JP2005018086A - Radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition as a chemically amplified resist, which is, in particular, excellent in resolution for a contact hole as well as excellent in transparency for radiation, dry etching durability, pattern profile, sensitivity, resolution or the like. <P>SOLUTION: The radiation-sensitive resin composition contains: (A) a resin having an alicyclic skeleton in the main chain and/or the side chain; (B) a resin having ≥60 %/μm transmittance for radiation at 100 to 300 nm wavelength; and (C) a radiation-sensitive acid generating agent. At least one of the component (C) and the component (B) contains an acid-cleaving group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a radiation sensitive resin composition, and more particularly to a radiation sensitive resin composition that can be suitably used as a chemically amplified resist.

In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, the development of lithography technology that enables microfabrication on the order of sub-half microns (0.4 μm or less) has recently been advanced. In the near future, it is said that a fine processing technique at a sub-quarter micron (0.25 μm or less) level will be required.
In the conventional lithography process, near ultraviolet rays such as i-rays are generally used as radiation, but it is said that fine processing at the subquarter micron level is extremely difficult with near ultraviolet rays.
Therefore, in order to enable fine processing at the sub-quarter micron level, use of radiation having a shorter wavelength is being studied. Examples of such short-wavelength radiation include an emission line spectrum of a mercury lamp, far-ultraviolet rays typified by an excimer laser, X-rays, electron beams, and the like. Alternatively, an ArF excimer laser (wavelength 193 nm) has been attracting attention.

As such a radiation-sensitive resin composition suitable for irradiation with an excimer laser, a chemistry of a component having an acid-dissociable functional group and a component that generates an acid upon irradiation with radiation (hereinafter referred to as “acid generator”). Many compositions utilizing the amplification effect (hereinafter referred to as “chemically amplified radiation-sensitive compositions”) have been proposed.
As such a chemically amplified radiation-sensitive composition, for example, Patent Document 1 contains a polymer having a t-butyl ester group of carboxylic acid or a t-butyl carbonate group of phenol and an acid generator. Compositions have been proposed. In this composition, the t-butyl ester group or t-butyl carbonate group present in the polymer is cleaved by the action of an acid generated by irradiation with radiation, and the polymer is separated from a carboxyl group or a phenolic hydroxyl group. As a result, the irradiation region of the resist film becomes easily soluble in an alkaline developer.

JP-B-2-27660

  By the way, many of the conventional chemically amplified radiation-sensitive compositions are based on phenolic resins. However, in such resins, when far ultraviolet rays are used as radiation, the aromatic ring in the resin is added to the aromatic ring. Due to the absorption of far-ultraviolet rays, there is a drawback that the irradiated far-ultraviolet rays cannot sufficiently reach the lower layer part of the resist film, so the irradiation amount is higher in the upper layer part of the resist film, and is lower in the lower layer part, There is a problem that the resist pattern after the development becomes thicker and trapezoidal as the upper part is thinner and lower, and a sufficient resolution cannot be obtained. In addition, when the resist pattern after development has a trapezoidal shape, a desired dimensional accuracy cannot be achieved in the next step, that is, etching or ion implantation, which is a problem. In addition, if the shape of the upper part of the resist pattern is not rectangular, there is a problem that the resist disappearing rate by dry etching is increased and it becomes difficult to control the etching conditions.

On the other hand, the shape of the resist pattern can be improved by increasing the radiation transmittance of the resist film. For example, a (meth) acrylate resin typified by polymethyl methacrylate is a highly preferable resin from the viewpoint of radiation transmittance because it is highly transparent to far ultraviolet rays. A chemically amplified radiation-sensitive resin composition using a base resin has been proposed. However, although this composition is excellent in terms of microfabrication performance, it does not have an aromatic ring and thus has a drawback of low dry etching resistance. In this case as well, it is difficult to perform highly accurate etching. It is.
Furthermore, as one of the measures for improving the resist characteristics of the chemically amplified radiation-sensitive composition, many multi-component compositions of three or more components containing a high-molecular or low-molecular additive have been proposed. However, the relationship between the radiation transmittance of the resist film and the action of the additive has not been sufficiently studied yet, and in particular, it is not satisfactory in terms of the resolution of the contact hole, and further, dry etching resistance, pattern shape In addition, the balance of characteristics including sensitivity, resolution, etc. is still not sufficient.

JP-A-4-226461

  The object of the present invention is to provide a chemically amplified resist that is sensitive to actinic radiation, for example, far ultraviolet rays typified by ArF excimer laser, and has excellent transparency to radiation, sufficient dry etching resistance, and particularly resolution of contact holes. Is to provide a radiation-sensitive resin composition that can be suitably used as a chemically amplified resist having excellent characteristics such as pattern shape, sensitivity, and resolution.

The gist of the present invention is as follows.
(A) a resin having an alicyclic skeleton in the main chain and / or side chain,
(B) A radiation-sensitive acid containing a resin having a transmittance of 60% / μm or more for radiation within a wavelength range of 100 to 300 nm as a film, and (C) a radiation-sensitive acid generator that generates an acid upon irradiation with radiation. A radiation-sensitive resin composition (hereinafter referred to as “first invention”), wherein at least one of the component (A) and the component (B1) contains an acid-cleavable group. ),
Consists of.

Secondly, the gist of the present invention is as follows.
(A) a resin having an alicyclic skeleton in the main chain and / or side chain,
(B2) A radiation-sensitive resin composition comprising a compound represented by the following general formula (1) having a molecular weight of 1,000 or less, and (C) a radiation-sensitive acid generator that generates an acid upon irradiation with radiation. And at least one of the component (A) and the component (B2) contains an acid-cleavable group (hereinafter referred to as “second invention”),

[In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an acid-cleavable group, and Z represents a group having a cyclic hydrocarbon structure in which the total number of carbon atoms constituting the ring is 7 to 25 A and b satisfy 0 ≦ a ≦ 6, 0 ≦ b ≦ 6, and 1 ≦ (a + b). ]
Consists of.

Hereinafter, the present invention will be described in detail.
Resin (A)
The component (A) in the first and second inventions comprises a resin having an alicyclic skeleton in the main chain and / or side chain (hereinafter referred to as “resin (A)”).
The resin (A) in the first invention must contain an acid-cleavable group when the resin (B1) described later does not contain an acid-cleavable group, and the resin (A) in the second invention When the compound (B2) described later does not contain an acid-cleavable group, it must contain an acid-cleavable group. However, in the first invention or the second invention, both the resin (A) and the resin (B1) or the compound (B2) may contain an acid-cleavable group.
The acid-cleavable group in the resin (A) can be present at an appropriate position, but when the resin (A) has an alicyclic skeleton in the main chain, the acid-cleavable group is present in the alicyclic skeleton. Preferably it is present. In the resin (A), the acid-cleavable group itself can have an alicyclic skeleton. The alicyclic skeleton in the resin (A) may be monocyclic or polycyclic, and one or more alicyclic skeletons may be present. The alicyclic skeleton has, for example, a substituent such as a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms at an appropriate position. Can also have.
In the first invention and the second invention, the resin (A) has an alicyclic skeleton in its main chain and / or side chain, so that the resist is particularly sensitive to radiation and has excellent transparency and dry etching resistance. Resin composition can be obtained.

  Resin (A) is a resin having an alicyclic skeleton only in the main chain (hereinafter referred to as “resin (AI)”), and a resin having an alicyclic skeleton only in the side chain (hereinafter referred to as “resin (AII)”). And a resin having an alicyclic skeleton in both the main chain and the side chain (hereinafter referred to as “resin (AIII)”). Hereinafter, these resins will be sequentially described.

  First, in the resin (AI), the alicyclic skeleton is preferably a skeleton represented by the following general formula (2) or the general formula (3), and particularly preferably a skeleton represented by the following general formula (2). .

[In General Formula (2) and General Formula (3), n is 0 or 1, A and B are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a carbon number. 1 to 10 represents a monovalent halogenated hydrocarbon group, and X and Y are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 10 carbon atoms. A halogenated hydrocarbon group or an acid-cleavable group is shown, and at least one of X and Y is an acid-cleavable group. ]

As the acid-cleavable group of X and Y in the general formula (2) and the general formula (3) (hereinafter referred to as “acid-cleavable group (i)”), a group — (CH ₂ ) _x COOR ³ , — ( CH ₂ ) _x 0COR ⁴ or-(CH ₂ ) _x CN (where R ³ is a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group having 1 to 10 carbon atoms, a tetrahydrofuranyl group, or a tetrahydropyranyl group. An alkoxycarbonylmethyl group (wherein the alkoxyl group has 1 to 10 carbon atoms), a carbobutoxymethyl group, a carbobutoxyethyl group, a carbobutoxypropyl group or a trialkylylsilyl group (wherein the alkyl group has a carbon number of R ⁴ represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group having 1 to 10 carbon atoms, and x is an integer of 0 to 4. Or a formula formed by X and Y being bonded to a carbon atom in the alicyclic skeleton

{However, R ⁵ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or —SO ₂ R ⁶ having 1 to 4 carbon atoms (where R ⁶ is an alkyl group having 1 to 4 carbon atoms or 1 carbon atom) -4 halogenated alkyl groups). }
An oxygen-containing heterocyclic structure or a nitrogen-containing heterocyclic structure represented by

In the preferred acid-cleavable group (i) of X and Y in the general formula (2) and the general formula (3), the group — (CH ₂ ) _x COOR ³ is, for example,
Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl 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-butylcyclohexyloxycarbonyl group, (Cyclo) alkoxycarbonyl groups such as cycloheptyloxycarbonyl group and cyclooctyloxycarbonyl group;
Aryloxycarbonyl groups such as a phenoxycarbonyl group, 4-t-butylphenoxycarbonyl group, 1-naphthylcarbonyl group;
Aralkyloxycarbonyl groups such as benzyloxycarbonyl group and 4-t-butylbenzyloxycarbonyl group;

Methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group, n-propoxycarbonylmethoxycarbonyl group, isopropoxycarbonylmethoxycarbonyl group, n-butoxycarbonylmethoxycarbonyl group, 2-methylpropoxycarbonylmethoxycarbonyl group, 1-methylpropoxycarbonylmethoxy Alkoxycarbonylmethoxycarbonyl groups such as a carbonyl group and t-butoxycarbonylmethoxycarbonyl group;
Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, 2-methylpropoxycarbonylmethyl group, 1-methylpropoxycarbonylmethyl group, t-butoxycarbonyl (Cyclo) alkoxycarbonylmethyl groups such as methyl group, cyclohexyloxycarbonylmethyl group, 4-t-butylcyclohexyloxycarbonylmethyl group;
Aryloxycarbonylmethyl groups such as phenoxycarbonylmethyl group and 1-naphthyloxycarbonylmethyl group;
An aralkyloxycarbonylmethyl group such as a benzyloxycarbonylmethyl group or 4-t-butylbenzyloxycarbonylmethyl group;

2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propoxycarbonylethyl group, 2-isopropoxycarbonylethyl group, 2-n-butoxycarbonylethyl group, 2- (2-methylpropoxy) carbonylethyl (Cyclo) alkoxycarbonyl such as 2- (1-methylpropoxy) carbonylethyl group, 2-t-butoxycarbonylethyl group, 2-cyclohexyloxycarbonylethyl group, 2- (4-butylcyclohexyloxycarbonyl) ethyl group Ethyl group;
2-aryloxycarbonylethyl groups such as 2-phenoxycarbonylethyl group and 2- (1-naphthyloxycarbonyl) ethyl group;
Examples thereof include 2-aralkyloxycarbonylethyl groups such as 2-benzyloxycarbonylethyl group and 2- (4-t-butylbenzyloxycarbonyl) ethyl group.

Among these groups, those corresponding to the group —COOR ³ are preferred, and more preferably a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and 2-methylpropoxycarbonyl. Group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, n-octyloxycarbonyl group, n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, t-butoxycarbonyl It is a methoxycarbonyl group.

In addition, as the group-(CH ₂ ) _x 0COR ⁴ , for example,
Acetyloxy, propionyloxy, butyryloxy, valeryloxy, caproyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, cyclohexylcarbonyloxy, 4-t- (Cyclo) acyloxy groups such as butylcyclohexylcarbonyloxy group;
Arylcarbonyloxy groups such as benzoyloxy group, 4-t-butylbenzoyloxy group, 1-naphthoyloxy group;
An aralkylcarbonyloxy group such as a benzylcarbonyloxy group or 4-t-butylbenzylcarbonyloxy group;

(Cyclo) acyloxymethyl groups such as acetyloxycarbonylmethyl group, propionyloxycarbonylmethyl group, butyryloxycarbonylmethyl group, cyclohexylcarbonyloxymethyl group, 4-t-butylcyclohexylcarbonyloxymethyl group; benzoyloxymethyl group, Arylcarbonyloxymethyl groups such as 1-naphthoyloxymethyl group;
An aralkylcarbonyloxymethyl group such as a benzylcarbonyloxymethyl group or 4-t-butylbenzylcarbonyloxymethyl group;
2- (cyclooxy) ethyl groups such as 2-acetyloxyethyl group, 2-propionyloxyethyl group, 2-butyryloxyethyl group, 2-cyclohexylcarbonyloxyethyl group, 2- (4-t-butylcyclohexylcarbonyloxy) ethyl group, etc. ) An acyloxyethyl group;
2-arylcarbonyloxyethyl groups such as 2-benzoyloxyethyl group and 2- (1-naphthoyloxy) ethyl group; 2-benzylcarbonyloxyethyl group, 2- (4-t-butylbenzylcarbonyloxy) ethyl group And 2-aralkylcarbonyloxyethyl groups such as

Examples of the group — (CH ₂ ) _x CN include a cyano group, a cyanomethyl group, a 2-cyanoethyl group, a 2-cyanopropyl group, a 3-cyanopropyl group, and a 4-cyanobutyl group.

  Furthermore, examples of the halogen atoms of A, B, X, and Y in the general formula (2) and the general formula (3) include F, Cl, Br, I, and the like. Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group, and an n-hexyl group. Groups, n-octyl groups, n-decyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups and the like (cyclo) alkyl groups; phenyl groups, 4-t-butylphenyl groups, 1-naphthyl groups, etc. An aryl group; aralkyl groups such as benzyl group and 4-t-butylbenzyl group can be exemplified, and examples of the monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms include, for example, A monovalent halogenated derivative of a hydrocarbon group of prime 1-10 can be mentioned.

  The resin (AI) can be produced, for example, by the following methods (a) to (e). (A) At least one norbornene derivative represented by the following general formula (4) (hereinafter referred to as “norbornene derivative (α)”) may optionally be at least one other ring-opening copolymerizable. A method of undergoing a ring-opening (co) polymerization step with an unsaturated alicyclic compound,

〔一般式（４）において、ｎ、Ａ、Ｂ、ＸおよびＹは一般式（２）および一般式（３）と同義であり、Ｒ⁷ 、Ｒ⁸ 、Ｒ⁹ およびＲ¹⁰はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜１０の１価の炭化水素基または炭素数１〜１０の１価のハロゲン化炭化水素基を示す。〕

[In General Formula (4), n, A, B, X and Y are as defined in General Formula (2) and General Formula (3), and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen. An atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms is shown. ]

(B) a method of radical copolymerizing at least one norbornene derivative (α) and one or more unsaturated compounds capable of copolymerization such as ethylene and maleic anhydride;
(C) A method of partially hydrolyzing and / or solvolyzing each resin obtained by the method (a) or (b) by a conventional method,
(D) The carboxyl group or hydroxyl group in the resin obtained by the method (c) is at least partially esterified by a conventional method, and the group -COOR ³ or
-OCOR ⁴ (hereinafter, these groups are collectively referred to as “acid-cleavable ester groups”),
(E) obtained by ring-opening (co) polymerization or radical copolymerization of at least one norbornene derivative represented by the following general formula (5) (hereinafter referred to as “norbornene derivative (β)”). ) A method in which a carboxyl group or a hydroxyl group in a polymer is at least partially esterified by a conventional method to introduce an acid-cleavable ester group.

In [Formula (5), n, A and B have the general formula (2) and the general formula (3) in the above ^{formula, R 7, R 8, R} 9 and R ¹⁰ are the general formula (4) and interchangeably Each of C and D is independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms, or — (CH ₂ ) _x COOH or - (CH ₂₎ shows the _x OH, and at least one of C and D - (CH _{2) x} COOH or - (CH _{2) x} OH, x is x in acid-cleavable group (i) It is synonymous with. ]

Furthermore, each resin obtained by the methods (c) to (e)
(F) The carboxyl group or hydroxyl group in the resin can be further esterified and modified by a method of introducing another acid-cleavable group.

Hereinafter, the methods (a) to (f) will be described.
First, in the method (i), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in general formula (4) are each a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms and a carbon atom having 1 to 10 carbon atoms. Examples of the monovalent halogenated hydrocarbon group include the same groups as those exemplified for the general formula (2) and the general formula (3).

Among the norbornene derivatives (α), specific examples of the compound in which n in the general formula (4) 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-isopropoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-n-butoxycarbonylbicyclo [2.2.1] hept-2-ene,
5- (2-methylpropoxy) carbonylbicyclo [2.2.1] hept-2-ene,
5- (1-methylpropoxy) carbonylbicyclo [2.2.1] hept-2-ene,
5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene,
5- (4′-t-butylcyclohexyloxy) carbonylbicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-tetrahydrofuranyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-tetrahydropyranyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-acetyloxybicyclo [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-isopropoxycarbonylbicyclo [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-tetrahydrofuranyloxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-tetrahydropyranyloxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-acetyloxybicyclo [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 (isopropoxycarbonyl) bicyclo [2.2.1] hept-2-ene,
5,6-di (n-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene,
5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene,
5,6-di (phenoxycarbonyl) bicyclo [2.2.1] hept-2-ene,
5,6-di (tetrahydrofuranyloxycarbonyl) bicyclo [2.2.1] hept-2-ene,
5,6-di (tetrahydropyranyloxycarbonyl) bicyclo [2.2.1] hept-2-ene,
Examples include 5,6-dicarboxyanhydride bicyclo [2.2.1] hept-2-ene.

Further, among the norbornene derivatives (α), as specific examples of the derivatives in which n in the general formula (4) is 1,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8- (2-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8- (1-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-cyclohexyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8- (4′-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-acetyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

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 .
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-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Methyl-8- (2-methylpropoxy) carbonyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8- (1-methylpropoxy) carbonyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-cyclohexyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8- (4′-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Methyl-8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-Methyl-8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-acetyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8,9-di (methoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (ethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (n-propoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (isopropoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (n-butoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (t-butoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (cyclohexyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (phenoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (tetrahydrofuranyloxycarbonyl) tetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-di (tetrahydropyranyloxycarbonyl) tetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-dicarboxyanhydride tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

  In the present invention, when two or more kinds of the norbornene derivatives (α) are used in combination, it is preferable to use a compound in which n is 0 and a compound in which n is 1 in the general formula (4).

Furthermore, as specific examples of other unsaturated alicyclic compounds capable of ring-opening copolymerization with norbornene derivative (α),
Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-Dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8- (2,2,2-trifluorocarboxyethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8- (2,2,2-trifluorocarboxyethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

Cyclobutene, cyclopentene, cyclooctene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, norbornene, 5-ethylidenenorbornene, 5-methylnorbornene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tricyclo [5.2.1.0 ^2,6 ] dec-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 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, 8-ethylidenetetracyclo [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 ] dodec-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 ^8,13] pentadeca-3-ene, or the like can be mentioned.

  In the resin (AI), the content of repeating units derived from the other unsaturated alicyclic compounds is usually 50 mol% or less, preferably 40 mol%, based on all repeating units in the resin (AI). Hereinafter, it is more preferably 30 mol% or less. In this case, if the content of repeating units derived from other unsaturated alicyclic compounds exceeds 50 mol%, the dry etching resistance tends to decrease.

The ring-opening (co) polymerization in the method (a) can be carried out in a suitable solvent using, for example, a metathesis catalyst.
Such a metathesis catalyst is usually at least one selected from the group of W, Mo or Re compounds (hereinafter referred to as “specific transition metal compounds”), and a Deming periodic table IA, IIA, IIIA, IVA. Alternatively, it consists of a compound of a group IVB metal and a combination with at least one selected from the group of compounds having a metal-carbon bond or metal-hydrogen bond (hereinafter referred to as “specific organometallic compound etc.”).

Specific transition metal compounds include, for example, W, Mo or Re halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, and the like. And derivatives of these compounds. Among these compounds, W or Mo compounds, more specifically W or Mo halides, oxyhalides or alkoxy halides are preferred from the viewpoints of polymerization activity, practicality and the like.
The specific transition metal compound can also be a compound coordinated by a suitable complexing agent such as triphenylphosphine (P (C ₆ H ₅ ) ₃ ), pyridine (NC ₅ H ₅ ), or the like.

Specific examples of the specific transition metal compound include WCl ₆ , WCl ₅ , WCl ₄ , WBr ₆ , WF ₆ , WI ₆ , MoCl ₅ , MoCl ₄ , MoCl ₃ , ReCl ₃ , WOCl ₄ , WOCl ₃ , WOBr ₃ , MoOCl ₃ , MoOBr ₃ , ReOCl ₃ , ReOBr ₃ , WCl ₂ (OC ₂ H ₅ ) ₄ , W (OC ₂ H ₅ ) ₆ , MoCl ₃ (OC ₂ H ₅ ) ₂ , Mo (OC ₂ H ₅ ) ₅ , WO ₂ (acac) ₂ (where acac represents an acetylacetonate residue), MoO ₂ (acac) ₂ , W (OCOR) ₅ (where OCOR represents a carboxylic acid residue), Mo (OCOR) ₅ , W (CO) ₆ , Mo (CO) ₆ , Re ₂ (CO) ₁₀ , WCl ₅・ P (C ₆ H ₅ ) ₃ ,
MoCl ₅・ P (C ₆ H ₅ ) ₃ , ReOBr ₃・ P (C ₆ H ₅ ) ₃ , WCl ₆・ NC ₅ H ₅ , W (CO) ₅・ P (C ₆ H ₅ ) ₃ ,
W (CO) may be mentioned ₃ · (CH ₃ CN) ₃ and the like.
Of these compounds, WCl ₆ , MoCl ₅ , WCl ₂ (OC ₂ H ₅ ) ₄ , MoCl ₃ (OC ₂ H ₅ ) _{2 and the} like are particularly preferable.
The said specific transition metal compound can be used individually or in combination of 2 or more types.
Moreover, the specific transition metal compound component which comprises a metathesis catalyst can also be used as a mixture of 2 or more types of compounds which react within a polymerization system and produce | generate a specific transition metal compound.

Next, specific examples of the specific organometallic compound include nC ₄ H ₉ Li, nC ₅ H ₁₁ Na, C ₆ H ₅ Na,
CH ₃ MgI, C ₂ H ₅ MgBr, CH ₃ MgBr, nC ₃ H ₇ MgCl, tC ₄ H ₉ MgCl, CH ₂ = CHCH ₂ MgCl, (C ₂ H ₅ ) ₂ Zn, (C ₂ H ₅ ) ₂ Cd , CaZn (C ₂ H ₅ ) ₄ , (CH ₃ ) ₃ B, (C ₂ H ₅ ) ₃ B, (nC ₄ H ₉ ) ₃ B, (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, CH _{3 AlCl 2, (CH 3)} 3 Al 2 Cl 3, (C 2 H 5) 3 Al, (C 2 H 5) 3 Al 2 Cl 3, (C 2 H 5) 2 Al · O (C 2 H 5 ) ₂ ,
(C ₂ H ₅ ) ₂ AlCl, C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (C ₂ H ₅ ) ₂ AlCN, LiAl (C _{2 H 5) 2, (nC 3} H 7) 3 Al, (iC 4 H 9) 3 Al, (iC 4 H 9) 2 AlH, (nC 6 H 13) 3 Al, (nC 8 H 17) 3 Al,
(C ₆ H ₅ ) ₃ Al, (CH ₃ ) ₄ Ga, (CH ₃ ) ₄ Sn, (nC ₄ H ₉ ) ₄ Sn, (C ₂ H ₅ ) ₃ SnH, LiH, NaH, B ₂ H ₆ ,
NaBH ₄ , AlH ₃ , LiAlH ₄ , TiH _{4 and the} like can be mentioned.
Among these _{compounds, (CH 3) 3 Al,} (CH 3) 2 AlCl, CH 3 AlCl 2, (CH 3) 3 Al 2 Cl 3, (C 2 H 5) 3 Al, (C 2 H 5) ₂ AlCl, C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , (C ₂ H ₅ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ ,
(C ₂ H ₅ ) ₂ AlCN, (nC ₃ H ₇ ) ₃ Al, (iC ₄ H ₉ ) ₃ Al, (iC ₄ H ₉ ) ₂ AlH, (nC ₆ H ₁₃ ) ₃ Al,
(nC ₈ H ₁₇ ) ₃ Al, (C ₆ H ₅ ) ₃ Al and the like are preferable.
The specific organometallic compounds can be used alone or in combination of two or more.
The quantitative relationship between the specific transition metal compound and the specific organometallic compound is usually in the range of 1: 1 to 1: 100, preferably 1: 2 to 1:50, as the metal atomic ratio.

One or more of the following activators (i) to (ix) can be further added to the catalyst comprising a combination of the specific transition metal compound and the specific organometallic compound in order to increase the catalytic activity.
Activator (i): B, BF ₃ , BCl ₃ , B (OnC ₄ H ₉ ) ₃ , BF ₃ · O (CH ₃ ) ₂ , BF ₃ · O (C ₂ H ₅ ) ₂ ,
BF ₃・ O (nC ₄ H ₉ ) ₂ , BF ₃・ 2C ₆ H ₅ OH, BF ₃・ 2CH ₃ COOH, BF ₃・ CO (NH ₂ ) ₂ ,
Boron compounds such as BF ₃ · N (C ₂ H ₄ OH) ₃ , BF ₃ · piperidine, BF ₃ · NH ₂ C ₂ H ₅ , B ₂ O ₃ , H ₃ BO _3, etc .; Si (OC ₂ H ₅ ) ₄ , silicon compounds such as Si (Cl) ₄ ,
Activator (ii): alcohols, hydroperoxides, dialkyl peroxides, diacyl peroxides,
Activator (iii): water,
Activator (iv): oxygen,
Activator (v): carbonyl compounds such as aldehydes and ketones, oligomers or polymers thereof,
Activator (vi): cyclic ethers such as ethylene oxide, epichlorohydrin, oxetane,
Activator (vii): Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Amines such as aniline, morpholine and piperidine; Azo compounds such as azobenzene,
Activator (viii): N-nitroso compounds such as N-nitrosodimethylamine and N-nitrosodiphenylamine,
Activator (ix): A compound having a nitrogen-chlorine bond or a sulfur-chlorine bond, such as trichloromelamine, N-chlorosuccinimide, phenylsulfenyl chloride and the like.
Since the quantitative relationship between these activators and specific transition metal compounds varies greatly depending on the type of activator used, it cannot be defined unconditionally, but in many cases, as a molar ratio, It is in the range of 0.005: 1 to 10: 1, preferably 0.05: 1 to 3.0: 1.

The average molecular weight of the resin (A1) obtained by ring-opening (co) polymerization in the method (a) can be changed by changing the reaction conditions such as the type and concentration of the metathesis catalyst, the polymerization temperature, the type and amount of the solvent, and the monomer concentration. Although it can be adjusted, it is preferable to add an appropriate molecular weight regulator to the reaction system.
Examples of the molecular weight regulator include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene; -Α, ω-diolefins such as butadiene and 1,4-pentadiene; vinyl aromatic compounds such as styrene and α-methylstyrene; acetylenes; polar allyl compounds such as allyl chloride, allyl acetate, and trimethylallyloxysilane Can be mentioned.
These molecular weight regulators can be used alone or in admixture of two or more.
The usage-amount of a molecular weight modifier is 0.005-1 mol normally with respect to 1 mol of all monomers, Preferably it is 0.02-0.7 mol.
Examples of the solvent used in the method (a) include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; cyclohexane, cycloheptane, Cycloalkanes such as cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylenedibromide and chlorobenzene; Examples thereof include saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate, and methyl propionate.
These solvents can be used alone or in admixture of two or more.

The radical copolymerization in the method (b) should be carried out in a suitable solvent using a radical polymerization catalyst such as hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, etc. Can do.
Examples of the solvent used in the method (b) include tetrahydrofuran and the like in addition to the solvents exemplified for the method (a). These solvents can be used alone or in admixture of two or more.
The hydrolysis rate in the method (c) is usually 10 to 100 mol%, preferably 20 to 95 mol%.
The introduction rate of the acid-cleavable ester group by the method (d) is usually 10 to 70 mol%, preferably 20 to 60 mol%.
In the method (e), the halogen atoms of C and D, the monovalent hydrocarbon group having 1 to 10 carbon atoms, and the monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms in the general formula (4). Examples thereof include the same groups as those exemplified for the general formula (2) and the general formula (3).
Specific examples of the norbornene derivative (β) include compounds obtained by converting the ester group in the compound exemplified for the norbornene derivative (α) to a carboxyl group or a hydroxyl group.
In the present invention, when two or more kinds of norbornene derivatives (β) are mixed and used, it is preferable to use a compound in which n is 0 and a compound in which n is 1 in the general formula (4).
The (co) polymer used in the method (e) can be obtained by hydrolyzing each resin (A1) obtained by the method (b) or (b), or synthesized separately. Also good.
The introduction rate of the acid-cleavable ester group by the method (e) is usually 10 to 70 mol%, preferably 20 to 60 mol%.

Furthermore, in the method (f), examples of other acid-cleavable groups include:
Lines such as methoxymethyloxy group, ethoxymethyloxy group, n-propoxymethyloxy group, isopropoxymethyloxy group, n-butoxymethyloxy group, t-butoxymethyloxy group, phenoxymethyloxy group, trichloroethoxymethyloxy group Acetal group;
Cyclic acetal groups such as tetrahydrofuranyloxy group and tetrahydropyranyloxy group; isopropoxycarbonyloxy group, 2-butenyloxycarbonyloxy group, t-butoxycarbonyloxy group, 1-methyl-2-propenyloxycarbonyloxy group, Carbonate groups such as cyclohexyloxycarbonyloxy group and 2-cyclohexenyloxycarbonyloxy group;
Orthomethoxy groups such as trimethoxymethyloxy group, triethoxymethyloxy group, tri-n-propoxymethyloxy group, methoxydiethoxymethyloxy group; methyl ether group, ethyl ether group, n-propyl ether group, isopropyl ether group, (cyclo) alkyl ether groups such as an n-butyl ether group, 2-methylpropyl ether group, 1-methylpropyl ether group, t-butyl ether group, cyclohexyl ether group, t-butyl cyclohexyl ether group;
Alkenyl ether groups such as allyl ether group, 2-butenyl ether group, 2-cyclohexenyl ether group, 1-methyl-2-propenyl ether group;
Aralkyl ether groups such as a benzyl ether group and a t-butyl benzyl ether group;
Examples thereof include vinyl ether groups, 1-propenyl ether groups, 1-butenyl ether groups, 1,3-butadienyl ether groups, and enol ether groups such as phenyl vinyl ether groups.
As an example of the introduction reaction of other acid-cleavable groups by the method of (f),
(F-1) Esterification reaction by addition reaction between a carboxyl group in each resin and 2,3-dihydro-4H-pyran,
(F-2) etherification reaction by addition reaction of a hydroxyl group in each resin and 2,3-dihydro-4H-pyran,
(F-3) An esterification reaction by a reaction between a hydroxyl group in each resin and a dialkyl dicarbonate can be exemplified.
The introduction rate of other acid-cleavable groups by the method (f) is usually 10 to 70 mol%, preferably 20 to 60 mol%.

As the resin (AI) in the present invention, those having a small number of carbon / carbon unsaturated bonds are preferable from the viewpoint of transparency to radiation.
Such a resin (AI) can be produced, for example, by hydrogenation or water addition at an appropriate stage in the method (a) or the method (e) in which the ring-opening (co) polymerization is performed, or following these methods. The resin (AI) can be obtained by performing an addition reaction such as halogen addition, hydrogen halide addition, and the like, and the resin (AI) obtained by hydrogenation reaction is particularly preferable. The resin (AI) obtained by the method (b) and the radical (co) polymerization method (e) has substantially no carbon-carbon unsaturated bond.
The hydrogenation rate in the hydrogenated resin (AI) is preferably 70% or more, more preferably 90% or more, and particularly preferably 100%.
As a catalyst used for the said hydrogenation reaction, what is used for the hydrogenation reaction of the normal olefinic compound can be used, for example.
Among such hydrogenation catalysts, the heterogeneous catalyst includes, for example, a solid catalyst in which a noble metal such as Pd, Pt, Ni, Rh, and Ru is supported on a carrier such as carbon, silica, alumina, and titania. Can be mentioned. These heterogeneous catalysts can be used alone or in admixture of two or more.
Examples of the homogeneous catalyst include, for example, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, Examples thereof include rhodium such as chlorotris (triphenylphosphine) rhodium. These homogeneous catalysts can be used alone or in admixture of two or more.
Of the hydrogenation catalysts, heterogeneous catalysts are preferable in that the reaction activity is high, the catalyst can be easily removed after the reaction, and the color tone of the resulting resin (AI) is excellent.
The hydrogenation reaction is usually carried out at 0 to 200 ° C., preferably 20 to 180 ° C. in a hydrogen gas atmosphere of normal pressure to 300 atm, preferably 3 to 200 atm.

As the resin (AI), the following resin (AI-1), resin (AI-2) and resin (AI-3) are particularly preferable.
The resin (AI-1) is a resin composed of a repeating unit represented by the following general formula (6).

〔一般式（６）において、ｎおよびＡはそれぞれ一般式（２）および一般式（３）と同義であり、Ｘは酸開裂性基（ｉ）を示す。〕

[In General formula (6), n and A are synonymous with General formula (2) and General formula (3), respectively, and X shows acid-cleavable group (i). ]

As the resin (AI-1), the acid-cleavable group (i) of X is a group — (CH ₂ ) _x COOR ^{3 wherein} the acid-cleavable group (i) in the general formula (2) and the general formula (3) is mentioned. Is more preferably a resin in which the acid-cleavable group (i) of X is a group —COOR ³ , and particularly preferably the acid-cleavable group (i) of X is a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, n-octyloxycarbonyl group N-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group and t-butoxycarbonylmeth Sheet is a resin comprising a group selected from the group consisting of a carbonyl group.
In the resin (AI-1), one or more repeating units represented by the general formula (6) can be present.

  Resin (AI-2) is a random copolymer composed of a repeating unit represented by the following general formula (6) and a repeating unit represented by the following general formula (7).

[In General Formula (6) and General Formula (7), n and m are each independently 0 or 1, A and B are respectively synonymous with General Formula (2) and General Formula (3), and X is An acid cleavable group (i) is shown. ]

As the resin (AI-2), an acid-cleavable group (i) of X is a group — (CH ₂ ) _x COOR ^{3 wherein} the acid-cleavable group (i) in the general formula (2) and the general formula (3) is mentioned Is more preferably a resin in which the acid-cleavable group (i) of X is a group —COOR ³ , and particularly preferably the acid-cleavable group (i) of X is a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, n-octyloxycarbonyl group N-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group and t-butoxycarbonylmeth A resin comprising a group selected from the group of xyloxy groups.
The molar ratio of the repeating unit represented by the general formula (6) to the repeating unit represented by the general formula (7) in the resin (AI-2) is usually 95/5 to 20/80, preferably 90 / 10-30 / 70.
In the resin (AI-2), one or more repeating units represented by the general formula (6) and one represented by the general formula (7) may be present.

  Resin (AI-3) is a random copolymer composed of a repeating unit represented by the following general formula (8) and a repeating unit represented by the following general formula (9).

[In General formula (8) and General formula (9), A and B are synonymous with General formula (2) and General formula (3), respectively, X and Y are respectively independently a hydrogen atom, a halogen atom, and carbon number. 1 to 10 monovalent hydrocarbon group, a monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms or an acid-cleavable group (i), and at least one of X and Y is an acid-cleavable group (I). ]

As the resin (AI-3), the acid-cleavable group (i) of X and Y is the group — (CH ₂ ) _x mentioned for the acid-cleavable group (i) in the general formula (2) and the general formula (3). A resin comprising COOR ³ is preferred, more preferably a resin in which the X and Y acid-cleavable groups (i) comprise the group —COOR ³ , and particularly preferably the X and Y acid-cleavable groups (i) are represented by methoxycarbonyl. Group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, n-octyloxycarbonyl group, n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group and t It is a resin comprising a group selected from the group consisting of-butoxycarbonyl, methoxycarbonyl group.
The molar ratio of the repeating unit represented by the general formula (8) to the repeating unit represented by the general formula (9) in the resin (AI-3) is usually 95/5 to 10/90, preferably 90 / 10-20 / 80.
In the resin (AI-3), one or more repeating units represented by the general formula (8) and one represented by the general formula (9) may be present.

Next, examples of the resin (AII) include a resin having a structure in which the hydrogen atom of the carboxyl group in the carboxyl group-containing alkali-soluble resin is substituted with a group having an alicyclic skeleton.
Examples of the group having an alicyclic skeleton in the resin (II) include groups having a single ring such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, and a 4-methoxycyclohexyl group; a norbornyl group, an isobornyl group, Tricyclodecanyl group, tetracyclodecanyl group, dicyclopentenyl group, adamantyl group, adamantylmethyl group, 1-methyladamantyl group, tricyclo [5.2.1.0] decanyl group, carboxytricyclo [5.2 .1,0] decanyl group, carboxytetracyclodecanyl group, and the like.
Among these groups having an alicyclic skeleton, an adamantyl group, an adamantylmethyl group, a 1-methyladamantyl group, a tricyclo [5.2.1.0] decanyl group, a carboxytricyclo [5.2.1,0]. A decanyl group, a carboxytetracyclodecanyl group and the like are preferable.

  Examples of the acid-cleavable group (hereinafter referred to as “acid-cleavable group (ii)”) that can be contained in the resin (AII) include a substituted methyl group, a 1-substituted ethyl group, and a 1-branched alkyl group. Group, silyl group, germyl group, alkoxycarbonyl group, acyl group, cyclic acid-cleavable group and the like.

Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, and methoxyphenacyl. Group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group , Ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t-butoxy Rubonirumechiru group, and the like can be mentioned.
Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1- Diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1- Phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-isopropoxycarbonylethyl group, 1-n-butoxycarbonylethyl Group, 1-t-butoxycarbonylethyl group and the like. Examples of the 1-branched alkyl group include isopropyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, and the like. Can do.

Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, isopropyldimethylsilyl group, methyldiisopropylsilyl group, triisopropylsilyl group, t-butyldimethylsilyl group, methyldiethyl group. -T-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group and the like can be mentioned.
Examples of the germyl group include trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, isopropyldimethylgermyl group, methyldiisopropylgermyl group, triisopropylgermyl group, Examples thereof include a t-butyldimethylgermyl group, a methyldi-t-butylgermyl group, a tri-t-butylgermyl group, a phenyldimethylgermyl group, a methyldiphenylgermyl group, and a triphenylgermyl group.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a t-butoxycarbonyl group.

Examples of the acyl group include acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl Group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl group , Benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group Isonicotinoyl group, p- toluenesulfonyl group, and mesyl group.
Further, examples of the cyclic acid-cleavable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a group having an alicyclic skeleton such as a 4-methoxycyclohexyl group, a tetrahydropyranyl group, Tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-1,1- A dioxide group etc. can be mentioned.

  Among these acid-cleavable groups (ii), t-butyl group, t-butoxycarbonyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-butoxyethyl group, tetrahydropyranyl group, methyltetrahydro A pyranyl group, tetrahydrofuranyl group, methyltetrahydrofuranyl group, t-butoxycarbonylmethyl group and the like are preferable.

Resin (II) is, for example,
(G) A method of (co) polymerizing a polymerizable unsaturated compound having an alicyclic skeleton in the side chain, optionally together with another polymerizable unsaturated compound,
(H) It can be produced by a method of introducing a group having one or more alicyclic skeletons into the carboxyl group of a carboxyl group-containing alkali-soluble resin produced in advance.
In addition, the resin (II) containing an acid-cleavable group (ii)
(G-1) A compound in which the acid-cleavable group (ii) itself is a group having the alicyclic skeleton as a polymerizable unsaturated compound having an alicyclic skeleton in the side chain by the method of (g). How to use,
(G-2) A method of using a compound containing an acid-cleavable group (ii) as another polymerizable unsaturated compound in the method (G).
(Chi-1) In addition to the method of introducing the acid-cleavable group (ii) simultaneously into the carboxyl group of the carboxyl group-containing alkali-soluble resin by the method (Ci),
(I) One or more acid-cleavable groups (ii) are added to the carboxyl group in the copolymer of a polymerizable unsaturated compound having an alicyclic skeleton in the side chain and a carboxyl group-containing polymerizable unsaturated compound. It can be manufactured by a method to be introduced.

Hereinafter, these methods will be described.
In the method (g), examples of the polymerizable unsaturated compound having an alicyclic skeleton in the side chain include norbornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate. , (Meth) acrylic acid tetracyclodecanyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid adamantyl, (meth) acrylic acid adamantyl methyl, (meth) acrylic acid 1-methyladamantyl, (meth) acrylic acid Examples thereof include carboxytricyclodecanyl and carboxytetracyclodecanyl (meth) acrylate.
Among these polymerizable unsaturated compounds having an alicyclic skeleton in the side chain, tricyclodecanyl (meth) acrylate, tetracyclodecanyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic Preferred are acid carboxytricyclodecanyl, carboxytetracyclodecanyl (meth) acrylate, and the like.

In the method (g), as other polymerizable unsaturated compound, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate (Meth) acrylic esters such as propyl, 3-hydroxypropyl (meth) acrylate;
α-hydroxymethyl acrylate esters such as methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, n-butyl α-hydroxymethyl acrylate;
Aliphatic unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid;
Carboxyl group-containing aliphatic unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate Esters;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate; unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesaconnitrile, citracononitrile, itaconnitrile;
Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide;
Other nitrogen-containing vinyl compounds such as N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine and vinylimidazole can be mentioned.
These other polymerizable unsaturated compounds can be used alone or in admixture of two or more.

In the method of (to-1) above, the acid-cleavable group (ii) -containing polymerizable unsaturated compound in which the acid-cleavable group (ii) itself is a group having an alicyclic skeleton is, for example, (meta ) Cyclopropyl acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopropyloxycarbonylethyl (meth) acrylate , (Meth) acrylic acid 2-cyclopentyloxycarbonylethyl, (meth) acrylic acid 2-cyclohexyloxycarbonylethyl, (meth) acrylic acid 2-cyclohexenyloxycarbonylethyl, (meth) acrylic acid 2- (4-methoxycyclohexyl) ) Oxycarbonylethyl and the like.
Among these acid-cleavable groups (ii), the acid-cleavable group (ii) -containing polymerizable unsaturated compound which itself is a group having an alicyclic skeleton, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, Preference is given to cyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate and the like.
The acid-cleavable group (ii) -containing polymerizable unsaturated compound, which itself is a group having an alicyclic skeleton, can be used alone or in admixture of two or more.

In the method (to-2), examples of other polymerizable unsaturated compound containing an acid-cleavable group (ii) include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itacon. Aliphatic unsaturated carboxylic acids such as acid, citraconic acid, mesaconic acid; 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, (meth) acrylic The hydrogen atom of the carboxyl group of the carboxyl group-containing aliphatic unsaturated carboxylic acid ester such as 4-carboxybutyl acid is replaced with an acid-cleavable group (ii) (excluding a group having an alicyclic skeleton). And the like.
Among the other polymerizable unsaturated compounds containing these acid-cleavable groups (ii), tetrahydropyranyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, 2-oxocyclohexyl (meth) acrylate, ( Preference is given to t-butyl acrylate.
The other polymerizable unsaturated compound containing the acid-cleavable group (ii) can be used alone or in admixture of two or more.

Next, in the method (h), examples of the carboxyl group-containing alkali-soluble resin include aliphatic unsaturated carboxylic acids and carboxyl group-containing aliphatic unsaturated carboxylic acids exemplified for the method (g). (Co) polymers of the above and the like.
In the method (v), the carboxyl group-containing polymerizable unsaturated compounds can be used alone or in admixture of two or more.

Next, in the method (i), the polymerizable unsaturated compound having an alicyclic skeleton in the side chain is, for example, polymerizable having an alicyclic skeleton in the side chain exemplified for the method (g). Unsaturated compounds can be mentioned, and examples of the carboxyl group-containing polymerizable unsaturated compound include the aliphatic unsaturated carboxylic acids and carboxyl group-containing aliphatic unsaturated carboxylic acid esters exemplified for the method (2) above. And the like compounds.
In the method (i), as the polymerizable unsaturated compound having an alicyclic skeleton in the side chain, the same compounds as those mentioned in the method (g) are preferable, and carboxyl group-containing polymerizable unsaturated compounds are also included. As the compound, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and the like are preferable.
In the method (i), the polymerizable unsaturated compound having an alicyclic skeleton in the side chain and the carboxyl group-containing polymerizable unsaturated compound can be used alone or in admixture of two or more.

In the methods (v) and (v), other polymerizable unsaturated compounds can be used in combination.
Examples of the other polymerizable unsaturated compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic acid esters such as 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, α Α-hydroxymethyl acrylate esters such as n-propyl hydroxymethyl acrylate and n-butyl α-hydroxymethyl acrylate; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; (meth) acrylonitrile, α- Chloroacrylonitrile, crotonnitrile, maleinonitrile, Unsaturated nitrile compounds such as malonitrile, mesaconitrile, citracon nitrile, itacon nitrile; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumaramide, mesaconamide, citraconamide, itaconamide, etc. Unsaturated amide compounds; other nitrogen-containing vinyl compounds such as N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, vinylimidazole, and other polymerizable unsaturated compounds having an alicyclic skeleton in the side chain described above An acid-cleavable group (ii) itself is a group having an alicyclic skeleton, an acid-cleavable group (ii) containing a polymerizable unsaturated compound, an acid-cleavable group (ii) (however, a group having an alicyclic skeleton) ) -Containing polymerizable unsaturated compounds can be appropriately selected and used.
These other polymerizable unsaturated compounds can be used alone or in admixture of two or more.

  (Co) polymerization in the method of (g), polymerization for producing a carboxyl group-containing alkali-soluble resin in the method of (h), and a polymerizable unsaturated compound having an alicyclic skeleton in the side chain in the method of (i) Copolymerization for producing a copolymer with a carboxyl group-containing polymerizable unsaturated compound is, for example, appropriately selecting a radical polymerization initiator, an anionic polymerization catalyst, a coordination anionic polymerization catalyst, a cationic polymerization catalyst, etc., bulk polymerization, The polymerization can be carried out by an appropriate polymerization method such as solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, bulk-suspension polymerization.

  The content of the repeating unit having an alicyclic skeleton in the side chain in the resin (AII) is usually from 30 to 80 mol%, preferably from 40 to 70 mol%, based on the total repeating units, and also has acid cleavability. The content of the repeating unit containing the group (ii) is usually 70 to 20 mol%, preferably 60 to 30 mol%, based on all repeating units.

As resin (II), the following are preferable.
(Meth) isobornyl acrylate / methyl (meth) acrylate copolymer, isobornyl (meth) acrylate / (meth) acrylic acid copolymer, isobornyl (meth) acrylate / methyl (meth) acrylate / (meth) Acrylic acid copolymer, isobornyl (meth) acrylate / t-butyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer, isobornyl (meth) acrylate / (meth) acrylic acid Tetrahydropyranyl / methyl (meth) acrylate / (meth) acrylic acid copolymer, isobornyl (meth) acrylate / 3-oxocyclohexyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer Polymer, tricyclodecanyl (meth) acrylate / t-butyl (meth) acrylate / (meth) acrylic Acid copolymer, tricyclodecanyl (meth) acrylate / t-butoxycarbonyl (meth) acrylate / (meth) acrylic acid copolymer, tricyclodecanyl (meth) acrylate / (meth) acrylic acid 1 -Ethoxyethyl / (meth) acrylic acid copolymer, tricyclodecanyl (meth) acrylate / (meth) acrylic acid 1-n-butoxyethyl / (meth) acrylic acid copolymer, (meth) acrylic acid tri Cyclodecanyl / (meth) acrylic acid tetrahydropyranyl / (meth) acrylic acid copolymer, (meth) acrylic acid tricyclodecanyl / (meth) acrylic acid methyltetrahydropyranyl / (meth) acrylic acid copolymer , (Meth) acrylic acid tricyclodecanyl / (meth) acrylic acid tetrahydrofuranyl / (meth) acrylic acid copolymer, (meth) Acrylic acid tricyclodecanyl / (meth) acrylate tetrahydrofuranyl / (meth) acrylic acid copolymer,

(Meth) acrylic acid tricyclodecanyl / (meth) acrylic acid t-butyl / (meth) acrylic acid 2-hydroxypropyl copolymer, (meth) acrylic acid tricyclodecanyl / (meth) acrylic acid t-butoxy Carbonyl / (meth) acrylic acid 2-hydroxypropyl copolymer, (meth) acrylic acid tricyclodecanyl / (meth) acrylic acid 1-ethoxyethyl / (meth) acrylic acid 2-hydroxypropyl copolymer, (meta ) Tricyclodecanyl acrylate / 1-n-butoxyethyl (meth) acrylate / 2-hydroxypropyl copolymer (meth) acrylate, tricyclodecanyl (meth) acrylate / tetrahydropyrani (meth) acrylate / (Meth) acrylic acid 2-hydroxypropyl copolymer, (meth) acrylic acid tricyclodecane / (Meth) acrylic acid methyltetrahydropyranyl / (meth) acrylic acid 2-hydroxypropyl copolymer, (meth) acrylic acid tricyclodecanyl / (meth) acrylic acid tetrahydrofuranyl / (meth) acrylic acid 2-hydroxy Propylene copolymer, (meth) acrylic acid tricyclodecanyl / (meth) methyl methacrylate tetrahydrofuranyl / (meth) acrylic acid 2-hydroxypropyl copolymer, (meth) acrylic acid tricyclodecanyl / (meth) Tetrahydropyranyl acrylate / ethyl α-hydroxymethyl acrylate copolymer, tricyclodecanyl (meth) acrylate / t-butyl (meth) acrylate / ethyl α-hydroxymethyl acrylate copolymer,

(Meth) acrylic acid tetracyclodecanyl / (meth) acrylic acid t-butyl / (meth) methyl acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid tetracyclodecanyl / (meth) acrylic acid Tetrahydropyranyl / methyl (meth) acrylate / (meth) acrylic acid copolymer, tetracyclodecanyl (meth) acrylate / 3-oxocyclohexyl (meth) acrylate / methyl (meth) acrylate / (meth) Acrylic acid copolymer, adamantyl (meth) acrylate / t-butyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer, adamantyl methyl (meth) acrylate / (meth) acrylic T-butyl acid / methyl (meth) acrylate / (meth) acrylic acid copolymer, adamantyl (meth) acrylate / Tetrahydropyranyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer, adamantyl methyl copolymer (meth) acrylate / tetrahydropyranyl (meth) acrylate / methyl (meth) acrylate / (Meth) acrylic acid, (meth) acrylic acid adamantyl / (meth) acrylic acid 3-oxocyclohexyl / (meth) acrylic acid methyl / (meth) acrylic acid copolymer, (meth) acrylic acid adamantyl methyl / (meta ) 3-oxocyclohexyl acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer, isobornyl (meth) acrylate / tricyclodecanyl (meth) acrylate / methyl (meth) acrylate / (meta ) Acrylic acid copolymer, isobornyl (meth) acrylate / (meth) acrylic acid Tracyclodecanyl / methyl (meth) acrylate / (meth) acrylic acid copolymer, isobornyl (meth) acrylate / adamantyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer , Isobornyl (meth) acrylate / adamantylmethyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer, and the like.

Furthermore, as the resin (AIII), for example, a copolymer of the norbornene derivative (β) and a polymerizable unsaturated compound having an alicyclic skeleton in the side chain (hereinafter referred to as “resin (AIII-1)”). In addition, as a resin (AIII) containing an acid-cleavable group, a copolymer of the norbornene derivative (α) and a polymerizable unsaturated compound having an alicyclic skeleton in the side chain (hereinafter referred to as “resin (AIII)”. -2) "), a polymer containing the norbornene derivative (β), a polymerizable unsaturated compound having an alicyclic skeleton in the side chain, and an acid-cleavable group (excluding a group having an alicyclic skeleton). And a copolymer with an unsaturated compound (hereinafter referred to as “resin (AIII-3)”).
Examples of the polymerizable unsaturated compound having an alicyclic skeleton in the side chain in the resins (AIII-1) to (AIII-3) include, for example, polymerization having an alicyclic skeleton in the side chain exemplified for the resin (AII). And the like, and examples of the acid-cleavable group-containing polymerizable unsaturated compound in the resin (AIII-3) include the acid-cleavable groups exemplified for the resin (AII). (Ii) A polymerizable unsaturated compound or an acid-cleavable group (ii) (excluding a group having an alicyclic skeleton), which itself is a group having an alicyclic skeleton. A compound etc. can be mentioned.

In the resins (AIII-1) to (AIII-3), other polymerizable unsaturated compounds may be used in combination with the polymerizable unsaturated compounds.
Examples of the other polymerizable unsaturated compounds include, in the resin (AIII-1), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid. (meth) acrylic acid esters such as n-butyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate; methyl α-hydroxymethyl acrylate, α-hydroxymethyl acrylates such as ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, n-butyl α-hydroxymethyl acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumar Aliphatic unsaturated carboxylic acids such as acid, itaconic acid, citraconic acid, mesaconic acid; (meth) a Carboxyl group-containing aliphatic unsaturated carboxylic esters such as 2-carboxyethyl acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate; unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesaconnitrile, citracononitrile, itaconnitrile; Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumaramide, mesaconamide, citraconic amide, itaconamide; N-vinyl-ε-caprolacta And other nitrogen-containing vinyl compounds such as N-vinylpyrrolidone, vinylpyridine, vinylimidazole, and norbornene derivatives (β).
These other polymerizable unsaturated compounds can be used alone or in admixture of two or more.

In the resin (AIII-2), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, α Α-hydroxymethyl acrylate esters such as n-propyl hydroxymethyl acrylate and n-butyl α-hydroxymethyl acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesacone Aliphatic unsaturated carboxylic acids such as acids; 2-carboxyethyl (meth) acrylate, Carboxyl group-containing aliphatic unsaturated carboxylic esters such as (meth) acrylic acid 2-carboxypropyl, (meth) acrylic acid 3-carboxypropyl, and (meth) acrylic acid 4-carboxybutyl; vinyl acetate, vinyl propionate, Vinyl esters such as vinyl butyrate; unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itaconnitrile; (meth) acrylamide, N, N- Unsaturated amide compounds such as dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide; N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinyl In addition to other nitrogen-containing vinyl compounds such as rupyridine and vinylimidazole, the norbornene derivative (β), the acid-cleavable group (ii) itself has an alicyclic skeleton and an acid-cleavable group (ii) -containing polymerizable unsaturated compound And an acid-cleavable group (ii) (excluding a group having an alicyclic skeleton) -containing polymerizable unsaturated compound.
These other polymerizable unsaturated compounds can be used alone or in admixture of two or more.

In the resin (AIII-3), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate; methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, α Α-hydroxymethyl acrylate esters such as n-propyl hydroxymethyl acrylate and n-butyl α-hydroxymethyl acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesacone Aliphatic unsaturated carboxylic acids such as acids; 2-carboxyethyl (meth) acrylate, Carboxyl group-containing aliphatic unsaturated carboxylic esters such as (meth) acrylic acid 2-carboxypropyl, (meth) acrylic acid 3-carboxypropyl, and (meth) acrylic acid 4-carboxybutyl; vinyl acetate, vinyl propionate, Vinyl esters such as vinyl butyrate; unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citracononitrile, itaconnitrile; (meth) acrylamide, N, N -Unsaturated amide compounds such as dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide; N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinyl Other nitrogen-containing vinyl compounds such as rupyridine and vinylimidazole can be mentioned.
These other polymerizable unsaturated compounds can be used alone or in admixture of two or more.

  The total content of the repeating unit having an alicyclic skeleton in the main chain and the repeating unit having an alicyclic skeleton in the side chain in the resin (AIII) is usually 30 to 90 mol% with respect to all the repeating units, Preferably it is 40-80 mol%, and content of the repeating unit containing an acid-cleavable group is 10-70 mol% normally with respect to all the repeating units, Preferably it is 20-60 mol%.

In the first and second inventions, the resin (A) is preferably a resin having an alicyclic skeleton at least in the main chain, and particularly preferably a resin (AI).
The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) by gel permeation chromatography (GPC) of the resin (A) is usually 5,000 to 300,000, preferably 5,000 to 200,000, More preferably, it is 10,000-100,000. In this case, if the Mw of the resin (A) is less than 5,000, the heat resistance as a resist tends to be lowered, and if it exceeds 300,000, the developability as a resist tends to be lowered.
In the 1st invention and the 2nd invention, resin (A) can be used individually or in mixture of 2 or more types.

The resin (A) in the first and second inventions is more preferable as there are fewer impurities. This impurity is mainly derived from the catalyst used in manufacturing each resin. Examples of impurities that should be considered in particular from the viewpoint of resist include halogens such as F, Cl, Br, and deming. In the periodic table, metals of Group IV, Group V, Group VI, Group VII and Group VIII can be exemplified. In this case, the residual halogen content in the resin is preferably 3 ppm or less, particularly 2 ppm or less, and the residual metal content is preferably 300 ppb or less, particularly 100 ppb or less. In addition, the residual metal content is preferably 300 ppb or less, particularly preferably 100 ppb or less. By making these impurity contents below the above values, sensitivity, resolution, process stability, pattern shape and the like are further improved.
As a method for reducing impurities in the resin, in the case of residual halogen, a method of sufficiently washing and removing can be mentioned. In the case of residual metal, washing of the resin solution with pure water or liquid-liquid extraction, resin solution Examples of the method include a combination of washing with pure water or liquid-liquid extraction and physical purification methods such as ultrafiltration and centrifugation.

Next, the component (B1) in the first invention is made of a resin (hereinafter referred to as “resin (B1)”) having a transmittance of 60% / μm or more for radiation within a wavelength range of 100 to 300 nm as a film. .
When the resin (A) does not contain an acid cleavable group, the resin (B1) in the first invention must contain an acid cleavable group.
When the radiation-sensitive resin composition in the first invention is used as a chemically amplified resist, the radiation has a wavelength in the range of 100 to 300 nm, preferably ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm) is used. The transmittance of the resin (B1) with respect to the ArF excimer laser and the KrF excimer laser is preferably 65% or more, particularly preferably 70% or more.

Examples of the resin (B1) (hereinafter referred to as “resin (B1-I)”) having a transmittance with respect to an ArF excimer laser of 60% or more include:
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Homopolymers or copolymers of (meth) acrylic esters such as propyl and 3-hydroxypropyl (meth) acrylate; one or more of the (meth) acrylic esters and other polymerizable unsaturation Compounds, for example, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and other aliphatic unsaturated carboxylic acids; (meth) acrylic acid 2-carboxyethyl, (meth) acrylic 2-carboxypropyl acid, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, etc. Carboxyl group-containing aliphatic unsaturated carboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citracone Unsaturated nitrile compounds such as nitrile and itacone nitrile; Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumaramide, mesaconamide, citraconic amide, itaconamide; N- In addition to copolymers with one or more other nitrogen-containing vinyl compounds such as vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, vinylimidazole,

As a resin (B1-I) containing an acid-cleavable group (ii), for example,
(Meth) acrylic acid t-butyl homopolymer, (meth) acrylic acid t-butyl / (meth) methyl acrylate copolymer, (meth) acrylic acid t-butyl / (meth) acrylic acid copolymer, T-butyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer, t-butyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid / (meth) (Meth) acrylic acid such as tetrahydropyranyl acrylate copolymer, t-butyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid 3-oxocyclohexyl copolymer (co) polymer of t-butyl; homopolymer of tetrahydropyranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate / methyl (meth) acrylate copolymer , Tetrahydropyranyl (meth) acrylate / (meth) acrylic acid copolymer, tetrahydropyranyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid (Co) polymers of tetrahydropyranyl (meth) acrylates such as tetrahydropyranyl / methyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid 3-oxocyclohexyl copolymer; (meth) acrylic Homopolymer of 3-oxocyclohexyl acid, 3-oxocyclohexyl (meth) acrylate / methyl (meth) acrylate copolymer, 3-oxocyclohexyl (meth) acrylate / (meth) acrylic acid copolymer, ( (Meth) acrylic acid 3-oxocyclohexyl / (meth) methyl acrylate / (meth) acrylic acid copolymer, etc. (Meth) can be mentioned acrylic acid 3-oxo-cyclohexyl (co) polymer and the like.

  The Mw of the resin (B1-I) is usually 3,000 to 30,000, preferably 4,000 to 20,000, and more preferably 5,000 to 15,000. In this case, if the Mw of the resin (B1-I) is less than 3,000, the dry etching resistance tends to decrease, and if it exceeds 30,000, the compatibility with the resin (A) is deteriorated and the developability is poor. Tends to decrease.

In the 1st invention, resin (B1) can be used individually or in mixture of 2 or more types.
The usage-amount of resin (B1) in 1st invention is 5-50 weight part normally with respect to 100 weight part of resin (A), Preferably it is 5-40 weight part. In this case, if the amount of the resin (B-1) used is less than 5 parts by weight, the effect of improving the transmittance for radiation may be insufficient, and if it exceeds 50 parts by weight, sufficient dry etching resistance or good It tends to be difficult to obtain a simple pattern shape.

The component (B2) in the second invention comprises a compound represented by the general formula (1) having a molecular weight of 1,000 or less (hereinafter referred to as “compound (B2)”). In the general formula (1), when a plurality of R ¹ or R ² are present, they may be the same or different from each other.
When the resin (A) does not contain an acid cleavable group, the compound (B2) in the second invention must contain an acid cleavable group.
In the general formula (1), examples of the acid-cleavable group for R ¹ and R ² include the same groups as the acid-cleavable group (ii).
When the radiation-sensitive resin composition in the second invention is used as a chemically amplified resist, ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm) is preferably used as radiation.
As a compound (B2) suitable for the ArF excimer laser, for example,
T-butyl adamantanecarboxylate, tetrahydropyranyl adamantanecarboxylate, 3-oxocyclohexyl adamantanecarboxylate, t-butoxycarbonylmethyl adamantanecarboxylate, t-butyl adamantyl acetate, tetrahydropyranyl adamantyl acetate, 3-oxocyclohexyl adamantyl acetate, T-butoxycarbonylmethyl adamantyl acetate, t-butyl tricyclodecanylcarboxylate, tetrahydropyranyl tricyclodecanylcarboxylate, 3-oxocyclohexyl tricyclodecanylcarboxylate, t-butoxycarbonylmethyl tricyclodecanylcarboxylate , Di-t-butyl tricyclodecanyl dicarboxylate, ditetrahydropyranyl tricyclodecanyl dicarboxylate, dicyclodecanyl dicarboxylate 3-oxocyclohexyl, di-t-butoxycarbonylmethyl tricyclodecanyldicarboxylate, t-butyl cholate, tetrahydropyranyl cholate, 3-oxocyclohexyl cholate, t-butoxycarbonylmethyl cholate, t-litholic acid t- Butyl, lithocholic acid tetrahydropyranyl, lithocholic acid 3-oxocyclohexyl, lithocholic acid t-butoxycarbonylmethyl, dihydrocholate t-butyl, dihydrocholate tetrahydropyranyl, dihydrocholate 3-oxocyclohexyl, dihydrocholic acid t- Butoxycarbonylmethyl, 1-t-butoxycarbonyloxynaphthalene, 2-t-butoxycarbonyloxynaphthalene, 1-carbo-t-butoxymethoxynaphthalene, 2-carbo-t-butene Shi methoxynaphthalene, and the like.
Among these compounds (B2), t-butyl adamantanecarboxylate, t-butoxycarbonylmethyl adamantanecarboxylate, t-butyl adamantyl acetate, t-butoxycarbonylmethyl adamantyl acetate, t-butyl tricyclodecanylcarboxylate, tri Di-t-butyl cyclodecanyl dicarboxylate, t-butyl cholate, t-butoxycarbonylmethyl cholate, t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, t-butyl dihydrocholate, t-dihydrocholic acid t -Butoxycarbonylmethyl and the like are preferable.
In the second invention, the compound (B2) can be used alone or in admixture of two or more.
The usage-amount of the compound (B2) in 2nd invention is 5-50 weight part normally with respect to 100 weight part of resin (A), Preferably it is 5-40 weight part. In this case, if the amount of the compound (B2) used is less than 5 parts by weight, the effect of improving the transmittance with respect to radiation may be insufficient, and if it exceeds 50 parts by weight, the heat resistance and the adhesion to the substrate may be increased. There is a tendency to decrease.
In the first invention or the second invention, the resin (B1) and the compound (B2) can be used in combination.

Acid generator (C)
Furthermore, the component (C) in the first and second inventions is a radiation-sensitive acid generator (hereinafter referred to as “acid generator (C)”) that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”). It consists of).
The acid generator (C) cleaves the acid-cleavable group present in the resin (A), the resin (B1) or the compound (B2) by the action of the acid generated by exposure, and as a result, the resist film is exposed. The portion becomes readily soluble in an alkali developer and has a function of forming a positive resist pattern.
Examples of the acid generator (C) include onium salts, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds.

The following can be mentioned as an example of these acid generators (C).
Onium Salt Examples of the onium salt include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, and pyridinium salts.
Specific examples of preferred onium salts include
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t -Butylphenyl) iodonium naphthalenesulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzenemethyl Sulfonium toluenesulfonate, cyclo Xylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium camphorsulfonate, 4-hydroxyphenyl) benzylmethylsulfonium toluenesulfonate,
1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1- Naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy- 1-naphthyldimethylsulfonium trifluoromethanesulfonate,

4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy- 1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (1-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- ( 2-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxycarbonyloxy 1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i -Propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium Trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiopheny Mutrifluoromethanesulfonate, 4- (2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (naphthylacetomethyl) Examples thereof include tetrahydrothiophenium trifluoromethanesulfonate.

Halogen-containing compounds Examples of halogen-containing compounds include haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like.
Specific examples of preferred halogen-containing compounds include (trichloro, phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, etc. And methyl) -s-triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.
Diazoketone compound Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like.
Specific examples of preferred diazo ketones include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2, naphthoquinonediazide of 2,3,4,4′-tetrahydrobenzophenone. -4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-naphthoquinonediazide-4-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane Examples include 2-naphthoquinonediazide-5-sulfonic acid ester.

Sulfone Compound Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds.
Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like.
Sulfonic acid compounds Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, alkyl sulfonic acid imides, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5. -Ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate, and the like.

Among these acid generators (C), in particular, diphenyliodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoro Lomethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiofe Nitrotrifluoromethanesulfonate, 1- (naphthylacetate Til) tetrahydrothiophenium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic Acid imide trifluoromethanesulfonate and the like are preferable.
In the first and second inventions, the acid generator (C) can be used alone or in admixture of two or more.

  The amount of the acid generator (C) used is usually 0.1 to 10 parts by weight, preferably 0.5 to 100 parts by weight of the resin (A) from the viewpoint of ensuring the sensitivity and developability as a resist. ~ 7 parts by weight. In this case, if the amount of the acid generator (C) used is less than 0.1 parts by weight, the sensitivity and developability are lowered, and if it exceeds 10 parts by weight, the transparency to radiation is lowered, and a rectangular resist pattern Tends to be difficult to obtain.

Various additives The radiation-sensitive resin compositions of the first and second inventions are compounds that act as Lewis bases with respect to acids generated from the acid generator (C) (hereinafter referred to as “Lewis base additives”). By blending, it is possible to more effectively improve the verticality of the sidewall of the resist pattern.
Examples of such Lewis base additives include nitrogen-containing basic compounds and salts thereof, carboxylic acids, alcohols and the like, with nitrogen-containing basic compounds being preferred.
Specific examples of the nitrogen-containing basic compound include triethylamine, tri-n-propylamine, tri-i-propylamine, tri-n-butylamine, tri-n-hexylamine, triethanolamine, triphenylamine, aniline, N, N -Amines such as dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 1-naphthylamine, 2-naphthylamine, diphenylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, pyrrolidine, piperidine Compound: Imidazole compounds such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole and thiabendazole; pyridine, 2-methylpyridine, 4-ethylpyridine, 2-hydroxypyridine, 4 Pyridine compounds such as hydroxypyridine, 2-phenylpyridine, 4-phenylpyridine, nicotinic acid, nicotinamide, quinoline, acridine; purine, 1,3,5-triazine, triphenyl-1,3,5-triazine, 1 , 2,3-triazole, 1,2,4-triazole, urazole and other nitrogen-containing heterocyclic compounds.
These nitrogen-containing basic compounds can be used alone or in admixture of two or more.
The compounding quantity of a Lewis base additive is 1 mol or less normally with respect to 1 mol of acid generators (C), Preferably it is 0.05-1 mol. In this case, if the compounding amount of the Lewis base additive exceeds 1 mol, the sensitivity as a resist tends to decrease.

Furthermore, other various additives can be blended with the radiation sensitive resin compositions of the first invention and the second invention, if necessary.
As such an additive, for example, a surfactant exhibiting an effect of improving coatability, developability and the like can be mentioned.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate. In addition to nonionic surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (manufactured by Dainippon Ink & Chemicals), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass) and the like.
These surfactants can be used alone or in admixture of two or more.
The blending amount of the surfactant is usually 2 parts by weight or less with respect to 100 parts by weight in total of the resin (A) and the resin (B1) or the compound (B2) and the acid generator (C).
Examples of additives other than those described above include antihalation agents, adhesion assistants, storage stabilizers, and antifoaming agents.

Preparation of Composition Solution The radiation-sensitive resin compositions of the first and second inventions usually have a total solid content of, for example, 5 to 50% by weight, preferably 10 to 25% by weight. Further, after being dissolved in a solvent, it is prepared as a composition solution by, for example, filtering with a filter having a pore size of about 0.2 μm.

Examples of the solvent used for the preparation of the composition solution include:
2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, Linear ketones such as 2-octanone;
Cyclic ketones such as cyclopentanone, 3-methyl-2-cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Propylene glycol such as mono n-propyl ether acetate, propylene glycol mono i-propyl ether acetate, propylene glycol mono n-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono sec-butyl ether acetate, propylene glycol mono t-butyl ether acetate Monoalkyl ether acetates;
Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, In addition to alkyl 2-hydroxypropionates such as sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate,

n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether, propylene Glycol monoethyl Ether, propylene glycol mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, Ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, dihexyl A Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, Examples include propylene carbonate.

  These solvents can be used alone or in admixture of two or more. Among them, cyclic ketones, linear ketones, propylene glycol monoalkyl ether acetates and alkyl 2-hydroxypropionate In particular, a mixed solvent of cyclic ketones and at least one selected from the group of linear ketones, propylene glycol monoalkyl ether acetates and alkyl 2-hydroxypropionates is preferable.

Method for Forming Resist Pattern The radiation-sensitive resin compositions of the first and second inventions are particularly useful as chemically amplified positive resists.
In the chemically amplified positive resist, an acid-cleavable group in the resin (A), or the resin (B1) or the compound (B2) is formed by, for example, the action of an acid generated from the acid generator (C) by exposure. ,
(Nu) Reaction in which an alkoxycarbonyl group is cleaved and converted to a carboxyl group,
(L) Reaction in which an alkylcarbonyloxy group is cleaved and converted to a hydroxyl group,
(Wo) a reaction in which the cyano group is cleaved and converted to a carboxyl group,
(W) causing a reaction in which the acid anhydride group is cleaved and converted into a carboxyl group, and as a result, the solubility of the exposed portion of the resist in the alkali developer is increased, and the exposed portion is dissolved by the alkali developer. This is removed to obtain a positive resist pattern.

When forming a resist pattern from the radiation-sensitive resin composition of the first invention and the second invention, the radiation-sensitive resin composition is applied by appropriate application means such as spin coating, cast coating, roll coating, etc. Then, a resist film is formed by coating on a substrate such as a silicon wafer or a wafer coated with aluminum, and after pre-baking in some cases, the resist film is exposed to form a predetermined resist pattern. . The radiation used at that time is preferably an ArF excimer laser (wavelength 193 nm) or a KrF excimer laser (wavelength 248 nm).
In the first invention and the second invention, it is preferable to perform heat treatment after exposure (hereinafter referred to as “post-exposure bake”). By this post-exposure baking, the reactions (n) to (wa) proceed smoothly. The heating conditions for post-exposure baking vary depending on the composition of the composition, but are usually 30 to 200 ° C, preferably 50 to 170 ° C.
In the first invention and the second invention, in order to maximize the potential of the radiation-sensitive resin composition, as disclosed in, for example, Patent Document 3, etc., an organic or inorganic system is used on the substrate to be used. In order to prevent the influence of basic impurities contained in the environmental atmosphere, for example, as disclosed in Patent Document 4 and the like, a protective film is formed on the resist film. Can be provided, or these techniques can be used in combination.

Japanese Examined Patent Publication No. 6-12458 JP-A-5-188598

Next, the exposed resist film is developed to form a predetermined resist pattern.
Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine. , Triethylamine, methyldiethylamine, dimethylethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [ 4.3.0] An alkaline aqueous solution in which at least one alkaline compound such as 5-nonene is dissolved is preferable. The concentration of the alkaline aqueous solution is usually 10% by weight or less. In this case, if the concentration of the alkaline aqueous solution exceeds 10% by weight, the unexposed area is also dissolved in the developer, which is not preferable.
In addition, for example, an organic solvent can be added to the developer composed of the alkaline aqueous solution.

Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 3-methyl-2-cyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane And the like; esters such as ethyl acetate, butyl acetate and isoamyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone and dimethylformamide.
These organic solvents can be used alone or in admixture of two or more.
The amount of the organic solvent used is preferably 100% by volume or less with respect to the alkaline aqueous solution. In this case, if the amount of the organic solvent used exceeds 100% by volume, the developability deteriorates and the undeveloped residue in the exposed area becomes remarkable, which is not preferable.
In addition, an appropriate amount of a surfactant or the like can be added to the developer composed of an alkaline aqueous solution.
In addition, after developing with the developing solution which consists of alkaline aqueous solution, generally it wash | cleans with water and dries.

  The radiation-sensitive resin compositions of the first and second inventions, as a chemically amplified resist, are excellent in transparency to radiation, have sufficient dry etching resistance, in particular, have excellent contact hole resolution, and have a pattern shape. It is also excellent in the balance of characteristics such as sensitivity and resolution, and can be used very suitably for the manufacture of semiconductor devices that are expected to be further miniaturized in the future.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, parts and% are based on weight unless otherwise specified.
Each measurement and evaluation in Examples and Comparative Examples was performed as follows.
Mw:
Using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, with a monodisperse polystyrene as the standard under the analysis conditions of flow rate 1.0 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. Measured by gel permeation chromatography (GPC).
Radiation transmittance:
For a film having a dry film thickness of 1.0 μm obtained by spin-coating the composition solution on quartz glass, the radiation transmittance was calculated from the absorbance at a wavelength of 193 nm, and used as a measure of transparency in the far ultraviolet region.

Relative etching rate:
Composition solution against a dry thickness 1.0μm of film was spin-coated onto a quartz glass, a dry etching apparatus (Nichiden Anerva, DEM451) used, and the etching gas and CF _4, the gas flow rate 30 sccm, pressure 5Pa Then, dry etching was performed under the condition of an output of 100 W, the etching rate was measured, and the relative etching rate was evaluated based on the relative value with respect to the etching rate of the coating made of cresol novolac resin. The smaller the etching rate, the better the dry etching resistance.
Pattern shape:
Measure the lower side dimension L ₁ and the upper and lower side dimension L _{2 of the} rectangular cross section of the line and space pattern (1L1S) with a line width of 0.30 μm with a scanning electron microscope,
The pattern shape was considered good when 0.85 ≦ L ₂ / L ₁ ≦ 1 was satisfied and the pattern shape was not trailing.

sensitivity:
The composition was spin-coated on a silicone wafer and then pre-baked for 90 seconds on a hot plate maintained at the temperature shown in Table 2 to form a resist film having a thickness of 0.5 μm. This resist film was exposed through a mask pattern by an ArF excimer laser exposure apparatus (lens numerical aperture 0.55, exposure wavelength 193 nm) manufactured by Nikon Corporation. Next, after 90 seconds post-exposure baking on a hot plate maintained at the temperature shown in Table 2, development was performed with a 2.38% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 1 minute, washed with water, and dried. A positive resist pattern was formed. At that time, an exposure amount for forming a line-and-space pattern (1L1S) having a line width of 0.30 μm in a one-to-one line width was defined as an optimum exposure amount, and this optimum exposure amount was defined as sensitivity.
resolution:
The minimum resist pattern dimension that can be resolved when exposed at the optimum exposure dose is taken as the resolution.

Contact hole resolution:
The resist film formed on the silicon wafer is exposed to light and immediately post-exposure baked, then developed with an alkaline developer, washed with water, and dried to form a resist pattern of 0.25 μm × 0.25 μm. Using a square reticle, obtain an exposure amount at which the diameter of the contact hole having a circular cross section is 0.25 μm, and determine the minimum diameter (μm) of the contact hole that is resolved when exposed at this exposure amount. The contact hole resolution was used.

Synthesis example 1
(1) 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] Synthesis of dodec-3-ene In a reaction vessel with an internal volume of 50 liters maintained at a temperature of 180 ° C. and a pressure of 3.5 kg / cm ² · G, a methyl methacrylate, dicyclo Pentadiene and 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene are mixed in a reaction vessel at a molar ratio of 1: 2.4 (in terms of cyclopentadiene units): 2.4. The total feed rate was continuously set at 4 kg / hour so that the residence time of the reaction raw materials became an average of 8 hours. Moreover, p-methoxyphenol was dissolved in methyl methacrylate as a polymerization inhibitor and supplied in an amount of 300 ppm (weight conversion) with respect to the total supply amount of the reaction raw materials.
During the reaction, the reaction product was withdrawn from the reaction vessel at a rate of 4 kg / h and continuously supplied to a flash distillation column maintained at a pressure of 300 torr and a temperature of 105 ° C. to separate a part of the unreacted raw material.
The distillate from the flash distillation column is a distillation column having a column diameter of 3 inches in which the packing height (trade name: Sulzer Packing BX, manufactured by Sumitomo Heavy Industries) is 119 cm in the concentrating part and 102 cm in the collecting part. The unreacted raw material that could not be separated in the flash distillation column was recovered from the top of the column, and the following formula (10) was recovered from the bottom of the column. 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
A solution containing 67% of ^1,7,10 ] dodec-3-ene was obtained.

(2) Polymerization The inside of a separable flask equipped with a stirrer, a reflux condenser and a three-way cock was purged with nitrogen, and under a nitrogen stream, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 100 parts, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene 100 parts, 1-hexene (molecular weight regulator) 35 parts, toluene 200 Parts were charged and heated to 80 ° C. Next, 2.7 parts of a toluene solution of diethylaluminum chloride (concentration 0.19 mol / liter) and 1.03 part of a toluene solution of WCl ₆ (concentration 0.025 mol / liter) were added as metathesis catalysts, and 3 parts at 80 ° C. Polymerization was conducted with stirring for a time to obtain a resin solution (yield 90%) composed of repeating units represented by the following formulas. This resin is referred to as “resin (AI-1)”.

(3) Hydrogenation Add 400 parts of resin (AI-1) and 0.075 part of chlorohydrocarbonyltriphenylphosphine ruthenium as a hydrogenation catalyst to the autoclave, hydrogen gas pressure 100 kg / cm ² · G, temperature 165 ° C. The hydrogenation reaction was carried out under the conditions described above for 4 hours.
Next, 400 parts of the resulting reaction solution and 100 parts of toluene were charged into another reaction vessel, 0.71 part of lactic acid and 1.15 parts of water were added, and the mixture was stirred at 60 ° C. for 30 minutes, and then 260 parts of methyl alcohol. Was added and stirred at 60 ° C. for an additional hour. Thereafter, the reaction vessel was cooled to room temperature and separated into a poor solvent phase (methyl alcohol phase) and a good solvent phase (resin solution phase), and then only the poor solvent phase was extracted. Thereafter, methyl alcohol corresponding to 4.5% of the extracted methyl alcohol and toluene corresponding to 55% were added to the reaction vessel and stirred at 60 ° C. for 1 hour. Thereafter, the mixture was cooled again to room temperature, separated into a poor solvent phase and a good solvent phase, and only the poor solvent phase was extracted. After repeating this extraction operation with methyl alcohol several times, the good solvent phase was separated, the solvent was distilled off from the good solvent phase, and the resin was recovered. Next, this resin was redissolved in tetrahydrofuran and then re-coagulated with a large amount of methyl alcohol, and the coagulated resin was dried under reduced pressure to obtain a purified resin.
This resin was a random copolymer having a hydrogenation rate of 100% measured by NMR spectrum, consisting of repeating units represented by the following formulas, and Mw of 22,000. This resin is referred to as “resin (AI-2)”.

(4) Hydrolysis 100 parts of resin (AI-2), 200 parts of propylene glycol, 10 parts of distilled water and 50 parts of potassium hydroxide were placed in a flask and hydrolyzed at 185 ° C. for 4 hours in a nitrogen atmosphere. Subsequently, after cooling the reaction solution, it was dripped in the aqueous solution which melt | dissolved 1.1 equivalent of oxalic acid dihydrate with respect to potassium hydroxide, and the resin was solidified.
This resin had a hydrolysis rate of 100% as measured by infrared absorption spectrum and acid-alkali titration, and was a random copolymer composed of repeating units represented by the following formulas. This resin is referred to as “resin (AI-3)”.

(5) Introduction of protective group 100 parts of resin (AI-3), 200 parts of tetrahydrofuran, 200 parts of distilled water, 52 parts of t-butyl α-bromoacetate and 41 parts of potassium carbonate were placed in a flask and refluxed in a nitrogen atmosphere. And stirred for 6 hours. Next, 200 parts of ethyl acetate, 400 parts of distilled water and 45 parts of oxalic acid dihydrate were added, stirred, and allowed to stand to separate the organic layer. The organic layer was washed several times with water and then dried under vacuum to obtain a purified resin.
This resin has a rate of esterification by t-butoxycarbonylmethyl group measured by NMR spectrum of 48%, and consists of repeating units represented by the following formulas (11-1) to (11-4). Is a random copolymer having a molar ratio of (11-1) / (11-2) / (11-3) / (11-4) = 24/18/28/30 and Mw of 18,000. there were. This resin is referred to as “resin (AI-4)”.

Synthesis example 2
(1) 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Synthesis of dodec-3-ene 8-t-butoxy in the same manner as in Synthesis Example 1 (1) except that t-butyl acrylate and dicyclopentadiene were used in a molar ratio of 3: 1. Carbonyltetracyclo [4.4.0.1 ^2,5 . A solution containing 30% of ^1,7,10 ] dodec-3-ene was obtained.
(2) Polymerization In the separable flask used in (2) of Synthesis Example 1, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 26 parts of dodec-3-ene, 10 parts of maleic anhydride, 3 parts of azobisisobutyronitrile and 36 parts of propylene glycol monomethyl ether were charged and polymerized at 70 ° C. for 6 hours. After completion of the polymerization, the reaction solution is poured into a large amount of methanol to solidify the resin, and the solidified resin is washed several times with methanol, and then vacuum-dried, and consists of repeating units represented by the following formulas. Of 3,000 was obtained (yield 52%). This copolymer is referred to as “resin (AI-5)”.

Synthesis example 3
In a separable flask used in (2) of Synthesis Example 1, under a nitrogen stream, 60 parts of tricyclodecanyl acrylate, 35 parts of tetrahydropyranyl acrylate, 11 parts of ethyl α-hydroxymethylacrylate, azobisiso 1.5 parts of butyronitrile, 3 parts of t-dodecyl mercaptan and 250 parts of dimethoxyethane were charged and polymerized at 75 ° C. for 6 hours. Thereafter, the obtained resin is reprecipitated and solidified from n-hexane, and the solidified resin is filtered and then vacuum-dried. The resin is composed of repeating units represented by the following formulas, and Mw is 11,000. A polymer (yield 90%) was obtained. This copolymer is referred to as “resin (AII-1)”.

Synthesis example 4
In a separable flask used in Synthesis Example 1 (2), under a nitrogen stream, 60 parts of t-butyl methacrylate, 40 parts of methyl methacrylate, 2 parts of azobisisobutyronitrile, t-dodecyl mercaptan 1.5 And 250 parts of ethylene glycol dimethyl ether were charged and polymerized at 75 ° C. for 6 hours. Thereafter, the obtained resin is reprecipitated and solidified from n-hexane, and the solidified resin is filtered and then vacuum-dried. The white resin is composed of repeating units represented by the following formulas and has a Mw of 9,200. Random copolymer (yield 90%) was obtained. This copolymer is referred to as “resin (B1-1)”.

Synthesis example 5
After adding 200 parts of tetrahydrofuran and 200 parts of distilled water to the separable flask used in (2) of Synthesis Example 1, 100 parts of lithocholic acid, 57 parts of α-bromoacetate and 40 parts of potassium carbonate were dissolved. The reaction was carried out under reflux for 18 hours under a nitrogen stream. Thereafter, the reaction solution was cooled to room temperature, 400 parts of ethyl acetate and 400 parts of distilled water were added, the aqueous layer was separated, and the organic layer was washed twice with a 10% aqueous solution of potassium hydroxide. Lithocholic acid was removed. Next, the reaction product was washed with distilled water three times, and the solvent and the like were distilled off, followed by vacuum drying to obtain a white solid.
This solid was identified as t-butoxycarbonylmethyl lithocholic acid (96% yield) by NMR measurement. This compound is referred to as “compound (B2-1)”.

Synthesis Example 6
After adding 200 parts of dioxane to the separable flask used in (2) of Synthesis Example 1, 100 parts of adamantanecarboxylic acid, 140 parts of dihydropyran and 2 parts of pyridinium p-toluenesulfonate are dissolved at 10 ° C. for 48 hours. The reaction was carried out with stirring. Thereafter, 400 parts of a 5% aqueous solution of potassium carbonate and 400 parts of ethyl acetate were added, the aqueous layer was separated, the organic layer was washed with water three times, the solvent and the like were distilled off, and colorless oily adamantanecarboxylate tetrahydro Pyranyl (90% yield) was obtained. This compound is referred to as “compound (B2-2)”.

Examples 1 to 4 and Comparative Example 1
With respect to the film formed using the composition solution composed of each component shown in Table 1, the radiation transmittance and the relative etching rate were evaluated.
The evaluation results are shown in Table 1.

Examples 5 to 8 and Comparative Example 2
A resist pattern was formed using a composition solution composed of each component shown in Table 2, and the pattern shape, sensitivity, resolution, and contact hole resolution were evaluated.
The evaluation results are shown in Table 3.

Components other than Resin (A), Resin (B1) and Compound (B2) in Tables 1 and 2 are as follows.
(C-1): 4-hydroxynaphthyltetrahydrothiophenium trifluoromethanesulfonate (C-2): 4,4'-di-t-butyliodonium trifluoromethanesulfonate (C-3): cyclohexyl (2-oxocyclohexyl) ) Sulfonium trifluoromethanesulfonate (D-1): cyclohexanone (D-2): 2-heptanone (E-1): tri-n-butylamine (E-2): nicotinamide

Claims (1)

(A) a resin having an alicyclic skeleton in the main chain and / or side chain,
(B) A radiation-sensitive acid containing a resin having a transmittance of 60% / μm or more for radiation within a wavelength range of 100 to 300 nm as a film, and (C) a radiation-sensitive acid generator that generates an acid upon irradiation with radiation. A radiation-sensitive resin composition, wherein at least one of the component (A) and the component (B) contains an acid-cleavable group.