JPH11218924A - Radiation-sensitive resin composition - Google Patents

Abstract

(57) [Problem] To provide a radiation-sensitive resin composition having excellent storage stability, high transparency to radiation, and excellent dry etching resistance, sensitivity, resolution, pattern shape, etc. as a chemically amplified resist. provide. SOLUTION: The radiation-sensitive resin composition is (A) an alkali-insoluble or alkali-insoluble resin having a group represented by the following general formula (1) as an acid-dissociable group, (B) a resin which becomes alkali-soluble when itself and / or the group R ⁴ in the acid-dissociable group is dissociated;
Contains a radiation-sensitive acid generator. Embedded image [In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ¹ and R 2
^{And 2} represent a 3- to 6-membered cyclic alkyl group bonded to each other, and R ⁴ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition, and more particularly, to charged particles such as far-ultraviolet rays such as KrF excimer laser or ArF excimer laser, X-rays such as synchrotron radiation, and electron beams. The present invention relates to a radiation-sensitive resin composition that can be suitably used as a chemically amplified resist useful for microfabrication using various radiations such as lines.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit elements, recently, it is said that a fine processing technique at a level of 0.20 μm or less is required in order to obtain a higher degree of integration. . In the conventional lithography process, near-ultraviolet rays such as i-rays are generally used as radiation, but it is said that it is extremely difficult to perform sub-quarter micron level fine processing with near-ultraviolet rays.
Therefore, in order to enable fine processing at a level of 0.20 μm or less, utilization of radiation having a shorter wavelength is being studied. Examples of such short wavelength radiation include, for example,
The emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, X-rays, electron beams, and the like can be given.
Among them, a KrF excimer laser (wavelength 24
8 nm) or ArF excimer laser (wavelength 193)
nm) has received attention. Such a radiation-sensitive resin composition suitable for irradiation with an excimer laser includes a component having an acid-dissociable functional group and a component that generates an acid upon irradiation with radiation (hereinafter, referred to as “exposure”) (hereinafter, referred to as “acid”). (Hereinafter referred to as "chemically amplified radiation-sensitive composition").
Many have been proposed. As such a chemically amplified radiation-sensitive composition, for example, Japanese Patent Publication No. 2-27660 discloses a polymer having a t-butyl ester group of carboxylic acid or a t-butyl carbonate group of phenol and acid generation. And compositions containing the agent. In this composition, the t-butyl ester group or t-butyl carbonate group present in the polymer is dissociated by the action of the acid generated by the exposure, and the polymer is formed of a carboxyl group or a phenolic hydroxyl group. This makes use of the phenomenon that the exposed region of the resist film becomes easily soluble in an alkali developing solution. By the way, many of the conventional chemically amplified radiation-sensitive compositions are based on phenolic resins, but in the case of such resins, when far-ultraviolet rays are used as radiation,
Because of the absorption of far ultraviolet rays due to the aromatic ring in the resin, there is the disadvantage that the exposed far ultraviolet rays cannot reach the lower layer of the resist film sufficiently. However, there is a problem that the resist pattern after development becomes smaller and the resist pattern after development becomes thicker and trapezoidal as the upper part becomes thinner toward the lower part, and a sufficient resolution cannot be obtained. In addition, when the resist pattern after development has a trapezoidal shape, desired dimensional accuracy cannot be achieved in the next step, ie, etching or ion implantation, which has been a problem. In addition, if the shape of the upper part of the resist pattern is not rectangular, the rate of disappearance of the resist by dry etching is increased, and there is a problem that it is difficult to control the etching conditions. The shape of the resist pattern can be improved by increasing the radiation transmittance of the resist film. For example, a (meth) acrylate resin represented by polymethyl methacrylate has high transparency to far ultraviolet rays and is a very preferable resin from the viewpoint of radiation transmittance.
Japanese Patent No. 226461 proposes a chemically amplified radiation-sensitive resin composition using a methacrylate resin. However, although this composition is excellent in terms of fine processing performance, it does not have an aromatic ring, and thus has a drawback that dry etching resistance is low. In this case, it is difficult to perform high-precision etching processing. However, it cannot be said that both the transparency to radiation and the resistance to dry etching are combined. On the other hand, for a resist composed of a chemically amplified radiation-sensitive composition, as one of measures for improving dry etching resistance without impairing transparency to radiation, a resin component in the composition is replaced with an aromatic ring. A method for introducing an alicyclic ring is known.
JP-A-234511 discloses (meth) having an alicyclic ring.
A chemically amplified radiation-sensitive resin composition using an acrylate resin has been proposed. However, in the conventional chemically amplified radiation-sensitive resin composition, as the acid-dissociable functional group, a group which is relatively easily dissociated by an acid (for example, an acetal-based functional group such as a tetrahydropyranyl group) or a relatively dissociated by an acid. Groups that are difficult to perform (for example, t-butyl-based functional groups such as t-butyl ester groups and t-butyl carbonate groups)
Is generally used, when using the former resin component having an acid-dissociable functional group, the basic physical properties of the resist, particularly sensitivity and pattern shape are good, but there is a problem in storage stability as a composition, On the other hand, when the latter resin component having an acid-dissociable functional group is used, storage stability is good, but there is a disadvantage that the basic physical properties of the resist, particularly sensitivity and pattern shape, are impaired. Particularly in recent years, Japanese Patent Laid-Open No. 8-3
JP 05023, the general formula ^{-COOC (R 1) (R 2} ) -CH (R 3) -C0R
⁴ (where R ¹ , R ² , R ³ and R ⁴ are a linear or branched (substituted) alkyl group, an alicyclic hydrocarbon group and a group derived therefrom). Chemically amplified radiation-sensitive resin compositions containing a base polymer having an acid-dissociable functional group consisting of
The main purpose is to prevent peeling or cracking of the resist pattern from the substrate, and no particular study has been made on the storage stability of the composition. Therefore, the development of a chemically amplified radiation-sensitive resin composition that is not only highly transparent to radiation and excellent in dry etching resistance, sensitivity, resolution, pattern shape, etc., but also excellent in storage stability as a composition has been developed. It has been demanded.

[0003]

An object of the present invention is to provide an actinic radiation such as a KrF excimer laser or ArF
As a chemically amplified resist that is sensitive to far ultraviolet rays typified by excimer lasers, it has excellent storage stability as a composition, high transparency to radiation, and resists dry etching resistance, sensitivity, resolution, pattern shape, etc. To provide a radiation-sensitive resin composition having excellent basic physical properties.

[0004]

According to the present invention, an object of the present invention is to provide (A) an alkali-insoluble or alkali-insoluble resin having a group represented by the following general formula (1) as an acid-dissociable group. A resin which becomes alkali-soluble when the acid-dissociable group itself and / or the group R ⁴ in the acid-dissociable group is dissociated, and (B) a radiation-sensitive resin composition containing a radiation-sensitive acid generator;

[0005]

Embedded image

[In the general formula (1), R ¹ and R ²
Are each independently a hydrogen atom or a straight-chain having 1 to 6 carbon atoms,
Represents a branched or cyclic alkyl group;
¹ and R ² are mutually bonded to form a 3- to 6-membered cyclic alkyl group; R ³ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; ⁴ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. ], Is achieved.

Hereinafter, the present invention will be described in detail. Resin (A) The component (A) in the present invention is a group represented by the general formula (1) as an acid-dissociable group (hereinafter referred to as “acid-dissociable group (1)”).
That. A) a resin which becomes alkali-soluble when the acid-dissociable group (1) itself and / or the group R ⁴ in the acid-dissociable group (1) is dissociated (hereinafter, referred to as "Resin (A)"). Here, the acid dissociable group (1) in the resin (A)
When showing an aspect group R ⁴ in itself and / or acid-dissociable group (1) is dissociated more specifically, there are the following cases (i) ~ (iii). (I) an ester bond present in the acid dissociable group (1) (-
A case where the bond between the oxygen atom and the group R ^{4 in} COOR ⁴ ) is dissociated by the action of an acid to form a group represented by the following general formula (2).

[0008]

Embedded image

(Ii) The bond between the acid-dissociable group (1) itself and an atom adjacent to the acid-dissociable group (1) is dissociated by the action of an acid, and a phenolic hydroxyl group (including a naphtholic hydroxyl group).
The same applies hereinafter. ) Or when a carboxyl group is generated. (Iii) When the reactions (i) and (ii) occur simultaneously.

Examples of the resin (A) include the following resin (AI) or resin (A-II). The resin (A-I) is an alkali-soluble resin containing at least one kind of acidic functional group such as a phenolic hydroxyl group and a carboxyl group. And is a resin which is insoluble in alkali or hardly soluble in alkali as such.
In addition, the resin (A-II) has an alicyclic skeleton in the main chain and a group —COOZ (where Z represents an acid dissociable group (1)) in a side chain. Is a resin insoluble in alkali or hardly soluble in alkali. Here, the term “alkali-insoluble or alkali-poorly soluble” refers to the alkaline development conditions employed when forming a resist pattern from a resist film formed using a radiation-sensitive resin composition containing the resin (A). This means that when a film using only the resin (A) instead of the resist film is developed, 50% or more of the initial film thickness of the film remains after development.

Specific examples of the acid dissociable group (1) include (methoxycarbonylmethyl) methyl, (ethoxycarbonylmethyl) methyl, (n-propoxycarbonylmethyl) methyl, (i-propoxycarbonylmethyl)
Methyl group, (n-butoxycarbonylmethyl) methyl group, (i-butoxycarbonylmethyl) methyl group, (s
ec-butoxycarbonylmethyl) methyl group, (t-butoxycarbonylmethyl) methyl group, (n-pentyloxycarbonylmethyl) methyl group, (n-hexyloxycarbonylmethyl) methyl group, (cyclopentyloxycarbonylmethyl) methyl group, {(Cyclo) alkoxycarbonylmethyl} methyl group such as (cyclohexyloxycarbonylmethyl) methyl group; 1- (methoxycarbonylmethyl) ethyl group, 1- (ethoxycarbonylmethyl) ethyl group, 1- (n-propoxycarbonylmethyl) Ethyl group, 1- (i-propoxycarbonylmethyl) ethyl group, 1- (n-butoxycarbonylmethyl)
Ethyl group, 1- (i-butoxycarbonylmethyl) ethyl group, 1- (sec-butoxycarbonylmethyl) ethyl group, 1- (t-butoxycarbonylmethyl) ethyl group, 1- (n-pentyloxycarbonylmethyl) ethyl A 1-{(cyclo) alkoxycarbonylmethyl} ethyl group such as a 1- (n-hexyloxycarbonylmethyl) ethyl group, a 1- (cyclopentyloxycarbonylmethyl) ethyl group, a 1- (cyclohexyloxycarbonylmethyl) ethyl group ;

A 1- (methoxycarbonylmethyl) propyl group, a 1- (ethoxycarbonylmethyl) propyl group,
A 1- (n-propoxycarbonylmethyl) propyl group,
1- (i-propoxycarbonylmethyl) propyl group,
1- (n-butoxycarbonylmethyl) propyl group, 1
-(I-butoxycarbonylmethyl) propyl group, 1-
(Sec-butoxycarbonylmethyl) propyl group, 1
-(T-butoxycarbonylmethyl) propyl group, 1-
(N-pentyloxycarbonylmethyl) propyl group,
1-{(cyclo) alkoxycarbonylmethyl} propyl group such as 1- (n-hexyloxycarbonylmethyl) propyl group, 1- (cyclopentyloxycarbonylmethyl) propyl group, 1- (cyclohexyloxycarbonylmethyl) propyl group; -(Methoxycarbonylmethyl) -1-methylethyl group, 1- (ethoxycarbonylmethyl) -1-methylethyl group, 1- (n-propoxycarbonylmethyl) -1-methylethyl group, 1- (i
-Propoxycarbonylmethyl) -1-methylethyl group, 1- (n-butoxycarbonylmethyl) -1-methylethyl group, 1- (i-butoxycarbonylmethyl)-
1-methylethyl group, 1- (sec-butoxycarbonylmethyl) -1-methylethyl group, 1- (t-butoxycarbonylmethyl) -1-methylethyl group, 1- (n-
Pentyloxycarbonylmethyl) -1-methylethyl group, 1- (n-hexyloxycarbonylmethyl) -1
1-{(cyclo) alkoxycarbonylmethyl} -1 such as -methylethyl group, 1- (cyclopentyloxycarbonylmethyl) -1-methylethyl group, 1- (cyclohexyloxycarbonylmethyl) -1-methylethyl group.
A methylethyl group;

A 1- (methoxycarbonylmethyl) butyl group, a 1- (ethoxycarbonylmethyl) butyl group,
(N-propoxycarbonylmethyl) butyl group, 1-
(I-propoxycarbonylmethyl) butyl group, 1-
(N-butoxycarbonylmethyl) butyl group, 1- (i
-Butoxycarbonylmethyl) butyl group, 1- (sec
-Butoxycarbonylmethyl) butyl group, 1- (t-butoxycarbonylmethyl) butyl group, 1- (n-pentyloxycarbonylmethyl) butyl group, 1- (n-hexyloxycarbonylmethyl) butyl group, 1- (cyclopentyl) 1 such as an oxycarbonylmethyl) butyl group and a 1- (cyclohexyloxycarbonylmethyl) butyl group;
-{(Cyclo) alkoxycarbonylmethyl} butyl group; 1- (methoxycarbonylmethyl) -1-methylpropyl group, 1- (ethoxycarbonylmethyl) -1-methylpropyl group, 1- (n-propoxycarbonylmethyl)- 1-methylpropyl group, 1- (i-propoxycarbonylmethyl) -1-methylpropyl group, 1- (n-
Butoxycarbonylmethyl) -1-methylpropyl group,
1- (i-butoxycarbonylmethyl) -1-methylpropyl group, 1- (sec-butoxycarbonylmethyl)
-1-methylpropyl group, 1- (t-butoxycarbonylmethyl) -1-methylpropyl group, 1- (n-pentyloxycarbonylmethyl) -1-methylpropyl group,
1- (n-hexyloxycarbonylmethyl) -1-methylpropyl group, 1- (cyclopentyloxycarbonylmethyl) -1-methylpropyl group, 1- (cyclohexyloxycarbonylmethyl) -1-methylpropyl group, etc. {(Cyclo) alkoxycarbonylmethyl}-
1-methylpropyl group;

A 1- (methoxycarbonylmethyl) pentyl group, a 1- (ethoxycarbonylmethyl) pentyl group,
A 1- (n-propoxycarbonylmethyl) pentyl group,
A 1- (i-propoxycarbonylmethyl) pentyl group,
1- (n-butoxycarbonylmethyl) pentyl group, 1
-(I-butoxycarbonylmethyl) pentyl group, 1-
(Sec-butoxycarbonylmethyl) pentyl group, 1
-(T-butoxycarbonylmethyl) pentyl group, 1-
(N-pentyloxycarbonylmethyl) pentyl group,
1-{(cyclo) alkoxycarbonylmethyl} pentyl group such as 1- (n-hexyloxycarbonylmethyl) pentyl group, 1- (cyclopentyloxycarbonylmethyl) pentyl group, 1- (cyclohexyloxycarbonylmethyl) pentyl group; 1 -(Methoxycarbonylmethyl) -1-methylbutyl group, 1- (ethoxycarbonylmethyl) -1-methylbutyl group, 1- (n-propoxycarbonylmethyl) -1-methylbutyl group, 1- (i
-Propoxycarbonylmethyl) -1-methylbutyl group, 1- (n-butoxycarbonylmethyl) -1-methylbutyl group, 1- (i-butoxycarbonylmethyl)-
1-methylbutyl group, 1- (sec-butoxycarbonylmethyl) -1-methylbutyl group, 1- (t-butoxycarbonylmethyl) -1-methylbutyl group, 1- (n-
Pentyloxycarbonylmethyl) -1-methylbutyl group, 1- (n-hexyloxycarbonylmethyl) -1
1-{(cyclo) alkoxycarbonylmethyl} -1 such as -methylbutyl group, 1- (cyclopentyloxycarbonylmethyl) -1-methylbutyl group, 1- (cyclohexyloxycarbonylmethyl) -1-methylbutyl group.
-Methylbutyl group; 1- (methoxycarbonylmethyl)
-1-ethylpropyl group, 1- (ethoxycarbonylmethyl) -1-ethylpropyl group, 1- (n-propoxycarbonylmethyl) -1-ethylpropyl group, 1- (i
-Propoxycarbonylmethyl) -1-ethylpropyl group, 1- (n-butoxycarbonylmethyl) -1-ethylpropyl group, 1- (i-butoxycarbonylmethyl)
-1-ethylpropyl group, 1- (sec-butoxycarbonylmethyl) -1-ethylpropyl group, 1- (t-butoxycarbonylmethyl) -1-ethylpropyl group, 1
-(N-pentyloxycarbonylmethyl) -1-ethylpropyl group, 1- (n-hexyloxycarbonylmethyl) -1-ethylpropyl group, 1- (cyclopentyloxycarbonylmethyl) -1-ethylpropyl group, 1
1-{(cyclo) alkoxycarbonylmethyl} -1-ethylpropyl group such as-(cyclohexyloxycarbonylmethyl) -1-ethylpropyl group;

A 1- (methoxycarbonylmethyl) hexyl group, a 1- (ethoxycarbonylmethyl) hexyl group,
A 1- (n-propoxycarbonylmethyl) hexyl group,
A 1- (i-propoxycarbonylmethyl) hexyl group,
1- (n-butoxycarbonylmethyl) hexyl group, 1
-(I-butoxycarbonylmethyl) hexyl group, 1-
(Sec-butoxycarbonylmethyl) hexyl group, 1
-(T-butoxycarbonylmethyl) hexyl group, 1-
(N-pentyloxycarbonylmethyl) hexyl group,
1-{(cyclo) alkoxycarbonylmethyl} hexyl group such as 1- (n-hexyloxycarbonylmethyl) hexyl group, 1- (cyclopentyloxycarbonylmethyl) hexyl group, 1- (cyclohexyloxycarbonylmethyl) hexyl group; -(Methoxycarbonylmethyl) -1-methylpentyl group, 1- (ethoxycarbonylmethyl) -1-methylpentyl group, 1- (n-propoxycarbonylmethyl) -1-methylpentyl group, 1
-(I-propoxycarbonylmethyl) -1-methylpentyl group, 1- (n-butoxycarbonylmethyl) -1
-Methylpentyl group, 1- (i-butoxycarbonylmethyl) -1-methylpentyl group, 1- (sec-butoxycarbonylmethyl) -1-methylpentyl group, 1-
(T-butoxycarbonylmethyl) -1-methylpentyl group, 1- (n-pentyloxycarbonylmethyl)-
1-methylpentyl group, 1- (n-hexyloxycarbonylmethyl) -1-methylpentyl group, 1- (cyclopentyloxycarbonylmethyl) -1-methylpentyl group, 1- (cyclohexyloxycarbonylmethyl)
1-{(cyclo) alkoxycarbonylmethyl} -1-methylpentyl group such as -1-methylpentyl group;
(Methoxycarbonylmethyl) -1-ethylbutyl group,
1- (ethoxycarbonylmethyl) -1-ethylbutyl group, 1- (n-propoxycarbonylmethyl) -1-ethylbutyl group, 1- (i-propoxycarbonylmethyl) -1-ethylbutyl group, 1- (n-butoxycarbonyl) Methyl) -1-ethylbutyl group, 1- (i-butoxycarbonylmethyl) -1-ethylbutyl group, 1- (s
ec-butoxycarbonylmethyl) -1-ethylbutyl group, 1- (t-butoxycarbonylmethyl) -1-ethylbutyl group, 1- (n-pentyloxycarbonylmethyl) -1-ethylbutyl group, 1- (n-hexyloxy Carbonylmethyl) -1-ethylbutyl group, 1- (cyclopentyloxycarbonylmethyl) -1-ethylbutyl group, 1- (cyclohexyloxycarbonylmethyl)
1-{(cyclo) alkoxycarbonylmethyl} -1-ethylbutyl group such as -1-ethylbutyl group;

A 1- (methoxycarbonylmethyl) heptyl group, a 1- (ethoxycarbonylmethyl) heptyl group,
A 1- (n-propoxycarbonylmethyl) heptyl group,
A 1- (i-propoxycarbonylmethyl) heptyl group,
1- (n-butoxycarbonylmethyl) heptyl group, 1
-(I-butoxycarbonylmethyl) heptyl group, 1-
(Sec-butoxycarbonylmethyl) heptyl group, 1
-(T-butoxycarbonylmethyl) heptyl group, 1-
(N-pentyloxycarbonylmethyl) heptyl group,
1-{(cyclo) alkoxycarbonylmethyl} heptyl group such as 1- (n-hexyloxycarbonylmethyl) heptyl group, 1- (cyclopentyloxycarbonylmethyl) heptyl group, 1- (cyclohexyloxycarbonylmethyl) heptyl group; -(Methoxycarbonylmethyl) -1-methylhexyl group, 1- (ethoxycarbonylmethyl) -1-methylhexyl group, 1- (n-propoxycarbonylmethyl) -1-methylhexyl group, 1
-(I-propoxycarbonylmethyl) -1-methylhexyl group, 1- (n-butoxycarbonylmethyl) -1
-Methylhexyl group, 1- (i-butoxycarbonylmethyl) -1-methylhexyl group, 1- (sec-butoxycarbonylmethyl) -1-methylhexyl group, 1-
(T-butoxycarbonylmethyl) -1-methylhexyl group, 1- (n-pentyloxycarbonylmethyl)-
1-methylhexyl group, 1- (n-hexyloxycarbonylmethyl) -1-methylhexyl group, 1- (cyclopentyloxycarbonylmethyl) -1-methylhexyl group, 1- (cyclohexyloxycarbonylmethyl)
1-{(cyclo) alkoxycarbonylmethyl} -1-methylhexyl group such as -1-methylhexyl group;
(Methoxycarbonylmethyl) -1-ethylpentyl group, 1- (ethoxycarbonylmethyl) -1-ethylpentyl group, 1- (n-propoxycarbonylmethyl)-
1-ethylpentyl group, 1- (i-propoxycarbonylmethyl) -1-ethylpentyl group, 1- (n-butoxycarbonylmethyl) -1-ethylpentyl group, 1-
(I-butoxycarbonylmethyl) -1-ethylpentyl group, 1- (sec-butoxycarbonylmethyl) -1
-Ethylpentyl group, 1- (t-butoxycarbonylmethyl) -1-ethylpentyl group, 1- (n-pentyloxycarbonylmethyl) -1-ethylpentyl group, 1-
1-{(-n-hexyloxycarbonylmethyl) -1-ethylpentyl group, 1- (cyclopentyloxycarbonylmethyl) -1-ethylpentyl group, 1- (cyclohexyloxycarbonylmethyl) -1-ethylpentyl group, etc. Cyclo) alkoxycarbonylmethyl} -1-
Ethylpentyl group; 1- (methoxycarbonylmethyl)
-1-propylbutyl group, 1- (ethoxycarbonylmethyl) -1-propylbutyl group, 1- (n-propoxycarbonylmethyl) -1-propylbutyl group, 1- (i
-Propoxycarbonylmethyl) -1-propylbutyl group, 1- (n-butoxycarbonylmethyl) -1-propylbutyl group, 1- (i-butoxycarbonylmethyl)
-1-propylbutyl group, 1- (sec-butoxycarbonylmethyl) -1-propylbutyl group, 1- (t-butoxycarbonylmethyl) -1-propylbutyl group, 1
-(N-pentyloxycarbonylmethyl) -1-propylbutyl group, 1- (n-hexyloxycarbonylmethyl) -1-propylbutyl group, 1- (cyclopentyloxycarbonylmethyl) -1-propylbutyl group,
1-{(cyclo) alkoxycarbonylmethyl} -1-propylbutyl group such as-(cyclohexyloxycarbonylmethyl) -1-propylbutyl group;

1- (methoxycarbonylmethyl) cyclopentyl group, 1- (ethoxycarbonylmethyl) cyclopentyl group, 1- (n-propoxycarbonylmethyl)
Cyclopentyl group, 1- (i-propoxycarbonylmethyl) cyclopentyl group, 1- (n-butoxycarbonylmethyl) cyclopentyl group, 1- (i-butoxycarbonylmethyl) cyclopentyl group, 1- (sec-butoxycarbonylmethyl) cyclopentyl group , 1- (t-
Butoxycarbonylmethyl) cyclopentyl group, 1-
1- such as (n-pentyloxycarbonylmethyl) cyclopentyl group, 1- (n-hexyloxycarbonylmethyl) cyclopentyl group, 1- (cyclopentyloxycarbonylmethyl) cyclopentyl group, 1- (cyclohexyloxycarbonylmethyl) cyclopentyl group, etc.
{(Cyclo) alkoxycarbonylmethyl} cyclopentyl group; 1- (methoxycarbonylmethyl) cyclohexyl group, 1- (ethoxycarbonylmethyl) cyclohexyl group, 1- (n-propoxycarbonylmethyl) cyclohexyl group, 1- (i-propoxycarbonyl Methyl) cyclohexyl group, 1- (n-butoxycarbonylmethyl) cyclohexyl group, 1- (i-butoxycarbonylmethyl) cyclohexyl group, 1- (sec-butoxycarbonylmethyl) cyclohexyl group, 1- (t-butoxycarbonylmethyl) A cyclohexyl group, 1- (n
1-{(cyclo) group such as -pentyloxycarbonylmethyl) cyclohexyl group, 1- (n-hexyloxycarbonylmethyl) cyclohexyl group, 1- (cyclopentyloxycarbonylmethyl) cyclohexyl group, 1- (cyclohexyloxycarbonylmethyl) cyclohexyl group ) Alkoxycarbonylmethylcyclohexyl group;

{1- (methoxycarbonyl) ethyl} methyl group, {1- (ethoxycarbonyl) ethyl} methyl group, {1- (n-propoxycarbonyl) ethyl} methyl group, {1- (i-propoxycarbonyl) methyl group Ethyl @ methyl group, {1- (n-butoxycarbonyl) ethyl} methyl group, {1- (t-butoxycarbonyl) ethyl} methyl group, {1- (cyclopentyloxycarbonyl) ethyl} methyl group, {1- ( [1-{(cyclo) alkoxycarbonyl} ethyl] methyl group such as cyclohexyloxycarbonyl) ethyl} methyl group; 1- {1 ′-(methoxycarbonyl) ethyl} ethyl group, 1- {1′-
(Ethoxycarbonyl) ethyl｝ ethyl group, 1- {1 ′
-(N-propoxycarbonyl) ethyl @ ethyl group, 1
-{1 ′-(i-propoxycarbonyl) ethyl} ethyl group, 1- {1 ′-(n-butoxycarbonyl) ethyl} ethyl group, 1- {1 ′-(cyclopentyloxycarbonyl) ethyl} ethyl group, 1 1- such as-{1 '-(cyclohexyloxycarbonyl) ethyl} ethyl group;
[1 ′-{(cyclo) alkoxycarbonyl} ethyl]
Ethyl group;

1- {1 ′-(methoxycarbonyl) ethyl} propyl group, 1- {1 ′-(ethoxycarbonyl)
Ethyl {propyl group, 1- {1 ′-(n-propoxycarbonyl) ethyl} propyl group, 1- {1 ′-(i-propoxycarbonyl) ethyl} propyl group, 1- {1 ′
-(N-butoxycarbonyl) ethyl @ propyl group, 1
1- (1 ′-(t-butoxycarbonyl) ethyl} propyl, 1- {1 ′-(cyclopentyloxycarbonyl) ethyl} propyl, 1- {1 ′-(cyclohexyloxycarbonyl) ethyl} propyl, etc. −
[1 ′-{(cyclo) alkoxycarbonyl} ethyl]
Propyl group; 1- {1 ′-(methoxycarbonyl) ethyl} -1-methylethyl group, 1- {1 ′-(ethoxycarbonyl) ethyl} -1-methylethyl group, 1- {1 ′
-(N-propoxycarbonyl) ethyl} -1-methylethyl group, 1- {1 ′-(i-propoxycarbonyl)
Ethyl {-1-methylethyl group, 1- {1 ′-(n-butoxycarbonyl) ethyl} -1-methylethyl group, 1
-{1 ′-(t-butoxycarbonyl) ethyl} -1-
Methylethyl group, 1- {1 ′-(cyclopentyloxycarbonyl) ethyl} -1-methylethyl group, 1-
{1 ′-(cyclohexyloxycarbonyl) ethyl}
1- [1 ′-{(cyclo) alkoxycarbonyl} ethyl] -1-methylethyl group such as -1-methylethyl group;
1- {1 ′-(methoxycarbonyl) ethyl} butyl group, 1- {1 ′-(ethoxycarbonyl) ethyl} butyl group, 1- {1 ′-(n-propoxycarbonyl) ethyl} butyl group, 1- { 1 ′-(i-propoxycarbonyl) ethyl @ butyl group, 1- {1 ′-(n-butoxycarbonyl) ethyl} butyl group, 1- {1 ′-(t-butoxycarbonyl) ethyl} butyl group, 1- {1 ′-(cyclopentyloxycarbonyl) ethyl} butyl group, 1
1- [1 ′-{(cyclo) alkoxycarbonyl} ethyl] butyl group such as-{1 ′-(cyclohexyloxycarbonyl) ethyl} butyl group; 1- {1 ′-(methoxycarbonyl) ethyl} -1-methyl Propyl group, 1-
{1 ′-(ethoxycarbonyl) ethyl} -1-methylpropyl group, 1- {1 ′-(n-propoxycarbonyl) ethyl} -1-methylpropyl group, 1- {1′-
(I-propoxycarbonyl) ethyl {-1-methylpropyl group, 1- {1 ′-(n-butoxycarbonyl) ethyl} -1-methylpropyl group, 1- {1′-t-butoxycarbonyl) ethyl}- 1-methylpropyl group, 1
1- [1 ′-} (cyclo) such as-{1 ′-(cyclopentyloxycarbonyl) ethyl} -1-methylpropyl group and 1- {1 ′-(cyclohexyloxycarbonyl) ethyl} -1-methylpropyl group Alkoxycarbonyldiethyl] -1-methylpropyl group;

1- {1 ′-(methoxycarbonyl) ethyl} cyclopentyl group, 1- {1 ′-(ethoxycarbonyl) ethyl} cyclopentyl group, 1- {1 ′-(n-
Propoxycarbonyl) ethyl @ cyclopentyl group, 1
-{1 ′-(i-propoxycarbonyl) ethyl} cyclopentyl group, 1- {1 ′-(n-butoxycarbonyl) ethyl} cyclopentyl group, 1- {1 ′-(t-butoxycarbonyl) ethyl} cyclopentyl group, 1-
{1 ′-(cyclopentyloxycarbonyl) ethyl}
1- such as cyclopentyl group, 1- {1 ′-(cyclohexyloxycarbonyl) ethyl} cyclopentyl group
[1 ′-{(cyclo) alkoxycarbonyl} ethyl]
Cyclopentyl group; 1- {1 ′-(methoxycarbonyl) ethyl} cyclohexyl group, 1- {1 ′-(ethoxycarbonyl) ethyl} cyclohexyl group, 1- {1 ′
-(N-propoxycarbonyl) ethyl} cyclohexyl group, 1- {1 ′-(i-propoxycarbonyl) ethyl} cyclohexyl group, 1- {1 ′-(n-butoxycarbonyl) ethyl} cyclohexyl group, 1- {1 '-
(T-butoxycarbonyl) ethyl} cyclohexyl group, 1- {1 ′-(cyclopentyloxycarbonyl)
1- [1 ′-{(cyclo) alkoxycarbonyl} ethyl] cyclohexyl group such as ethyl @ cyclohexyl group, 1- {1 ′-(cyclohexyloxycarbonyl) ethyl} cyclohexyl group;

{1- (methoxycarbonyl) propyl}
Methyl group, {1- (ethoxycarbonyl) propyl} methyl group, {1- (n-propoxycarbonyl) propyl} methyl group, {1- (i-propoxycarbonyl) propyl} methyl group, {1- (n-butoxy) Carbonyl)
[1] such as propyl @ methyl group, {1- (t-butoxycarbonyl) propyl} methyl group, {1- (cyclopentyloxycarbonyl) propyl} methyl group, and {1- (cyclohexyloxycarbonyl) propyl} methyl group;
-{(Cyclo) alkoxycarbonyl {propyl} methyl group; 1- {1 ′-(methoxycarbonyl) propyl}
Ethyl group, 1- {1 ′-(ethoxycarbonyl) propyl} ethyl group, 1- {1 ′-(n-propoxycarbonyl) propyl} ethyl group, 1- {1 ′-(i-propoxycarbonyl) propyl} ethyl Group, 1- {1 ′-(n
-Butoxycarbonyl) propyldiethyl group, 1-
{1 ′-(t-butoxycarbonyl) propyl} ethyl group, 1- {1 ′-(cyclopentyloxycarbonyl)
1- [1′- such as propyl @ ethyl group, 1- {1 ′-(cyclohexyloxycarbonyl) propyl} ethyl group, etc.
{(Cyclo) alkoxycarbonyl {propyl] ethyl group;

1- {1 ′-(methoxycarbonyl) propyl} propyl group, 1- {1 ′-(ethoxycarbonyl) propyl} propyl group, 1- {1 ′-(n-propoxycarbonyl) propyl} propyl group, 1- {1'-
(I-propoxycarbonyl) propyl @ propyl group,
1- {1 ′-(n-butoxycarbonyl) propyl} propyl group, 1- {1 ′-(t-butoxycarbonyl) propyl} propyl group, 1- {1 ′-(cyclopentyloxycarbonyl) propyl} propyl group, 1- {1'-
1- [1 ′-{(cyclo) alkoxycarbonyl} propyl] propyl group such as (cyclohexyloxycarbonyl) propyl} propyl group; 1- {1 ′-(methoxycarbonyl) propyl} -1-methylethyl group, 1-
{1 ′-(ethoxycarbonyl) propyl} -1-methylethyl group, 1- {1 ′-(n-propoxycarbonyl) propyl} -1-methylethyl group, 1- {1′-
(I-propoxycarbonyl) propyl {-1-methylethyl group, 1- {1 ′-(n-butoxycarbonyl) propyl} -1-methylethyl group, 1- {1 ′-(t-butoxycarbonyl) propyl} -1-methylethyl group,
1- [1 ′-{(cyclo) such as 1- {1 ′-(cyclopentyloxycarbonyl) propyl} -1-methylethyl group and 1- {1 ′-(cyclohexyloxycarbonyl) propyl} -1-methylethyl group ) Alkoxycarbonyl {propyl] -1-methylethyl group; 1- {1′-
(Methoxycarbonyl) propyl @ butyl group, 1-
{1 ′-(ethoxycarbonyl) propyl} butyl group,
1- {1 ′-(n-propoxycarbonyl) propyl}
Butyl group, 1- {1 ′-(i-propoxycarbonyl)
Propyl @ butyl group, 1- {1 ′-(n-butoxycarbonyl) propyl} butyl group, 1- {1 ′-(t-butoxycarbonyl) propyl} butyl group, 1- {1′-
(Cyclopentyloxycarbonyl) propyl} butyl group, 1- {1 ′-(cyclohexyloxycarbonyl)
1- [1 ′-{(cyclo) alkoxycarbonyl} propyl] butyl group such as propyl @ butyl group; 1- {1′-
(Methoxycarbonyl) propyl {-1-methylpropyl group, 1- {1 ′-(ethoxycarbonyl) propyl}
-1-methylpropyl group, 1- {1 ′-(n-propoxycarbonyl) propyl} -1-methylpropyl group, 1
-{1 ′-(i-propoxycarbonyl) propyl}-
1-methylpropyl group, 1- {1 ′-(n-butoxycarbonyl) propyl} -1-methylpropyl group, 1-
{1 ′-(t-butoxycarbonyl) propyl} -1-
Methylpropyl group, 1- {1 ′-(cyclopentyloxycarbonyl) propyl} -1-methylpropyl group, 1
1- [1 '-{(cyclo) alkoxycarbonyl} propyl] -1-methylpropyl group such as-{1'-(cyclohexyloxycarbonyl) propyl} -1-methylpropyl group;

1- {1 ′-(methoxycarbonyl) propyl} cyclopentyl group, 1- {1 ′-(ethoxycarbonyl) propyl} cyclopentyl group, 1- {1′-
(N-propoxycarbonyl) propyl} cyclopentyl group, 1- {1 ′-(i-propoxycarbonyl) propyl} cyclopentyl group, 1- {1 ′-(n-butoxycarbonyl) propyl} cyclopentyl group, 1- {1 ′
1- [1 ′ such as-(t-butoxycarbonyl) propyl} cyclopentyl group, 1- {1 ′-(cyclopentyloxycarbonyl) propyl} cyclopentyl group, 1- {1 ′-(cyclohexyloxycarbonyl) propyl} cyclopentyl group; -{(Cyclo) alkoxycarbonyl} propyl] cyclopentyl group; 1- {1 ′-(methoxycarbonyl) propyl} cyclohexyl group, 1-
{1 ′-(ethoxycarbonyl) propyl} cyclohexyl group, 1- {1 ′-(n-propoxycarbonyl) propyl} cyclohexyl group, 1- {1 ′-(i-propoxycarbonyl) propyl} cyclohexyl group, 1-
{1 ′-(n-butoxycarbonyl) propyl} cyclohexyl group, 1- {1 ′-(t-butoxycarbonyl)
Propyl @ cyclohexyl group, 1- {1 ′-(cyclopentyloxycarbonyl) propyl} cyclohexyl group, 1- {1 ′-(cyclohexyloxycarbonyl)
Examples thereof include 1- [1 ′-{(cyclo) alkoxycarbonyl} propyl] cyclohexyl group such as propyl @ cyclohexyl group.

Of these acid dissociable groups (1), 1-
(Methoxycarbonylmethyl) -1-methylethyl group,
1- (ethoxycarbonylmethyl) -1-methylethyl group, 1- (t-butoxycarbonylmethyl) -1-methylethyl group, 1- (cyclohexyloxycarbonylmethyl) -1-methylethyl group, 1- (methoxycarbonyl Methyl) -1-methylpropyl group, 1- (ethoxycarbonylmethyl) -1-methylpropyl group, 1- (t-
Butoxycarbonylmethyl) -1-methylpropyl group,
1- (cyclohexyloxycarbonylmethyl) -1-
Methylpropyl group, 1- (methoxycarbonylmethyl)
Cyclopentyl group, 1- (ethoxycarbonylmethyl)
Cyclopentyl group, 1- (i-propoxycarbonylmethyl) cyclopentyl group, 1- (t-butoxycarbonylmethyl) cyclopentyl group, 1- (cyclohexyloxycarbonylmethyl) cyclopentyl group, 1- (methoxycarbonylmethyl) cyclohexyl group, 1- (Ethoxycarbonylmethyl) cyclohexyl group, 1- (t-
Butoxycarbonylmethyl) cyclohexyl group, 1-
(Cyclohexyloxycarbonylmethyl) cyclohexyl and the like are preferred.

The resin (A) can further contain an acid-dissociable group other than the acid-dissociable group (1) (hereinafter referred to as “another acid-dissociable group”. Examples of the group include a t-butyl group, a t-butoxycarbonyl group, an acetyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-butoxyethyl group, a 1-n-pentyloxyethyl group, and a tetrahydro group. Pyranyl group, methyltetrahydropyranyl group, tetrahydrofuranyl group, methyltetrahydrofuranyl group, 3-oxo-1-methylbutyl group, 3-oxo-1,1-dimethylbutyl group, 3-
Oxo-1-i-propylbutyl group, the following general formula (3)
(Hereinafter referred to as “lactone group (3)”), a lactone group represented by the following general formula (4) (hereinafter referred to as “lactone group (4)”), and the like. it can.

[0026]

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[In the general formula (3), R ⁵ represents a hydrogen atom, a methyl group or an ethyl group. ]

[0028]

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[In the general formula (4), R ⁶ represents a hydrogen atom, a methyl group or an ethyl group. Of these other acid dissociable groups, t-butyl group, t-butoxycarbonyl group, 1-ethoxyethyl group, tetrahydropyranyl group, methyltetrahydropyranyl group, tetrahydrofuranyl group, methyltetrahydrofuranyl group,
3-oxo-1-methylbutyl group, 3-oxo-1,1
-Dimethylbutyl group, 3-oxo-1-i-propylbutyl group, lactone group (3), lactone group (4) and the like are preferable.

Hereinafter, resin (AI) and resin (AI)
I) will be described sequentially. The resin (AI) may be, for example, (a) a method of introducing one or more acid-dissociable groups (1) into a previously produced alkali-soluble resin, or (b) one method having an acid-dissociable group (1). The above polymerizable unsaturated compounds (co)
It can be produced by a method of polymerizing, a method of (co) polycondensing (c) one or more polycondensable components having an acid dissociable group (1), and the like.

Examples of the alkali-soluble resin used in the method (a) include an addition polymerization resin or a polycondensation resin having at least one kind of a repeating unit having an acidic functional group. Examples of the repeating unit having an acidic functional group in the addition-polymerizable alkali-soluble resin include, for example, a unit in which a polymerizable unsaturated bond in a polymerizable unsaturated compound having an acidic functional group described below is cleaved. o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, p-carboxystyrene, p-carboxy Methyl styrene, p
(Α-methyl) such as-(2-carboxyethyl) styrene, p-carboxymethoxystyrene, p- (2-carboxyethoxy) styrene, p-carboxymethylcarbonyloxystyrene, and p- (2-carboxyethyl) carbonyloxystyrene ) Styrene derivatives; 2-hydroxy-1-vinylnaphthalene, 3-hydroxy-1-vinylnaphthalene, 4-hydroxy-1-vinylnaphthalene, 5-hydroxy-1-vinylnaphthalene, 6-hydroxy-1-vinylnaphthalene, 7 -Hydroxy-1-
Vinyl naphthalene, 8-hydroxy-1-vinyl naphthalene, 2-hydroxy-1-isopropenyl naphthalene, 3-hydroxy-1-isopropenyl naphthalene,
4-hydroxy-1-isopropenylnaphthalene, 5-
Hydroxy-1-isopropenylnaphthalene, 6-hydroxy-1-isopropenylnaphthalene, 7-hydroxy-1-isopropenylnaphthalene, 8-hydroxy-
1-isopropenylnaphthalene, 2-carboxy-1-
Vinyl naphthalene, 3-carboxy-1-vinylnaphthalene, 4-carboxy-1-vinylnaphthalene, 5-carboxy-1-vinylnaphthalene, 6-carboxy-1
Vinyl naphthalene derivatives such as -vinyl naphthalene, 7-carboxy-1-vinyl naphthalene, 8-carboxy-1-vinyl naphthalene or isopropenyl naphthalene derivatives;

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and cinnamic acid; 2-carboxyethyl (meth) acrylate, (meth) acrylate 2-carboxypropyl acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate,
A compound represented by the following general formula (5) (hereinafter referred to as “(meth)
Acrylic ester (5) ". And carboxylic acid-containing esters of unsaturated carboxylic acids.

[0033]

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[In the general formula (5), R ⁷ represents a hydrogen atom or a methyl group. Among these polymerizable unsaturated compounds, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-carboxystyrene, (meth) acrylic acid, (meth) acrylate (5) and the like are preferable.

The addition-polymerization-based alkali-soluble resin may be composed of only a repeating unit having an acidic functional group. One or more kinds of repeating units in which a saturated bond is cleaved can be contained. Examples of the other polymerizable unsaturated compound include, for example, styrene, α-methylstyrene, 4-t-butylstyrene, 4-t-butyl-α-methylstyrene, 4-chlorostyrene, 4-chloro-α-methyl Styrene, 4-methoxystyrene, 4-
Methoxy-α-methylstyrene, 1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene, 5-methyl-
1-vinylnaphthalene, 1-isopropenylnaphthalene, 4-chloro-1-vinylnaphthalene, 5-chloro-
Vinyl aromatic compounds such as 1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene and 5-methoxy-1-vinylnaphthalene; methyl (meth) acrylate, (meth)
Ethyl acrylate, n-propyl (meth) acrylate,
N-butyl (meth) acrylate, 2 (meth) acrylate
-Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, norbornyl (meth) acrylate, (meth) acrylate
Isobornyl acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate,
(Meth) acrylates such as (meth) acrylates having an alicyclic skeleton in the ester group such as adamantyl (meth) acrylate, 1-methyladamantyl (meth) acrylate, and adamantylmethyl (meth) acrylate Vinyls esters such as vinyl acetate, vinyl propionate and vinyl butyrate; (meth) acrylonitrile, α
-Unsaturated nitrile compounds such as chloroacrylonitrile, crotonitrile, maleinitrile, fumaronitrile, mesaconnitrile, citraconitrile, itaconitrile; etc .; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramid And other nitrogen-containing vinyl compounds such as N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine and vinylimidazole.

Of these other polymerizable unsaturated compounds,
Styrene, α-methylstyrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate , Dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, 1- (meth) acrylate
Methyl adamantyl, adamantyl methyl (meth) acrylate and the like are preferred.

The polycondensation-based alkali-soluble resin may comprise one or more phenols and one or more aldehydes, together with a polycondensation component which may optionally form another repeating unit, in the presence of an acidic catalyst. It can be produced by polycondensation in an aqueous medium or a mixed medium of water and a hydrophilic solvent. Examples of the phenols include phenol, o-cresol, m-cresol, p
-Cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol , Resorcinol, catechol, pyrogallol, 1-naphthol, 2-naphthol and the like. Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde,
Acetaldehyde, propylaldehyde, phenylacetaldehyde and the like can be mentioned. The content of the repeating unit having an acidic functional group in the alkali-soluble resin of the addition polymerization system and the polycondensation system cannot be specified unconditionally depending on the type of the repeating unit and other repeating units.
It is 10 to 100 mol%, preferably 15 to 100 mol%.

In the method (a), the acid dissociable group (1) is introduced by converting an acidic functional group in the alkali-soluble resin into a compound synthesized through a reaction represented by the following general formula (6). It can be carried out by esterification or etherification by a conventional method using a secondary alcohol.

[0039]

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[In the general formula (6), R ¹ , R ² , R
³ and R ⁴ are respectively R ¹ in the general formula (1),
It is synonymous with R ² , R ³ and R ⁴ . Examples of the polymerizable unsaturated compound having an acid dissociable group (1) used in the method (B) include the above (A)
Compounds in which the hydrogen atom of the acidic functional group in the polymerizable unsaturated compound having an acidic functional group exemplified in the method described in the above method is substituted with the acid dissociable group (1). Examples of the polycondensable component having an acid dissociable group (1) include compounds in which the hydrogen atom of the phenolic hydroxyl group of the phenols exemplified in the method (a) is replaced with the acid dissociable group (1). And aldehydes. The polymerizable unsaturated compound having an acid-dissociable group (1) or the polycondensable component having an acid-dissociable group (1) used in the method (b) or (c) is, for example, their acid-dissociable compounds. A compound in which a group is substituted with a hydrogen atom is represented by the formula (6):
Can be synthesized by esterification or etherification by a conventional method using a tertiary alcohol synthesized through the reaction represented by the following formula. In the method (b), the ratio of the polymerizable unsaturated compound having the acid dissociable group (1) to the total polymerizable unsaturated compound is determined by the ratio of the polymerizable unsaturated compound having the acid dissociable group (1) and other polymerizable unsaturated compounds. Although it cannot be specified unconditionally depending on the type of the polymerizable unsaturated compound, it is usually 10 to 10
0 mol%, preferably 15 to 100 mol%, and in the method (c), the ratio of the polycondensable component having the acid dissociable group (1) to the total polycondensable component is not more than the acid dissociable group. Depending on the type of the polycondensable component having (1) and the other polycondensable components, it cannot be unconditionally specified, but is usually from 10 to 10.
It is 100 mol%, preferably 15 to 100 mol%.
The polymerization in producing the addition-polymerization-based alkali-soluble resin in the method (A) and the polymerization in the method (B) are, for example, a radical polymerization initiator, an anionic polymerization catalyst,
A coordination anionic polymerization catalyst, a cationic polymerization catalyst or the like is appropriately selected, and the polymerization can be carried out by an appropriate polymerization method such as bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, or bulk-suspension polymerization.

Specific examples of the preferred resin (AI) in the present invention include the following. 4
-{1 ′-(methoxycarbonylmethyl) -1′-methylethoxy} styrene / p-hydroxystyrene copolymer, 4- {1 ′-(t-butoxycarbonylmethyl)-
1′-methylethoxy} styrene / p-hydroxystyrene copolymer, 4- {1 ′-(methoxycarbonylmethyl) cyclohexyloxy} styrene / p-hydroxystyrene copolymer, 4- {1 ′-(t-butoxy) Styrene-based resins such as carbonylmethyl) cyclohexyloxy} styrene / p-hydroxystyrene copolymer;
{1 ′-(methoxycarbonylmethyl) -1′-methylethoxy} -1-vinylnaphthalene / 4-hydroxy-
1-vinylnaphthalene copolymer, 4- {1 ′-(t-butoxycarbonylmethyl) -1′-methylethoxy}-
1-vinylnaphthalene / 4-hydroxy-1-vinylnaphthalene copolymer, 4- {1 ′-(methoxycarbonylmethyl) cyclohexyloxy} -1-vinylnaphthalene / 4-hydroxy-1-vinylnaphthalene copolymer,
Vinyl naphthalene resins such as 4- {1 ′-(t-butoxycarbonylmethyl) cyclohexyloxy} -1-vinylnaphthalene / 4-hydroxy-1-vinylnaphthalene copolymer;

(Meth) acrylic acid {1- (methoxycarbonylmethyl) -1-methylethyl} / tricyclodecanyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (T-butoxycarbonylmethyl) -1-methylethyl} / tricyclodecanyl (meth) acrylate / (meth) acrylic acid copolymer,
{1- (methoxycarbonylmethyl) cyclohexyl} (meth) acrylate / tricyclodecanyl (meth) acrylate / (meth) acrylic acid copolymer, {1- (t-butoxycarbonylmethyl) methacrylate} Cyclohexyl｝ / tricyclodecanyl (meth) acrylate /
(Meth) acrylic acid copolymer, (meth) acrylic acid ｛1
-(Methoxycarbonylmethyl) -1-methylethyl}
/ Adamantyl (meth) acrylate / copolymer (meth) acrylate, {1- (t-butoxycarbonylmethyl) -1-methylethyl) (meth) acrylate / adamantyl (meth) acrylate / (meth) acrylic acid Acid copolymer,
(Meth) acrylic acid {1- (methoxycarbonylmethyl) cyclohexyl} / (meth) acrylic acid adamantyl / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (t-butoxycarbonylmethyl) cyclohexyl} / Adamantyl (meth) acrylate / copolymer of (meth) acrylic acid, {1- (methoxycarbonylmethyl) -1-methylethyl) (meth) acrylate / 1-methyladamantyl (meth) acrylate / (meth) acrylic acid Acid copolymer, (meth) acrylic acid {1- (t-butoxycarbonylmethyl) -1-methylethyl} / (meth) acrylic acid 1-methyladamantyl / (meth) acrylic acid copolymer, (meth) acrylic acid Acid {1- (methoxycarbonylmethyl) cyclohexyl} / (meth) acrylic acid 1-
Methyl adamantyl / (meth) acrylic acid copolymer,
(Meth) acrylic acid {1- (t-butoxycarbonylmethyl) cyclohexyl} / (meth) acrylic acid 1-methyladamantyl / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (methoxycarbonylmethyl) −
1-methylethyl} / adamantylmethyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (t-butoxycarbonylmethyl) -1-methylethyl} / (meth) acrylic acid Adamantylmethyl / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (methoxycarbonylmethyl) cyclohexyl}
/ Adamantylmethyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (t-butoxycarbonylmethyl) cyclohexyl} / (meth)
Adamantyl methyl acrylate / (meth) acrylic acid copolymer,

(Meth) acrylic acid {1- (methoxycarbonylmethyl) -1-methylethyl} / tricyclodecanyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, (meth) acrylic Acid ｛1-
(T-butoxycarbonylmethyl) -1-methylethyl} / tricyclodecanyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1- (methoxycarbonylmethyl) acrylate) Cyclohexyl} / tricyclodecanyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1- (t-butoxycarbonylmethyl) cyclohexyl) (meth) acrylate / tri (meth) acrylate Cyclodecanyl / 2-hydroxypropyl (meth) acrylate copolymer, {1- (methoxycarbonylmethyl) -1-methylethyl) (meth) acrylate / adamantyl (meth) acrylate / (meth) acrylic acid 2 -Hydroxypropyl copolymer, (meth) acrylic acid {1- (t)
-Butoxycarbonylmethyl) -1-methylethyl} /
Adamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, (meth) acrylic acid {1- (methoxycarbonylmethyl) cyclohexyl}
/ Adamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1- (t-butoxycarbonylmethyl) cyclohexyl) (meth) acrylate / adamantyl (meth) acrylate / (meth) acryl 2-hydroxypropyl acid copolymer, {1- (methoxycarbonylmethyl) -1-methylethyl) (meth) acrylate / 1-methyladamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer Union, (meth) acrylate {1- (t-butoxycarbonylmethyl) -1-methylethyl} / (meth) acrylate 1-methyladamantyl / (meth) acrylate 2-hydroxypropyl copolymer, (meth) Acrylic acid ｛1-
(Methoxycarbonylmethyl) cyclohexyl} / 1-methyladamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, (meth) acrylate {1- (t-butoxycarbonylmethyl) cyclohexyl} / ( 1-methyladamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1- (methoxycarbonylmethyl) -1-methylethyl) (meth) acrylate / adamantylmethyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1- (t-butoxycarbonylmethyl) -1-methylethyl) (meth) acrylate / adamantylmethyl (meth) acrylate / 2- (meth) acrylate Hydroxypropyl copolymer, (meth) acrylic acid {1- (methoxy) (Rubonylmethyl) cyclohexyl} / adamantylmethyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, (meth) acrylic acid {1- (t-butoxycarbonylmethyl) cyclohexyl} / (meth) acrylic acid Adamantyl methyl / 2-hydroxypropyl (meth) acrylate copolymer,

A polymerizable unsaturated compound represented by the following general formula (7) (hereinafter, referred to as “polymerizable unsaturated compound (7)”) / tricyclodecanyl (meth) acrylate / (meth) acrylic acid Copolymer,

[0045]

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[In the general formula (7), R ⁸ represents a hydrogen atom or a methyl group, W is a 1- (methoxycarbonylmethyl) -1-methylethyl group, 1- (t-butoxycarbonylmethyl) -1- Methylethyl group, 1- (methoxycarbonylmethyl) cyclohexyl group or 1- (t
-Butoxycarbonylmethyl) cyclohexyl group. Polymerizable unsaturated compound (7) / adamantyl (meth) acrylate / (meth) acrylic acid copolymer, polymerizable unsaturated compound (7) / 1-methyladamantyl (meth) acrylate / (meth) acrylic acid Copolymer, polymerizable unsaturated compound (7) / adamantylmethyl (meth) acrylate / (meth) acrylic acid copolymer, polymerizable unsaturated compound (7) /
Tricyclodecanyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, polymerizable unsaturated compound (7) / adamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate Copolymerized polymerizable unsaturated compound (7) / 1-methyladamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, polymerizable unsaturated compound (7) / adamantylmethyl (meth) acrylate / (Meth) acrylic acid 2-
(Meth) acrylic resins such as hydroxypropyl copolymer.

Next, as the resin (A-II), for example,
A norbornene-based resin having a repeating unit represented by the following general formula (8) (hereinafter, referred to as "repeating unit (8)") (hereinafter, referred to as "norbornene-based resin (8)") can be given.

[0048]

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[In the general formula (8), α and β are each independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or a monovalent halogenated carbon atom having 1 to 10 carbon atoms. X and Y each independently represent 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 a group -COOZ; Wherein Z represents an acid dissociable group (1), and at least one of X and Y is a group-
COOZ, and n is 0 or 1. The norbornene-based resin (8) corresponds to, for example, (d) a method of introducing one or more acid-dissociable groups (1) into a previously produced norbornene-based alkali-soluble resin, and (e) a repeating unit (8). It can be produced by a method of (co) polymerizing one or more norbornene-based compounds (hereinafter, referred to as "norbornene-based compound (8)").

Examples of the norbornene-based alkali-soluble resin used in the method (d) include a resin containing a repeating unit in which an unsaturated bond of a norbornene-based compound having an acidic functional group described below is cleaved. .
5-carboxybicyclo [2.2.1] hept-2-ene, 5-methyl-5-carboxybicyclo [2.2.
1] Hept-2-ene, 5-ethyl-5-carboxybicyclo [2.2.1] hept-2-ene, 5-n-propyl-5-carboxybicyclo [2.2.1] hept-
2-ene, 6-methyl-5-carboxybicyclo [2.
2.1] Hept-2-ene, 6-ethyl-5-carboxybicyclo [2.2.1] Hept-2-ene, 6-n-
Propyl-5-carboxybicyclo [2.2.1] hept-2-ene, 8-carboxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-
8-carboxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-ethyl-8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8-n-propyl-8-carboxytetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene, 9-methyl-8-carboxytetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 9-ethyl-8-carboxy-tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene, 9-n-propyl-
8-carboxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene and the like.

Of these norbornene compounds, 5
-Carboxybicyclo [2.2.1] hept-2-ene, 5-methyl-5-carboxybicyclo [2.2.
1] hept-2-ene, 8-carboxytetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-
Methyl-8-carboxytetracyclo [4.4.0.1
^2,5 . [ ^17,10 ] dodec-3-ene and the like are preferred.

The norbornene-based alkali-soluble resin used in the method (d) may be composed of only a repeating unit in which the unsaturated bond of the norbornene-based compound having an acidic functional group is cleaved, but the resulting resin Can contain one or more other repeating units, as long as is an alkali-soluble. Examples of such another repeating unit include a repeating unit in which a polymerizable unsaturated bond of another polymerizable unsaturated compound described below is cleaved. Norbornene (bicyclo [2.2.1] hept-2-ene), 5-methoxycarbonylbicyclo [2.2.1]
Hept-2-ene, 5-ethoxycarbonylbicyclo [
2.2.1] Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5-methyl Bicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-
2-ene,

Tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-methoxytetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-
Ethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
3. Dodeca-3-ene, 8-hydroxytetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-hydroxymethyl-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] dodeca-3-ene, 8-hydroxy-8-methyl-tetracyclo [4.4.0.1 ^{2, 5.} [ ^17,10 ] dodec-3-ene, 8-t-butoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-t-
3. Butoxycarbonyl-8-methyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8-Fluorotetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8-fluoromethyl-tetracyclo [4.4.0.1 ^{2, 5.} [ ^17,10 ] dodec-3-ene, 8-difluoromethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-trifluoromethyl-tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodec-3-ene, 8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8,8-difluorotetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-difluoro-tetracyclo [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 ] Dodeca
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.
^12.5 . 1 ^7,10] dodeca-3-ene, 8,8,9- tris (trifluoromethyl) tetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-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] dodeca-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 ] Dodeca
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 ] Dodeca-3
-Ene, 8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-chloro -8,9,9- trifluoro tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-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 . [ ^17,10 ] dodec-3-ene, 8-methyl-8- (2 ', 2', 2'-
3. trifluorocarboxyethyl) tetracyclo [4.
4.0.1 ^2,5 . [ ^17,10 ] norbornene-based compounds such as dodeca-3-ene;

Dicyclopentadiene, tricyclo [5.
2.1.0 ^2,6 ] deca-8-ene, tricyclo [5.
2.1.0 ^2,6 ] deca-3-ene, tricyclo [4.
4.0.1 ^2,5 ] undec-3-ene, tricyclo [
6.2.1.0 ^1,8 ] undec-9-ene, tricyclo
[6.2.1.0 ^1,8 ] undec-4-ene, tetracyclo [4.4.0.1 ^2,5 . ^17,10 . 0 ^1,6 ] Dodeca
3-ene, 8-methyltetracyclo [4.4.0.1
^2,5 . ^17,10 . 0 ^1,6 ] dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . [ ^1,7,12 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.
0.1 ^2,5 . ^17,10 . 0 ^1,6 ] dodeca-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, pentacyclo [7.4.0.1
^2,5 . ^19,12 . 0 ^8,13] pentadeca-3 other polymerizable alicyclic compounds such as ene;

Norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (meth) acryl Adamantyl acid, (meth) acrylic acid 1-
Methyl adamantyl, adamantyl methyl (meth) acrylate, carboxytricyclodecanyl (meth) acrylate, carboxytetracyclodecanyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) ) Cyclohexyl acrylate, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, (meth)
2- (cyclopropyloxycarbonyl) ethyl acrylate, 2- (cyclopentyloxycarbonyl) ethyl (meth) acrylate, 2- (cyclohexyloxycarbonyl) ethyl (meth) acrylate, 2- (cyclohexenyl) methacrylate Oxycarbonyl) ethyl,
2-((4'-methoxycyclohexyl) oxycarbonyl) ethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n- (meth) acrylate Butyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- (meth) acrylate
(Meth) acrylates such as hydroxypropyl; α-methyl such as methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, and n-butyl α-hydroxymethyl acrylate -Hydroxymethyl acrylates; maleic anhydride, vinyl acetate, vinyl propionate, vinyl butyrate, (meth) acrylonitrile, α-
Chloroacrylonitrile, crotonitrile, maleinitrile, fumaronitrile, mesaconitrile, citraconitrile, itaconitrile, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itacon Amides, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, vinylimidazole and the like.

Of these other polymerizable unsaturated compounds,
Norbornene (bicyclo [2.2.1] hept-2-ene), 5-methoxycarbonylbicyclo [2.2.1]
Hept-2-ene, 5-hydroxybicyclo [2.2.
1] Hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 8
-Methoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene, 8-hydroxytetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-
Hydroxy-8-methyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10] dodeca-3-ene, 8-hydroxymethyl-tetracyclo [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
-Tert-butoxycarbonyl-8-methyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate,
Tetracyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ( N-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
Maleic anhydride, maleic nitrile, fumalonitrile,
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, vinylimidazole, etc. Is preferred.

The introduction of the acid dissociable group (1) in the method (d) is carried out, for example, by synthesizing an acidic functional group in the norbornene-based alkali-soluble resin through a reaction represented by the above formula (6). It can be carried out by esterification using a tertiary alcohol by a conventional method. The content of the repeating unit derived from the norbornene-based compound having an acidic functional group in the norbornene-based alkali-soluble resin used in the method (d) cannot be specified unconditionally depending on the type of the repeating unit and other repeating units. , Usually 10 to 10
0 mol%, preferably 15 to 100 mol%. The norbornene-based compound (8) used in the method (e) is, for example, the acidic compound in the norbornene-based compound having an acidic functional group exemplified for the norbornene-based alkali-soluble resin used in the method (d). The functional group can be synthesized by esterification using a tertiary alcohol synthesized through the reaction represented by the above formula (6) by a conventional method. In the method (e), only the norbornene-based compound (8) may be (co) polymerized, but in some cases, another polymerizable unsaturated compound may be copolymerized. Such other polymerizable unsaturated compounds include:
For example, the same compounds as the norbornene-based compound having an acidic functional group and other polymerizable unsaturated compounds exemplified for the norbornene-based alkali-soluble resin used in the method (d) can be used. In the method (e),
The proportion of the norbornene-based compound (8) used relative to the total polymerizable unsaturated compound cannot be specified unconditionally depending on the types of the norbornene-based compound (8) and other polymerizable unsaturated compounds, but is usually 10 to 100 mol%, preferably Is 15 ~
100 mol%. In the resin (A-II), the total content of the repeating unit (8) and the repeating unit derived from another norbornene-based compound is usually 20 mol%.
Or more, preferably 30 mol% or more, more preferably 4 mol% or more.
The content is desirably 0 mol% or more, whereby a radiation-sensitive resin composition having particularly excellent dry etching resistance can be obtained.

The polymerization for producing the norbornene-based alkali-soluble resin in the method (d) and the polymerization in the method (e) may be carried out, for example, by radicals such as hydroperoxides, dialkyl peroxides, diacyl peroxides and azo compounds. It can be carried out in a suitable solvent using a polymerization initiator. As the solvent used for the polymerization,
For example, n-pentane, n-hexane, n-heptane,
alkanes such as n-octane, n-nonane and n-decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; Chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide,
Halogenated hydrocarbons such as chlorobenzene; saturated carboxylic esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and the like And the like. These solvents can be used alone or in combination of two or more.

Specific examples of preferred resins (A-II) in the present invention include the following. 8
-[{1 ′-(methoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4.
0.1 ^2,5 . [ ^17,10 ] dodec-3-ene / 5-carboxybicyclo [2.2.1] hept-2-ene copolymer,
8-[{1 ′-(t-butoxycarbonylmethyl)-
1'-methylethoxydicarbonyl] tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene / 5-
Carboxycyclo [2.2.1] hept-2-ene copolymer, 8- {1 ′-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.
4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene / 5-carboxybicyclo [2.2.1] hept-2-ene copolymer, 8- {1 '-(t-butoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [ 4.
4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene / 5-carboxybicyclo [2.2.1] hept-2-ene copolymer, 8-[{1 '-(methoxycarbonylmethyl)-
1'-methylethoxydicarbonyl] tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene / 5-
Methyl-5-carboxybicyclo [2.2.1] hept-2-ene copolymer, 8-[{1 ′-(t-butoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4 0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene / 5-methyl-5-carboxybicyclo [
2.2.1] Hept-2-ene copolymer, 8- {1′-
(Methoxycarbonylmethyl) cyclohexyloxycarbonyl @ tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene / 5-methyl-5-carboxybicyclo [2.2.1] hept-2-ene copolymer, 8-
{1 ′-(t-butoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.4.0.1
^2,5 . [ ^17,10 ] dodec-3-ene / 5-methyl-5-carboxybicyclo [2.2.1] hept-2-ene copolymer,

8-[{1 ′-(methoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene /
8-carboxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene copolymer, 8-[{1 ′-(t
-Butoxycarbonylmethyl) -1'-methylethoxy {carbonyl] tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] dodeca-3-ene / 8-carboxy-tetracyclo [4.4.0.1 ^{2, 5.} [ ^7,10 ] dodeca-3-ene copolymer, 8- {1 '-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / 8-carboxy-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodeca-3-ene copolymer, 8- {1 ′-(t-butoxycarbonylmethyl) cyclohexyloxycarbonyl}
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene / 8-carboxytetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodeca-3-ene copolymer, 8-
[{1 ′-(methoxycarbonylmethyl) -1-methylethoxy} carbonyl] tetracyclo [4.4.0.1
^2,5 . 1 ^7,10] dodeca-3-ene / 8-methyl-8-carboxy tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]
Dodeca-3-ene copolymer, 8-[{1 ′-(t-butoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene / 8-methyl-8-carboxytetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodeca-3-ene copolymer, 8- {1 ′-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene / 8-
Methyl-8-carboxytetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodeca-3-ene copolymer, 8- {1 ′
-(T-butoxycarbonylmethyl) cyclohexyloxycarbonyl @ tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] dodeca-3-ene / 8-methyl-8-carboxy tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodeca-3-ene copolymer,

8-[{1 ′-(methoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene /
Maleic anhydride copolymer, 8-[{1 ′-(t-butoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene / maleic anhydride copolymer, 8- {1 ′
-(Methoxycarbonylmethyl) cyclohexyloxycarbonyl @ tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene / maleic anhydride copolymer, 8
-{1 ′-(t-butoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.4.0.
^12.5 . [ ^1,7,10 ] dodec-3-ene / maleic anhydride copolymer, 8-[{1 ′-(methoxycarbonylmethyl)]
-1'-methylethoxydicarbonyl] tetracyclo [
4.4.0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene / maleic anhydride / tetracyclodecanyl (meth) acrylate copolymer, 8-[{1 ′-(t-butoxycarbonylmethyl) -1′-methylethoxy} carbonyl ] Tetracyclo [4.4.0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene / maleic anhydride / tetracyclodecanyl (meth) acrylate copolymer, 8- {1 ′-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo
[4.4.0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene / maleic anhydride / tetracyclodecanyl (meth) acrylate copolymer, 8- {1 ′-(t-butoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo
[4.4.0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene / maleic anhydride / tetracyclodecanyl (meth) acrylate copolymer,

8-[{1 ′-(methoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene /
Maleic acid / (meth) 2-hydroxypropyl acrylate copolymer anhydride, 8 - [{1 '- (t-butoxycarbonyl-methyl) -23,25-ethoxy} carbonyl] tetracyclo [4.4.0.1 ^{2 , 5} . 1 ^7,10 ] Dodeca-3
-Ene / maleic anhydride / 2-hydroxypropyl (meth) acrylate copolymer, 8- {1 '-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-
Ene / maleic anhydride / 2-hydroxypropyl (meth) acrylate copolymer, 8- {1 ′-(t-butoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene / maleic anhydride / (meth) acrylic acid 2-hydroxypropyl copolymer, 8-[{1 ′-(methoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / 8-t-butoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene /
Maleic anhydride copolymer, 8-[{1 ′-(methoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene / 8-hydroxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / maleic anhydride copolymers, 8 - [{1 '- (methoxycarbonylmethyl) -23,25 ethoxy} carbonyl] tetracyclo [4.4.0.1 ^{2, 5} ． 1 ^7,10 ] dodec-3-ene /
5-hydroxybicyclo [2.2.1] hept-2-ene / maleic anhydride copolymer, 8-[{1 ′-(methoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / 8-t-butoxycarbonyl-8-methyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodeca-3-ene / maleic anhydride copolymer, 8-[{1 ′
-(Methoxycarbonylmethyl) -1'-methylethoxy {carbonyl] tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] dodeca-3-ene / 8-hydroxy-8-methyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodeca-3-ene / maleic anhydride copolymer, 8-[{1′-
(Methoxycarbonylmethyl) -1′-methylethoxy {carbonyl] tetracyclo [4.4.0.1 ^2,5 .
[ ^1,7,10 ] dodec-3-ene / 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene / maleic anhydride copolymer,

8-[{1 ′-(t-butoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene / 8-t-butoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / maleic anhydride copolymers, 8 - [{1 '- (t-butoxycarbonyl-methyl) -23,25-ethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene / 8-hydroxytetracyclo [4.4.0.1
^2,5 . 1 ^7,10] dodeca-3-ene / maleic anhydride copolymers, 8 - [{1 '- (t-butoxycarbonyl-methyl) -23,25-ethoxy} carbonyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene /
5-hydroxybicyclo [2.2.1] hept-2-ene / maleic anhydride copolymer, 8-[{1 ′-(t-butoxycarbonylmethyl) -1′-methylethoxy} carbonyl] tetracyclo [4 .4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene / 8-t-butoxycarbonyl-8
-Methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene / maleic anhydride copolymer, 8-
[{1 ′-(t-butoxycarbonylmethyl) -1′-
Methylethoxy {carbonyl] tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / 8-hydroxy-8-methyl-tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodeca-3-ene / maleic anhydride copolymer, 8
-[｛1 ′-(t-butoxycarbonylmethyl) -1 ′
-Methylethoxy {carbonyl] tetracyclo [4.
4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene / 5-hydroxy-5-methylbicyclo [2.2.1] hept-2
An ene / maleic anhydride copolymer,

8- {1 ′-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene / 8-
t-butoxycarbonyltetracyclo [4.4.0.1
^2,5 . [ ^7,10 ] dodec-3-ene / maleic anhydride copolymer, 8- {1 '-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / 8-hydroxy-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodeca-3-ene / maleic anhydride copolymer, 8- {1′-
(Methoxycarbonylmethyl) cyclohexyloxycarbonyl @ tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene / 5-hydroxybicyclo [2.
2.1] hept-2-ene / maleic anhydride copolymer,
8- {1 ′-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.4.0.1
^2,5 . 1 ^7,10] dodeca-3-ene / 8-t-butoxycarbonyl-8-methyl tetracyclo [4.4.0.1
^2,5 . [ ^7,10 ] dodec-3-ene / maleic anhydride copolymer, 8- {1 '-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / 8-hydroxy-8-methyl-tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodeca-3-ene / maleic anhydride copolymer, 8
-{1 ′-(methoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.4.0.1
^2,5 . [ ^1,7,10 ] dodec-3-ene / 5-hydroxy-5
-Methylbicyclo [2.2.1] hept-2-ene / maleic anhydride copolymer,

8- {1 ′-(t-butoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene / 8
-T-butoxycarbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodeca-3-ene / maleic anhydride copolymer, 8- {1 ′-(t-butoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene / 8-
Hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene / maleic anhydride copolymer, 8-
{1 ′-(t-butoxycarbonylmethyl) cyclohexyloxycarbonyl} tetracyclo [4.4.0.1
^2,5 . [ ^17,10 ] dodec-3-ene / 5-hydroxybicyclo [2.2.1] hept-2-ene / maleic anhydride copolymer, 8- {1 '-(t-butoxycarbonylmethyl) cyclohexyloxy Carbonyl tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene / 8-
t-butoxycarbonyl-8-methyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / maleic anhydride copolymers, 8- {1 '- (t- butoxycarbonyl) cyclohexyl oxycarbonyl} tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodeca-3-
Ene / 8-hydroxy-8-methyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene / maleic anhydride copolymers, 8- {1 '- (t- butoxycarbonyl) cyclohexyl oxycarbonyl} tetracyclo [4.4.0.1 ^{2, 5.} [ ^17,10 ] dodec-3-ene / 5-hydroxy-5-methylbicyclo [2.2.1]
Hept-2-ene / maleic anhydride copolymer and the like.

Introduction rate of acid dissociable group (1) in resin (A) (ratio of number of acid dissociable groups (1) to total number of acid dissociable groups (1) and free acidic functional groups) Cannot be unconditionally defined by the type of the acid dissociable group (1) and the repeating unit, but is usually 15 to 100 mol%, preferably 20 to 100 mol%.
100 mol%. The resin (A) has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) (hereinafter, referred to as “Mw”).
Varies depending on the desired properties of the radiation-sensitive resin composition, but is preferably from 2,000 to 100,000, more preferably from 3,000 to 60,000. in this case,
When the Mw of the resin (A) is less than 2,000, the film-forming property tends to decrease, while when it exceeds 100,000, the developability as a resist and the resolution tend to decrease.
Further, the degree of dispersion of the resin (A) (Mw / Mn; Mn is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC)) is preferably 1 to 5, more preferably 1 to 3. It is. In the present invention, the resin (A) can be used alone or in combination of two or more.

Acid Generator (B) The component (B) in the present invention comprises a radiation-sensitive acid generator that generates an acid upon exposure (hereinafter, referred to as “acid generator (B)”). The acid generator (B) dissociates the acid-dissociable groups present in the resin (A) by the action of the acid generated by the exposure, and as a result, the exposed portion of the resist film becomes easily soluble in an alkali developing solution, It has the function of forming a mold resist pattern. Examples of such an acid generator (B) include an onium salt, a halogen-containing compound, a diazoketone compound, a sulfone compound, and a sulfonic acid compound. Examples of these acid generators (B) include the following. Onium salt: Examples of the onium salt include an iodonium salt, a sulfonium salt (including a tetrahydrothiophenium salt), a phosphonium salt, a diazonium salt, and a pyridinium salt. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro n-butanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, bis (4-t-butylphenyl) ) Iodonium trifluoromethanesulfonate,
Bis (4-t-butylphenyl) iodonium nonafluoro n-butanesulfonate, bis (4-t-butylphenyl) iodonium dodecylbenzenesulfonate,
Bis (4-t-butylphenyl) iodonium naphthalene sulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro n-butanesulfonate, triphenylsulfonium hexafluoro Antimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium camphorsulfonate, (4-hydroxyphenyl) benzenemethylsulfonium toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethane Sulfonate, dimethyl 2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluorofluoride Methanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate,
Nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate,
-Hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate,

4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
-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-propoxy Carbonyloxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2′-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2′-
Tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (1 ′
-Naphthyl acetomethyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

Halogen-containing compound: Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include phenyl-bis (trichloromethyl) -s-triazine and methoxyphenyl-bis (trichloromethyl)-
s-triazine, naphthyl-bis (trichloromethyl)
Examples thereof include (trichloromethyl) -s-triazine derivatives such as -s-triazine 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, and a diazonaphthoquinone compound. Specific examples of preferred diazoketones include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphtho of 2,3,4,4'-tetrahydroxybenzophenone. Quinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-
5-sulfonic acid ester, 1,1,1-tris (4′-
Examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester of (hydroxyphenyl) ethane. Sulfone compound: Examples of the sulfone compound include β
-Ketosulfone, β-sulfonylsulfone and α-diazo compounds of these compounds. Specific examples of preferable sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane. Sulfonic acid compound: Examples of the sulfonic acid compound include an alkylsulfonic acid ester, an alkylsulfonic acid imide, a haloalkylsulfonic acid ester, an arylsulfonic acid ester, and an iminosulfonate. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, tristrifluoromethanesulfonate of pyrogallol, and nitrobenzyl-9.1.
0-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate,
Examples thereof include 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

Among these acid generators (B), diphenyliodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dimethyl (2-oxocyclohexyl)
Sulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (1′-naphthyl acetomethyl) 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 present invention, the acid generator (B) can be used alone or in combination of two or more. The amount of the acid generator (B) used is
From the viewpoint of ensuring the sensitivity and developability as a resist, the amount is usually 0.1 to 100 parts by weight of the resin (A).
10 parts by weight, preferably 0.5 to 7 parts by weight. In this case, if the amount of the acid generator (B) used is less than 0.1 part by weight, sensitivity and developability tend to decrease, while 10
If the amount exceeds parts by weight, transparency to radiation decreases,
There is a tendency that it is difficult to obtain a rectangular resist pattern.

Various Additives In the present invention, furthermore, acid diffusion having an action of controlling the diffusion phenomenon of an acid generated from an acid generator by exposure in a resist film and suppressing an undesirable chemical reaction in a non-exposed area. Control agents can be included. By using such an acid diffusion controlling agent, the storage stability of the composition is further improved, the resolution as a resist is further improved, and the delay time from exposure to development (P
Variations in the line width of the resist pattern due to variations in ED) can be suppressed, and the process stability is further improved. As the acid diffusion controller, a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment during the resist pattern forming step is preferable. As such a nitrogen-containing organic compound, for example, the following general formula (9)

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[In the general formula (9), R ⁹ , R ¹⁰ and R ¹¹ independently represent a hydrogen atom, an alkyl group, an aryl group or an alkyl group. (Hereinafter, referred to as "nitrogen-containing compound (I)"), a diamino compound having two nitrogen atoms in the same molecule (hereinafter, referred to as "nitrogen-containing compound (II)"), and a nitrogen atom (Hereinafter, referred to as "nitrogen-containing compound (III)"), an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, and the like. Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine;
n-butylamine, di-n-pentylamine, di-n-
Dialkylamines such as hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, and di-n-decylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, -N-pentylamine, tri-n-hexylamine,
Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline And aromatic amines such as 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine and 1-naphthylamine.

Examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4'-aminophenyl) propane, 2- (3'-aminophenyl) -2- (4′-aminophenyl) propane, 2- (4′-aminophenyl)
-2- (3'-hydroxyphenyl) propane, 2-
(4'-aminophenyl) -2- (4'-hydroxyphenyl) propane, 1,4-bis [1 '- ^(4''- aminophenyl) ^-1' - methylethyl] benzene, 1,3
- bis can be mentioned [1 ^{'- (4''-} - aminophenyl) ^-1' methylethyl] benzene, and the like.

Examples of the nitrogen-containing compound (III) include polymers of polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide and the like. Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide,
N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like can be mentioned. Examples of the urea compound include urea, methylurea, 1,1-dimethylurea,
Examples thereof include 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tributylthiourea. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine and 2-ethylpyridine , 4-ethylpyridine, 2-phenylpyridine, 4-
In addition to pyridines such as phenylpyridine, N-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, and acridine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, Morpholine, 4
-Methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like.

Among these nitrogen-containing organic compounds, nitrogen-containing compounds (I), nitrogen-containing heterocyclic compounds and the like are preferable. Further, among the nitrogen-containing compounds (I), trialkylamines are particularly preferable, and among the nitrogen-containing heterocyclic compounds, pyridines are particularly preferable. The acid diffusion controllers can be used alone or in combination of two or more. The amount of the acid diffusion controller is 15 parts per 100 parts by weight of the resin (A).
It is at most 10 parts by weight, preferably at most 10 parts by weight, more preferably at most 5 parts by weight. In this case, if the amount of the acid diffusion controller exceeds 15 parts by weight, the sensitivity as a resist and the developability of an exposed portion tend to decrease. If the amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional fidelity as a resist may be reduced depending on the process conditions.

Further, as an additive other than the acid diffusion controlling agent, a surfactant having an effect of improving the coating property, the developing property 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,
In addition to nonionic surfactants such as polyethylene glycol dilaurate and polyethylene glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflow No. No. 75, the same No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo), F-Top EF301, EF303, and EF
352 (manufactured by Tochem Products), Megafax F1
71, F173 (manufactured by Dainippon Ink and Chemicals), Florado FC430, FC431 (manufactured by Sumitomo 3M),
Asahi Guard AG710, Surflon S-382, S
C-101, SC-102, SC-103, SC
-104, SC-105, SC-106 (manufactured by Asahi Glass) and the like. These surfactants are
They can be used alone or in combination of two or more. The amount of the surfactant is usually 2 parts by weight or less based on 100 parts by weight of the total of the resin (A) and the acid generator (B). In addition, examples of the additives other than the above include an antihalation agent, an adhesion aid, a storage stabilizer, and an antifoaming agent.

Preparation of Composition Solution The radiation-sensitive resin composition of the present invention is usually used such that the total solid content is, for example, 5 to 50% by weight, preferably 10 to 25% by weight when used. After being dissolved in a solvent, for example, the composition is prepared as a composition solution by filtering through a filter having a pore size of about 0.2 μm. Examples of the solvent used for preparing the composition solution include 2-
Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone,
Linear ketones such as -methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; cyclopentanone, 3-methyl-2-cyclopentanone, cyclohexanone, 2-ketone Cyclic ketones such as methylcyclohexanone, 2,6-dimethylcyclohexanone, and isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate; Propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene Propylene glycol monoalkyl ether acetates such as recohol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, 2 Alkyl 2-hydroxypropionates such as n-butyl hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate, and n-propyl alcohol I-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n Propyl ether, ethylene glycol monobutyl -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-methoxy Butyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, acetic acid - propyl acetate n- butyl,
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 ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, -Octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and the like.

These solvents can be used alone or in combination of two or more. Among them, cyclic ketones, linear ketones, propylene glycol monoalkyl ether acetates and 2-hydroxy Alkyl propionates are preferred, and a mixed solvent of a cyclic ketone and at least one selected from the group consisting of linear ketones, propylene glycol monoalkyl ether acetates and alkyl 2-hydroxypropionates is particularly preferred.

Method for Forming Resist Pattern The radiation-sensitive resin composition of the present invention is particularly useful as a chemically amplified positive resist. In the chemically amplified positive resist, the acid dissociable group (1) itself and / or the acid dissociable group (1) in the resin (A) is acted on by the action of an acid generated from the acid generator (B) upon exposure. Group R ^{4 in}
Is dissociated to produce a reaction that is converted into a phenolic hydroxyl group or a carboxyl group, and as a result, the solubility of the exposed portion of the resist in an alkali developing solution is increased, and the exposed portion is dissolved and removed by the alkali developing solution. Is obtained. When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the radiation-sensitive resin composition, by appropriate coating means such as spin coating, casting coating, roll coating, for example, silicon wafer, aluminum A resist film is formed by applying the resist film on a substrate such as a wafer covered with the above, and after pre-baking in some cases, the resist film is exposed so as to form a predetermined resist pattern. The radiation used at this time is an ArF excimer laser (wavelength 1).
93 nm) or KrF excimer laser (wavelength 24
8 nm) is preferred. In the present invention, it is preferable to perform a heat treatment (hereinafter, referred to as “post-exposure bake”) after the exposure. By the post-exposure bake, the conversion reaction of the acid dissociable group proceeds smoothly. The heating condition of the post-exposure bake varies depending on the composition of the radiation-sensitive resin composition, but is usually 30 to 200 ° C, preferably 50 to 170 ° C.
It is. In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, for example, Japanese Patent Publication No. 6-12
As disclosed in Japanese Patent No. 452,452, an organic or inorganic antireflection film can be formed on a substrate to be used, and the influence of basic impurities and the like contained in an environmental atmosphere can be reduced. To prevent this, see, for example, JP-A-5-1885.
As disclosed in JP-A-98-98 and the like, a protective film can be provided on the resist film, or these techniques can be used in combination.

Next, a predetermined resist pattern is formed by developing the exposed resist film. 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-
An alkaline aqueous solution in which at least one kind of alkaline compound such as [4.3.0] -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, unexposed portions also dissolve in the developer, which is not preferable. Further, in the developer comprising the alkaline aqueous solution,
For example, an organic solvent can be added. Specific examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 3-methyl-2-cyclopentanone, 2,6-
Ketones such as dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, i
Alcohols such as -propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; ethyl acetate And esters such as butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone, and dimethylformamide. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is preferably 100% by volume or less based on the alkaline aqueous solution. In this case, if the amount of the organic solvent used exceeds 100% by volume, the developability is reduced, and the undeveloped portion of the exposed portion becomes remarkable, which is not preferable. In addition, an appropriate amount of a surfactant or the like can be added to a developer composed of an alkaline aqueous solution. After development with a developer composed of an alkaline aqueous solution, generally,
Wash with water and dry.

[0084]

Embodiments of the present invention will be described below more specifically with reference to examples. However, the present invention is not limited to these embodiments. Here, parts and% are based on weight unless otherwise specified.
Each measurement and evaluation in Examples and Comparative Examples was performed in the following manner. Mw: Tosoh Corporation GPC column (G2000HXL 2
Gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analytical conditions of flow rate 1.0 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. It was measured. Storage stability: The composition solution was applied on a silicon wafer by spin coating, and prebaked on a hot plate maintained at 140 ° C. for 90 seconds to form a 1 μm-thick resist film onto 2.38% tetramethylammonium hydroxy. After developing with an aqueous solution at 25 ° C. for 1 minute, washing with water and drying, the film thickness was measured. This is defined as the initial remaining film thickness. Further, the composition solution was held in a constant temperature bath at 50 ° C., and a resist film was prepared, developed, washed with water and dried in the same manner as described above from the held composition solution every day. Was measured. At this time, the number of days required for the rate of change of the remaining film thickness after holding from the initial remaining film thickness to exceed 50% was determined and used as a measure of storage stability. The larger the number of days, the better the storage stability. Radiation transmittance: The transmittance of the composition solution was applied to quartz glass by spin coating, and prebaked on a hot plate maintained at 90 ° C. for 60 seconds to obtain a 1 μm-thick resist film from the absorbance at a wavelength of 193 nm. Was calculated as a measure of transparency in the deep ultraviolet region. Relative etching rate: For a coating having a dry film thickness of 0.5 μm obtained by spin-coating a composition solution on a silicon wafer,
Using a dry etching apparatus (Pinnacle8000) manufactured by PMT, using CF _{4 as} the etching gas and a gas flow rate of 75 scc
Dry etching was performed under the conditions of m, pressure 2.5 mToor, and output 2500 W, the etching rate was measured, and the relative etching rate was evaluated based on the relative value to the etching rate of the film made of cresol novolak resin. The lower the etching rate, the better the dry etching resistance. Sensitivity: After spin-coating the composition solution on a silicone wafer, 9
Prebaking was performed for 0 second to form a resist film having a thickness of 0.5 μm. An ArF excimer laser exposure apparatus manufactured by Nikon Corporation (lens numerical aperture 0.5
5, exposure wavelength 193 nm) through a mask pattern. Next, after baking for 90 seconds on a hot plate maintained at 90 ° C., 2.38%
With an aqueous solution of tetramethylammonium hydroxide,
The film was developed at 25 ° C. for 1 minute, washed with water, and dried to form a positive resist pattern. At this time, an exposure amount for forming a line-and-space pattern (1L1S) having a line width of 0.18 μm with a line width of 1: 1 was set as an optimum exposure amount, and this optimum exposure amount was set as a sensitivity. Resolution: The minimum resist pattern size resolved when exposed at the optimal exposure amount was defined as the resolution. Developability: The degree of scum and residual development was examined using a scanning electron microscope. Pattern shape: lower side dimension L of a rectangular cross section of a line and space pattern (1L1S) having a line width of 0.20 μm
₁ and the upper and lower side dimensions L ₂ were measured by a scanning electron microscope. When the pattern satisfies 0.85 ≦ L ₂ / L ₁ ≦ 1 and the pattern shape did not have a tail, the pattern shape was “good”. It was assumed to be.

[0085]

EXAMPLES [Synthesis of tertiary alcohol having acid dissociable group (1)] Synthesis Example 1 Synthesis of methyl 3-hydroxy-3-methylbutanoate After purging with nitrogen, the mixture was heated to 70 ° C. and stirred. Subsequently, acetone / methyl bromoacetate = 5.0 g / 19.6.
After the mixed solution was added over 1 hour, the mixture was stirred and reacted at 70 ° C. for 5 hours. After the reaction was completed, 50 ml of water was added, and 200 ml of ethyl acetate was further added. Then, an aqueous layer was separated using a separating funnel. Subsequently, water 5 was added to the organic layer.
The operation of adding 0 ml and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, after anhydrous magnesium sulfate was added to the organic layer and dried, ethyl acetate was distilled off under reduced pressure to obtain methyl 8.6-methyl-3-hydroxy-3-methylbutanoate.
g was obtained.

Synthesis Example 2 1- (t-butoxycarbonylmethyl) cyclohexano
9.5 g of synthetic zinc and 1.1 g of iodine were placed in a flask, and the inside of the flask was replaced with nitrogen, followed by heating to 70 ° C. and stirring. continue. Cyclohexanone / t-butyl bromoacetate = 8.4
g / 25 g of the mixed solution over 1 hour.
The mixture was reacted by stirring at 5 ° C. for 5 hours. After the reaction, water 50m
After addition of 1 ml of ethyl acetate and 200 ml of ethyl acetate, the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Then, after anhydrous magnesium sulfate was added to the organic layer and dried, ethyl acetate was distilled off under reduced pressure to obtain 14 g of 1- (t-butoxycarbonylmethyl) cyclohexanol.

[Synthesis of Polymerizable Unsaturated Compound Having Acid-Dissociable Group (1)] Synthesis Example 3 Methyl 3-hydroxy-3-methylbutanoate 56.8 g Compound represented by the following formula (10) 119 g Trifluoroacetic acid 90.4 g of anhydride was placed in a flask, and 300 m of anhydrous tetrahydrofuran was added.
After adding 1 to dissolve, the inside of the flask was replaced with dry air, stirred at 10 ° C. for 80 minutes, and further stirred at room temperature for 8 hours to react. After completion of the reaction, a saturated aqueous solution of NaHCO ₃ was added until the reaction solution became neutral, and then 500 ml of ethyl acetate was added. Then, the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed.
Subsequently, after anhydrous magnesium sulfate was added to the organic layer and dried, ethyl acetate was distilled off under reduced pressure to obtain the following formula (11)
145 g of the compound represented by was obtained. This compound is referred to as an ester compound (a).

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Synthesis Example 4 Methyl 3-hydroxy-3-methylbutanoate 56.8 g 8-carboxytetracyclo [4.4.0.1 ^2,5 . [ ^7,10 ] dodecane-3-ene 87.9 g trifluoroacetic anhydride 90.4 g was placed in a flask, and anhydrous tetrahydrofuran 50 ml was added.
Was added and dissolved, and then the inside of the flask was replaced with dry air, and the mixture was stirred at 10 ° C. for 80 minutes, and further stirred at room temperature for 8 hours to react. After completion of the reaction, a saturated aqueous solution of NaHCO ₃ was added until the reaction solution became neutral, and 200 ml of ethyl acetate was further added. Then, an aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, after anhydrous magnesium sulfate was added to the organic layer and dried, ethyl acetate was distilled off under reduced pressure to give 8-[｛1 ′-(methoxycarbonylmethyl) represented by the following formula (12).
-1'-methylethoxydicarbonyl] tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane-3-ene 12
3.7 g were obtained. This compound is converted to an ester compound (b)
And

[0091]

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Synthesis Example 5 Methyl 3-hydroxy-3-methylbutanoate 68.2 g Triethylamine 68 g was placed in a flask, 200 ml of anhydrous dichloromethane was added to dissolve the mixture, and the mixture was stirred at 0 ° C. for 10 minutes. Subsequently, after 56 g of acrylic acid chloride was added over 2 hours, the reaction solution was returned to room temperature, and reacted by stirring for 3 hours. After completion of the reaction, the hydrochloride of triethylamine was filtered off, 50 ml of water was added to the filtrate, and the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, after anhydrous magnesium sulfate was added to the organic layer and dried, dichloromethane was distilled off under reduced pressure to give acrylic acid {1- (methoxycarbonylmethyl) -1-methylethyl} represented by the following formula (13). 60 g were obtained. This compound is referred to as an ester compound (c).

[0093]

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Synthesis Example 6 1- (t-butoxycarbonylmethyl) cyclohexanol 92.1 g Compound represented by the above formula (10) 119 g Trifluoroacetic anhydride 90.4 g was placed in a flask, and anhydrous tetrahydrofuran 300 m
After adding 1 to dissolve, the inside of the flask was replaced with dry air, stirred at 10 ° C. for 80 minutes, and further stirred at room temperature for 8 hours to react. After completion of the reaction, a saturated aqueous solution of NaHCO ₃ was added until the reaction solution became neutral, and then 500 ml of ethyl acetate was added. Then, the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed.
Subsequently, after anhydrous magnesium sulfate was added to the organic layer and dried, ethyl acetate was distilled off under reduced pressure to obtain the following formula (14)
The compound represented by was obtained. This compound is referred to as an ester compound (d).

[0095]

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Synthesis Example 7 1- (t-butoxycarbonylmethyl) cyclohexanol 92.1 g 8-carboxytetracyclo [4.4.0.1 ^2,5 . [ ^7,10 ] dodecane-3-ene 87.9 g trifluoroacetic anhydride 90.4 g was placed in a flask, and anhydrous tetrahydrofuran 50 ml was added.
Was added and dissolved, and then the inside of the flask was replaced with dry air, and the mixture was stirred at 10 ° C. for 80 minutes, and further stirred at room temperature for 8 hours to react. After completion of the reaction, a saturated aqueous solution of NaHCO ₃ was added until the reaction solution became neutral, and 200 ml of ethyl acetate was further added. Then, an aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, after adding anhydrous magnesium sulfate to the organic layer and drying, ethyl acetate was distilled off under reduced pressure to give 8- {1 ′-(t-butoxycarbonylmethyl) cyclohexyloxy represented by the following formula (15). Carbonyl tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane-3-ene 17
0 g and 150 g were obtained. This compound is referred to as an ester compound (e).

Synthesis Example 8 10.5 g of 1- (t-butoxycarbonylmethyl) cyclohexanol was placed in a flask, 200 ml of anhydrous dichloromethane was added to dissolve the mixture, and the mixture was stirred at 0 ° C. for 10 minutes. Subsequently, after 56 g of acrylic acid chloride was added over 2 hours, the reaction solution was returned to room temperature, and reacted by stirring for 3 hours. After completion of the reaction, the hydrochloride of triethylamine was filtered off, 50 ml of water was added to the filtrate, and the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, anhydrous magnesium sulfate was added to the organic layer and dried, and then dichloromethane was distilled off under reduced pressure to obtain {1- (t-butoxycarbonylmethyl) cyclohexyl acrylate} 80 g. This compound is referred to as an ester compound (f).

[Production of Resin (A)] Polymerization Example 1 Ester compound (a) 26.1 g Tricyclodecanyl acrylate 15 g Azoisobutyronitrile 0.2 g t-Dodecyl mercaptan 0.1 g It was dissolved in 100 ml of ethoxyethane and reacted at 65 ° C. for 5 hours with stirring. After the reaction,
The reaction solution was administered in a large amount of methanol to reprecipitate the polymer, and then dried under reduced pressure to obtain 35 g of a white resin having an Mw of 18,000. In this resin, the content of the repeating unit derived from the ester compound (a) and the content of the repeating unit derived from tricyclodecanyl acrylate were 50 mol% and 50 mol%, respectively. This resin is referred to as resin (A-1).

Polymerization Example 2 32.2 g of ester compound (b) 9.4 g of maleic anhydride 3.3 g of azoisobutyronitrile was dissolved in 40 ml of 1,2-diethoxyethane and stirred at a reaction temperature of 65 ° C. for 5 hours. And reacted. After completion of the reaction, the reaction solution was administered into a large amount of methanol to reprecipitate the polymer, and then dried under reduced pressure to obtain 20 g of a white resin having Mw of 6,000. In this resin, the content of the repeating unit derived from the ester compound (b) and the content of the repeating unit derived from maleic anhydride were 45 mol% and 55 mol%, respectively. This resin is referred to as resin (A-2).

Polymerization Example 3 Ester compound (c) 19.8 g Tricyclodecanyl acrylate 21.9 g Azoisobutyronitrile 0.2 g t-Dodecyl mercaptan 0.1 g was dissolved in 1,2-diethoxyethane 100 ml. The reaction was stirred at a reaction temperature of 65 ° C. for 5 hours. After the reaction,
The reaction solution was administered in a large amount of methanol to reprecipitate the polymer, and then dried under reduced pressure to obtain 15 g of a white resin having an Mw of 15,000. In this resin, the content of the repeating unit derived from the ester compound (c) and the content of the repeating unit derived from tricyclodecanyl acrylate were 55 mol% and 45 mol%, respectively. This resin is referred to as resin (A-3).

Polymerization Example 4 31.5 g of ester compound (d) 15 g of tricyclodecanyl acrylate 0.2 g of azoisobutyronitrile 0.1 g of t-dodecyl mercaptan was dissolved in 100 ml of 1,2-diethoxyethane and reacted. The mixture was stirred and reacted at a temperature of 65 ° C. for 5 hours. After the reaction,
The reaction solution was administered in a large amount of methanol to reprecipitate the polymer, and then dried under reduced pressure to obtain 37 g of a white resin having an Mw of 15,000. In this resin, the content of the repeating unit derived from the ester compound (d) and the content of the repeating unit derived from tricyclodecanyl acrylate were 45 mol% and 55 mol%, respectively. This resin is referred to as resin (A-4).

Polymerization Example 5 Ester compound (e) 40.5 g Maleic anhydride 9.4 g Azoisobutyronitrile 3.3 g was dissolved in 1,2-diethoxyethane 40 ml, and the mixture was stirred at a reaction temperature of 65 ° C. for 5 hours. And reacted. After the completion of the reaction, the reaction solution was administered in a large amount of methanol to reprecipitate the polymer, and then dried under reduced pressure to obtain 22 g of a white resin having an Mw of 3,000. In this resin, the content of the repeating unit derived from the ester compound (e) and the content of the repeating unit derived from maleic anhydride were 50 mol% and 50 mol%, respectively. This resin is referred to as resin (A-5).

Polymerization Example 6 Ester compound (f) 28.5 g Tricyclodecanyl acrylate 21.9 Azoisobutyronitrile 0.2 g t-Dodecyl mercaptan 0.1 g was dissolved in 1,2-diethoxyethane 100 ml. The reaction was stirred at a reaction temperature of 65 ° C. for 5 hours. After the reaction,
The reaction solution was administered in a large amount of methanol to reprecipitate the polymer, and then dried under reduced pressure to obtain 17 g of a white resin having an Mw of 12,000. In this resin, the content of the repeating unit derived from the ester compound (f) and the content of the repeating unit derived from tricyclodecanyl acrylate were 50 mol% and 50 mol%, respectively. This resin is referred to as resin (A-6).

Comparative Polymerization Example 1 Tetrahydropyranyl acrylate 18.28 g Tricyclodecanyl acrylate 25 g Azoisobutyronitrile 0.2 g t-Dodecyl mercaptan 0.1 g was dissolved in 1,2-diethoxyethane 100 ml. The reaction was carried out by stirring at a reaction temperature of 65 ° C. for 5 hours. After the reaction,
The reaction solution was administered in a large amount of methanol to reprecipitate the polymer, and then dried under reduced pressure to obtain 15 g of a white resin having Mw of 20,000. This resin is referred to as a resin (a-1).

Examples 1 to 7 and Comparative Examples 1 to 2 The resins prepared in the above polymerization examples, the acid generator (B) and the solvent were mixed to form a uniform solution, and the mixture was then passed through a membrane filter having a pore size of 0.2 μm. After filtration, a composition solution having the composition shown in Table 1 (parts based on weight) was prepared, and various evaluations were made. The evaluation results are shown in Tables 1 and 2.
The types of the acid generator (B) and the solvent in each Example and Comparative Example are as follows. Acid generator (B) B-1: cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate B-2: triphenylsulfonium trifluoromethanesulfonate B-3: 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate B- 4: 4-hydroxy-1-naphthyltetramethylenethiophenium trifluoromethanesulfonate B-5: 4-n-butoxy-1-naphthyltetramethylenethiophenium trifluoromethanesulfonate Solvent C-1: 2-heptanone C- 2: Ethyl 2-hydroxypropionate

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

Industrial Applicability The radiation-sensitive resin composition of the present invention has excellent storage stability and, as a chemically amplified resist, has high transparency to radiation and excellent resolution, as well as dry etching resistance, sensitivity, pattern shape and the like. And can be used very suitably in the manufacture of semiconductor devices, for which further miniaturization is expected in the future.

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Continuation of front page (72) Inventor Haruo Iwasawa JSRL Co., Ltd. 2-1-1-24 Tsukiji, Chuo-ku, Tokyo

Claims (1)

[Claims] (A) An alkali-insoluble or alkali-soluble resin having a group represented by the following general formula (1) as an acid-dissociable group, wherein the acid-dissociable group itself and / or
Alternatively, a radiation-sensitive resin composition containing (B) a resin which becomes alkali-soluble when the group R ⁴ in the acid-dissociable group is dissociated, and (B) a radiation-sensitive acid generator. Embedded image [In the general formula (1), R ¹ and R ² independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ¹ and R ² represent A 3- to 6-membered cyclic alkyl group bonded to each other;
³ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and R ⁴ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. ]