365 mg prepared according to the description of WO 97/33198 International Publication was added, and the mixture was stirred at room temperature for 15 hours. After that, the reaction solution was dropped into methanol and solidified.
Then, the polymer coagulated by suction filtration is filtered off,
After vacuum drying at ℃, 11.4g of polymer (yield 61%) was obtained. The polymer obtained had a polystyrene-reduced weight average molecular weight (Mw, the same applies hereinafter) measured by gel permeation chromatography (GPC; the same applies below).
Met. At this point, the concentration of metallic impurities in the polymer was measured by an atomic absorption spectrophotometer to find that Na:
300 ppb, K: 200 ppb, Fe: 200 ppb, Al: 100 pp
b, Ni: 2500 ppb, Cu: 150 ppb.

57 g of toluene was added to this polymer, and the mixture was added dropwise to 274 g of methanol heated to 35 ° C., 2 g of 90% aqueous lactic acid solution was added, and the mixture was stirred for 5 minutes while maintaining the same temperature. Then, the obtained coagulated product of the polymer was collected by filtration. Methyl isobutyl ketone 90 was added to the obtained polymer.
g, 0.5 g of oxalic acid, 110 g of ion-exchanged water, and 30 g of propylene glycol monomethyl ether were added, the temperature was raised to 70 ° C., and the mixture was stirred at 69 to 71 ° C. for 10 hours and then left standing. As a result, the polymer solution layer and the water layer were separated, so the lower water layer was removed. To the obtained polymer solution layer, 180 g of ion-exchanged water was added again, the mixture was stirred for 1 minute in the temperature range of 25 to 30 ° C., and then allowed to stand to separate and remove the aqueous layer. Then, 101 g of the polymer solution was added dropwise to 404 g of methanol at room temperature, and after stirring for 1 minute, the coagulated product of the produced polymer was filtered. The solidified product was dried at 60 ° C and 10 atm for 5 hours to give 10 g of polymer.
Got With respect to the polymer thus purified, the concentration of metal impurities was measured by an atomic absorption spectrophotometer to find that Na: 2 ppb, K: 1 ppb, Fe: 3 ppb, Al: 3 p
The content of ppb, Ni: 95 ppb, Cu: 2 ppb and metal impurities was greatly reduced. This polymer is referred to as "polymer (A
-2) ”.

Example 3 5- [2-hydroxy-] was added to a 300 ml eggplant-shaped flask equipped with a Teflon (registered trademark) -coated stir bar.
2,2-Di (trifluoromethyl)] bicyclo [2.2.1] hept-2
-Ene 14.39 g (52.5 mmol) and 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene 4.37 g (22.5 mm
ol) was added. Next, in a nitrogen stream, 100 ml of oxygen-free distilled toluene was added and stirred. Furthermore, Macro
molecule, Vol. 29 (1996), p. 2755, prepared palladium (II) -nitrile complex: [Pd (CH ₃ CN)
₄ ] [BF ₄ ] ₂ 365 mg was added and stirred at room temperature. Furthermore, after stirring for 15 hours, the reaction solution was dropped into methanol to solidify. Then, the polymer coagulated by suction filtration was separated by filtration and vacuum dried at 50 ° C. to obtain 11.4 g of polymer (yield 61%). When the molecular weight was measured by GPC, it was MW = 25,000. At this point, the concentration of metallic impurities in the polymer was measured by an atomic absorption spectrophotometer to find that Na: 280
ppb, K: 170 ppb, Fe: 230 ppb, Al: 110 ppb, P
d: 3900 ppb and Cu: 250 ppb.

To this polymer was added 38.6 g of toluene, and the temperature was 40 ° C.
The mixture was added dropwise to 200 g of methanol whose temperature was raised to 4 g, 4 g of citric acid was added, and the mixture was stirred for 10 minutes while maintaining the same temperature. Then, the obtained coagulated product of the polymer was collected by filtration. Methyl isobutyl ketone 108.6 was added to the obtained polymer.
g, citric acid 0.6g, ion exchanged water 120g, acetone 40g
Was added, the temperature was raised to 70 ° C., the mixture was stirred in the range of 69 to 71 ° C. for 10 hours, and then left standing. As a result, the polymer solution layer and the water layer were separated, so the lower water layer was removed. To the obtained polymer solution layer, 180 g of ion exchanged water was added again, and the temperature was 25 to 30 ° C.
After stirring for 1 minute in the temperature range of 1, the mixture was allowed to stand and the aqueous layer was separated and removed. Then, 100 g of the polymer solution was added to methanol 400 at room temperature.
The resulting solidified product was collected by filtration. The obtained solidified product was dried at 60 ° C. and 10 atm for 5 hours to obtain 9.5 g of a polymer. With respect to the polymer purified in this manner, the concentration of metal impurities was measured by an atomic absorption spectrophotometer to find that Na: 3 ppb, K: 2 ppb,
Fe: 3 ppb, Al: 2 pppb, Pd: 85 ppb, Cu: 2p
The contents of pb and metallic impurities were significantly reduced. This polymer is referred to as "polymer (A-3)".

Example 4 5- [2-hydroxy-] was added to a 500 ml autoclave equipped with a Teflon coated stir bar.
2,2-Di (trifluoromethyl)] bicyclo [2.2.1] hept-2
-Ene 5.75 g (21 mmol) and 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene 1.75 g (9 mmol) were added, and further palladium (II) acetate 6.8 mg (0.030 mmo
l), 122 mg of copper (II) paratoluenesulfonate (0.30 m
mol), 140 mg (0.90 mmol) of 2,2'-bipyridine, 648 mg (6.0 mmol) of benzoquinone, and 30 ml of methanol were added. Carbon monoxide was blown into this container at 3 Mpa (30 bar) to apply pressure, and the mixture was stirred overnight while maintaining the internal temperature at 80 to 90 ° C. After completion of the reaction, carbon monoxide was degassed, and 200 ml of diethyl ether was added to dilute the polymer solution. The obtained organic layer was washed 6 times with 200 ml of 5% sodium carbonate, 2 times with 200 ml of saturated saline, and further 3 times with 200 ml of distilled water. Then, about 4 g of activated carbon was added to the organic layer, the mixture was stirred for 15 minutes, filtered, and the filtrate was concentrated. When the solution reached about 50 ml, it was filtered through a membrane filter and the filtrate was concentrated to dryness to obtain 7.8 g of a polymer (yield 93%). When the molecular weight was measured by GPC, it was MW = 1,300.

At this point, the concentration of metallic impurities in the polymer was measured by an atomic absorption photometer to find that N
a: 180 ppb, K: 110 ppb, Fe: 290 ppb, Al: 140
It was ppb, Pd: 1300 ppb, and Cu: 2900 ppb. To this polymer was added 39 g of toluene, and the mixture was added dropwise to 190 g of methanol heated to 30 ° C., 2 g of oxalic acid was added, and the mixture was stirred at the same temperature for 5 minutes. Then, the obtained coagulated product of the polymer was collected by filtration. 70 g of methyl isobutyl ketone, 0.16 g of oxalic acid, 80 g of ion-exchanged water, and 20 g of acetone were added to the obtained polymer, the temperature was raised to 80 ° C., and the mixture was stirred for 15 hours in the range of 79 to 81 ° C. and then left standing. As a result, the polymer solution layer and the water layer were separated, so the lower water layer was removed. To the obtained polymer solution layer, 120 g of ion-exchanged water was added again, and the mixture was stirred in the temperature range of 25 to 30 ° C for 1 minute and then left standing to separate and remove the aqueous layer. Thereafter, 77 g of the polymer solution was added dropwise to 308 g of methanol at room temperature, and after stirring for 1 minute, the coagulated product of the produced polymer was collected by filtration. The solidified product obtained was dried at 60 ° C. and 10 atm for 5 hours to give a polymer 7.2.
g was obtained. For the polymer thus purified,
When the concentration of metal impurities was measured by an atomic absorption spectrophotometer, Na: 3 ppb, K: 5 ppb, Fe: 5 ppb, Al:
The contents of 2 pppb, Pd: 75 ppb, Cu: 80 ppb and metallic impurities were greatly reduced. This polymer is referred to as "polymer (A-4)".

[Comparative Example 1] 5 ml of a commercially available strong acidic cation exchange resin (Amberlist 15: styrene sulfonic acid-divinylbenzene copolymer made by Organo, shape: granular) in a plastic bottle for 100 ml was used. 10 g of the obtained polymer solution (I) was added, and the bottle was shaken for 1 hour. The metal concentration of the polymer after shaking was Na: 2 ppb, K:
5 ppb, Fe: 40 ppb, Al: 5 ppb, Ni: 5500 ppb,
It was Cu: 10 ppb. [Comparative Example 2] The polymer solution (I) was treated in the same manner as in Comparative Example 1 except that the amount of the strongly acidic cation exchange resin in Comparative Example 1 was changed to 10 ml. The metal concentration of the polymer after the treatment was Na: 2 ppb, K: 5 ppb, Fe: 38 ppb, Al: 5
ppb, Ni: 5300 ppb, Cu: 8 ppb.

Evaluation Example 1 100 parts by weight of polymer (A-1), 2 parts by weight of bis (4-t-butylphenyl) iodonium perfluoro-n-octane sulfonate, N- (nonafluorobutyl sulfonyloxy) ) Bicyclo [2.2.1] hept
3 parts by weight of -5-ene-2,3-dicarboximide and 0.03 parts by weight of a compound represented by the following formula (C) as an acid diffusion inhibitor were dissolved in 800 parts by weight of propylene glycol monomethyl ether acetate to give A radioactive resin composition was obtained. This radiation-sensitive resin composition was applied by spin coating on a silicone wafer (ARC) having a DeepUV30 (manufactured by Brewer Science Co., Ltd.) film having a thickness of 520A formed on the surface thereof by spin coating, and at 90 ° C. at 130 ° C. on a hot plate. PB was performed for 2 seconds to form a resist film having a film thickness of 0.4 μm. ArF excimer laser exposure device (lens numerical aperture 0.55, exposure wavelength 193 nm) manufactured by Nikon Corporation was applied to the obtained film.
Was exposed through a mask pattern. Then 14
After performing PEB at 0 ° C. for 90 seconds, it is developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 1 minute, washed with water, and dried to form a positive resist pattern. The resolution was evaluated. As an evaluation method, a line and
The exposure amount for forming the space pattern (1L1S) with a line width of 1: 1 was taken as the optimum exposure amount, and this optimum exposure amount was taken as the sensitivity. Further, the minimum resist pattern size that can be resolved with the above optimum exposure dose was defined as the resolution. The results are shown in Table 1.

[0112]

[Chemical 25]

[Evaluation Example 2] A radiation sensitive resin composition was obtained in the same manner as in Evaluation Example 1 except that the polymer (A-2) was used in place of the polymer (A-1). Evaluation was performed in the same manner as in Evaluation Example 1 using the obtained radiation sensitive resin composition. The results are also shown in Table 1. [Evaluation Example 3] Polymer (A-3) instead of polymer (A-1)
A radiation-sensitive resin composition was obtained in the same manner as in Evaluation Example 1 except that was used. Evaluation was performed in the same manner as in Evaluation Example 1 using the obtained radiation sensitive resin composition. The results are also shown in Table 1. [Evaluation Example 4] Polymer (A-4) instead of polymer (A-1)
A radiation-sensitive resin composition was obtained in the same manner as in Evaluation Example 1 except that was used. Evaluation was performed in the same manner as in Evaluation Example 1 using the obtained radiation sensitive resin composition. The results are also shown in Table 1.

[0114]

[Table 1]

[0115]

According to the method of the present invention, an acid-added solution of an alicyclic hydrocarbon-based polymer in an organic solvent is dropped into a poor solvent of the alicyclic hydrocarbon-based polymer to form an alicyclic hydrocarbon-based polymer. With the operation of coagulating the hydrocarbon polymer and the operation of dissolving the coagulated alicyclic hydrocarbon polymer in a non-water-soluble organic solvent and contacting the solution with an acidic hot aqueous solution to extract the metal, Metals such as metals and heavy metals can be removed with high efficiency. Since the alicyclic hydrocarbon-based polymer treated by the method of the present invention has an extremely low metal content, it is suitable as a raw material for a radiation-sensitive resin composition used as a photoresist in the field of electronics such as semiconductor devices. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/38 501 G03F 7/38 501 H01L 21/027 H01L 21/30 502R (72) Inventor Haruo Iwasawa Tokyo 2-11-24, Tsukiji, Chuo-ku, Tokyo J-SR Co., Ltd. (72) Inventor Kimoyasu Sano 2--11-24, Tsukiji, Tokyo Chuo-ku, Tokyo F-Term (Reference) 2S025 AA01 AA02 AA03 AA11 AB16 AC04 AC08 AD03 BE00 BE10 BG00 BJ10 CB06 CB08 CB41 2H096 AA25 BA11 BA20 EA05 LA30 4J005 AB01 BC00 4J100 AG02Q AG04Q AJ01Q AJ02Q AJ08Q AJ09Q AL03Q AL09Q AL62Q AM01Q AM02Q AM14Q AM15Q AM32Q AM33Q AM43Q AM45Q AQ06Q AQ08Q AQ12Q AR03Q AR04Q AR11P AR11Q AR16Q AR21Q AR22Q AR25Q BA03P BA04Q BA15Q BA20Q BA22P BB18P CA01 CA04 FA08 GA17 JA38

Claims (6)

[Claims] 1. A step of mixing an alicyclic hydrocarbon-based polymer organic solvent solution with a poor solvent for the alicyclic hydrocarbon-based polymer and an acid to coagulate the alicyclic hydrocarbon-based polymer. And a step of mixing the solidified alicyclic hydrocarbon-based polymer, a water-insoluble organic solvent, an acid and water to extract the contained metal, the metal contained in the alicyclic hydrocarbon-based polymer. Removal method. 2. The alicyclic hydrocarbon-based polymer has the following formula:
The method according to claim 1, which is a polymer having a repeating unit represented by (2). [Chemical 1] (In the formula (2), A and B are the same or different and each is a hydrogen atom,
A monovalent acid having 20 or less carbon atoms which dissociates in the presence of a monovalent linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group or an acid to produce an acidic functional group. Represents a dissociable group, wherein at least one of A and B is a monovalent acid dissociable group having 20 or less carbon atoms, or A and B are carboxylic acid anhydrides bonded to each other to form an integral unit. Represents a ring, X and Y are the same or different and represent a hydrogen atom or a monovalent linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. ) 3. The alicyclic hydrocarbon-based polymer has the following formula:
3. The method according to claim 2, wherein the monomer represented by (1) is obtained by polymerizing in the presence of a metal compound catalyst. [Chemical 2] (In the formula (1), A, B, X, Y, and n are as defined in relation to the formula (2).) 4. The alicyclic hydrocarbon-based polymer has the following formula:
The method according to claim 1, which is a polymer having a repeating unit represented by (3) and / or formula (4). [Chemical 3] (In the formula (3), A, B, X, Y, and n are as defined in relation to the formula (2).) (In the formula (4), A, B, X, Y, and n are as defined in relation to the formula (2).) 5. The alicyclic hydrocarbon-based polymer according to claim 3,
The method according to claim 4, which is obtained by copolymerizing the monomer represented by the above formula (1) and carbon monoxide in the presence of a metal compound catalyst. 6. A radiation-sensitive product, comprising an alicyclic hydrocarbon-based polymer purified by the method for removing a contained metal according to any one of claims 1 to 5 and a radiation-sensitive acid generator. Sex composition.