JP2002311590A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition for forming a fine line pattern particularly even when the space width of a line-and-space pattern is wide and excellent also in transparency, sensitivity and resolution to radiation. SOLUTION: The radiation sensitive resin composition contains (A) an alkali- insoluble or slightly alkali-soluble resin containing repeating units derived from a compound obtained by substituting a group of formula (1), (2) or (3) (where R<2> , R<4> and R<6> are each H or lower alkyl; X is methylene, -O- or -S-; and (a) is 1-5) for the hydrogen atom of a carboxyl group in (meth)acrylic acid and repeating units derived from 2-methyl-2-adamantyl (meth)acrylate or the like and exhibiting alkali solubility under the action of an acid, (B) a radiation sensitive acid generator and (C) a polycyclic compound having a functional group such as a t-butoxycarbonyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the involvement in the radiation-sensitive resin composition, more particularly, KrF excimer laser, deep UV such as ArF excimer laser or F ₂ excimer laser, X-rays such as synchrotron radiation, electron The present invention relates to a radiation-sensitive resin composition that can be suitably used as a chemically amplified resist useful for fine processing using various radiations such as charged particle beams such as radiation.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit elements, lithography technology capable of microfabrication at a level of 0.20 μm or less has recently been required in order to obtain a higher degree of integration. Have been. However, in conventional lithography processes, i.
Near-ultraviolet rays such as lines are used, but it is said that it is extremely difficult to perform sub-quarter micron level fine processing with such 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. As such short-wavelength radiation, for example, the emission line spectrum of a mercury lamp,
Examples include far ultraviolet rays represented by excimer lasers, X-rays, and electron beams. Of these, KrF
An excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm) or an F ₂ excimer laser (wavelength: 157 nm) has been receiving attention. As a resist suitable for such excimer laser irradiation,
Irradiation with a component having an acid dissociable functional group and radiation (hereinafter, referred to as
This is called "exposure". ) To generate an acid (hereinafter, referred to as
It is referred to as "radiation-sensitive acid generator". (Hereinafter referred to as “chemically amplified resist”).
That. ) Have been proposed. As a chemically amplified resist, for example, Japanese Patent Publication No. 27660/1990 contains a polymer having a t-butyl ester group of carboxylic acid or a t-butyl carbonate group of phenol and a radiation-sensitive acid generator. Resists have been proposed.
This resist, by the action of the acid generated by exposure,
T-butyl ester group or t-butyl ester present in the polymer
Utilizing the phenomenon that the butyl carbonate group is dissociated and the polymer has an acidic functional group consisting of a carboxyl group or a phenolic hydroxyl group. It was done.

[0003] By the way, most of the conventional chemically amplified resists are based on phenolic resins,
In the case of such a resin, when far-ultraviolet rays are used as the radiation, the far-ultraviolet rays are absorbed due to the aromatic ring in the resin, so that the exposed far-ultraviolet rays cannot sufficiently reach the lower layer of the resist film. There is a drawback, so the exposure amount is large in the upper layer part of the resist film, it decreases in the lower layer part, and the resist pattern after development becomes a trapezoidal shape as the upper part becomes thinner and goes to the lower part, and sufficient resolution can not be obtained There was such a problem. 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. On the other hand, the shape of the resist pattern can be improved by increasing the radiation transmittance of the resist film. For example, a (meth) acrylate resin represented by polymethyl methacrylate has high transparency even with far ultraviolet rays and is a very preferable resin from the viewpoint of radiation transmittance. Has proposed a chemically amplified resist using a methacrylate resin. However, although this composition is excellent in terms of fine processing performance, it has no aromatic ring and thus has a drawback that dry etching resistance is low, and in this case also, it is difficult to perform high-precision etching processing. Therefore, it cannot be said that the film has both transparency to radiation and dry etching resistance.

As one of measures to improve dry etching resistance of a chemically amplified resist without impairing transparency to radiation, an aliphatic ring is introduced into the resin component of the resist instead of an aromatic ring. For example, Japanese Patent Application Laid-Open No. Hei 7-234511 proposes a chemically amplified resist using a (meth) acrylate resin having an aliphatic ring. However,
In this resist, as the acid dissociable functional group of the resin component, a group that is relatively easily dissociated by a conventional acid (for example, an acetal-based functional group such as a tetrahydropyranyl group) or a group that is relatively hard to be dissociated by an acid (for example, , A t-butyl-based functional group such as a t-butyl ester group or a t-butyl carbonate group). In the case of the former resin component having an acid-dissociable functional group, the basic physical properties of the resist, particularly the sensitivity and pattern Although the shape is good, there is a problem in storage stability as a composition, and in the latter resin component having an acid dissociable functional group, on the contrary, storage stability is good, but the basic physical properties of the resist, especially There is a disadvantage that sensitivity and pattern shape are impaired. Furthermore, since an aliphatic ring is introduced into the resin component in the resist, the hydrophobicity of the resin itself is extremely high, and there is a problem in the adhesiveness to the substrate.
In addition, when a resist pattern is formed using a chemically amplified resist, a heat treatment is usually performed after exposure to promote the dissociation of an acid dissociable functional group. It is inevitable that the line width also fluctuates to some extent. However, reflecting the recent miniaturization of integrated circuit elements, there has been a strong demand for the development of a resist having a small line width variation (that is, temperature dependency) even with a change in heating temperature after exposure. .

[0005] Further, as one of measures for improving the characteristics of the chemically amplified radiation-sensitive composition as a resist, a large number of multi-component compositions of three or more components in which a high-molecular or low-molecular additive is blended have been proposed. For example, Japanese Patent Application Laid-Open No. 7-2
No. 34511 discloses a resin having a hydrophilic group,
Copolymers of p-hydroxystyrene and tetrahydropyranyl (meth) acrylate or t-butyl (meth) acrylate, p-hydroxystyrene and p-tetrahydropyranyloxycarbonyloxystyrene or pt-butoxycarbonyloxy By blending t-butyl 3-adamantanecarboxylate as a hydrophobic compound into a resist containing a p-hydroxystyrene copolymer such as a copolymer with styrene, the process from exposure to heat treatment after exposure is delayed. It is disclosed that the influence of time is reduced, or that stable patterning is possible even in the case of a resist containing a group having strong hydrophobicity. However,
In conventional multi-component chemically amplified radiation-sensitive compositions, including those disclosed in JP-A-7-234511, particularly,
Variations in the line width of the line pattern due to the sparse density of the and space pattern are large, and the performance as a resist is still unsatisfactory. Under these circumstances, from the viewpoint of technology development that can cope with the progress of miniaturization and expansion of application fields in integrated circuit elements, it is applicable to short-wavelength radiation represented by far ultraviolet rays, There is a strong demand for the development of a new chemically amplified resist that has a small variation in the line width of the line pattern due to the sparseness of the space pattern and has excellent transparency, sensitivity, resolution, and the like to radiation.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to form a fine line pattern even when the space width of the line and space pattern is wide, and to further improve the transparency, sensitivity, resolution and the like with respect to radiation. Another object of the present invention is to provide a radiation-sensitive resin composition which is useful as a chemically amplified resist excellent in heat resistance.

[0007]

According to the present invention, the object is to provide (A) a repeating unit (I) represented by the following general formula (1):
-1), the repeating unit (I-2) and the repeating unit (I-
At least one type of repeating unit selected from the group of 3),
A repeating unit (II) represented by the following general formula (2),
An alkali-insoluble or alkali-insoluble resin showing alkali solubility by the action of an acid, (B) a radiation-sensitive acid generator, and (C) a compound of the formula -COOR ⁹ wherein R ⁹ is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, 1 substituted or unsubstituted C3-20 monovalent alicyclic hydrocarbon group or -CH ₂ CO
OR ¹⁰ (where R ¹⁰ is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted monovalent alicyclic carbon having 3 to 20 carbon atoms) A hydrogen group). A radiation-sensitive resin composition comprising a polycyclic compound having a group represented by the formula and having a molecular weight of 1,000 or less.

[0008]

Embedded image [In the general formula (1), R ¹ , R ³ and R ⁵ independently represent a hydrogen atom or a methyl group, and R ² , R ⁴ and R ⁶ independently represent a hydrogen atom or a carbon number of 1 to 4 X represents a methylene group, an oxygen atom or a sulfur atom, and a is an integer of 1 to 5. ]

[0009]

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[In the general formula (2), R ⁷ represents a hydrogen atom or a methyl group, and each R ⁸ independently has 4 carbon atoms.
To 20 monovalent alicyclic hydrocarbon groups or derivatives thereof,
Or a linear or branched alkyl group having 1 to 4 carbon atoms, and at least one or a alicyclic hydrocarbon group or a derivative thereof or any two of R ^8, the R ⁸ are mutually Bond to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which each is bonded, and the remaining R ⁸ has 1 to 1 carbon atoms
4 linear or branched alkyl group or 4 carbon atoms
To 20 monovalent alicyclic hydrocarbon groups or derivatives thereof. ] Is achieved.

Hereinafter, the present invention will be described in detail. At least component (A) in the resin (A) The present invention, repeating units shown by the general formula (1) (I-1) , selected from the group consisting of repeating units (I-2) and the repeating units (I-3) An alkali-insoluble or alkali-insoluble resin (hereinafter, referred to as an alkali-soluble resin) containing one type of repeating unit and the repeating unit (II) represented by the general formula (2) and showing alkali solubility by the action of an acid.
It is called “resin (A)”. ). The term “alkali-insoluble or poorly alkali-soluble” as used herein refers to an alkali developing condition employed when a resist pattern is formed from a resist film formed from a radiation-sensitive resin composition containing the resin (A). 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.

In the repeating unit (I-1) and the repeating unit (I-2), the carbonyloxy group bonded to the main chain carbon atom of each repeating unit is a carbon atom forming a lactone group in the ring. And any of the carbon atoms other than the carbon atom to which the group R ² or the group R ⁴ is bonded, and the preferred bonding position is the following formula (3-1) or the following formula (3- This is the position shown in 2).

In the repeating unit (I-3), the carbonyloxy group bonded to the main chain carbon atom of the repeating unit is bonded to the carbon atom forming the lactone group and the group R ⁶ . It is possible to bond at any carbon atom position other than the carbon atom, but a preferred bonding position is a position shown in the following formula (3-3) (that is, an α-position with respect to the carbonyl group in the lactone group) or The position shown in the formula (3-4) (that is, β-
Rank).

[0014]

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In the repeating unit (I-1), the repeating unit (I-2) and the repeating unit (I-3), a group R
² , the group R ⁴ and the group R ⁶ can be bonded at any carbon atom other than the carbon atom to which the carbonyloxy group is bonded and the carbon atom forming the lactone group in each repeating unit. . R ² , R ⁴ and R ⁶ have 1 carbon atom
Examples of the straight-chain or branched alkyl group of to 4 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, A t-butyl group and the like can be mentioned. Of these alkyl groups, a methyl group is preferred.
Further, a in the repeating unit (I-3) is preferably 1 or 2.

Preferred repeating units (I-1) include:
For example, an acrylic repeating unit in which R ² is a hydrogen atom, a carbonyloxy group bonded to a main chain carbon atom is bonded at the position shown in the above formula (3-1), and R ¹ is a hydrogen atom A methacrylic repeating unit wherein R ² is a hydrogen atom, a carbonyloxy group bonded to a main chain carbon atom is bonded at the position shown in the above formula (3-1), and R ¹ is a methyl group; An acrylic repeating unit in which R ² is a methyl group, a carbonyloxy group bonded to a main chain carbon atom is bonded at the position shown in the above formula (3-1), and R ¹ is a hydrogen atom; ² is a methyl group, and the carbonyloxy group bonded to the main chain carbon atom is represented by the above formula (3-1)
And a methacrylic repeating unit in which R ¹ is a methyl group.

[0017] Preferred repeating units (I-2), for example, R ⁴ is a hydrogen atom, a position carbonyl group attached to the main chain carbon atoms is shown in the equation (3-2) An acrylic repeating unit wherein R ³ is a hydrogen atom; R ⁴ is a hydrogen atom and the carbonyloxy group bonded to the main chain carbon atom is represented by the formula (3-2)
A methacrylic repeating unit wherein R ³ is a methyl group; R ⁴ is a methyl group and the carbonyloxy group bonded to the main chain carbon atom is represented by the formula (3-
An acrylic repeating unit bonded to the position shown in 2), wherein R ³ is a hydrogen atom; R ⁴ is a methyl group, and the carbonyloxy group bonded to the main chain carbon atom is represented by the formula (3)
And a methacrylic repeating unit in which R ³ is a methyl group bonded to the position shown in -2).

Further, as a preferred repeating unit (I-3), for example, R ⁶ is a hydrogen atom, and a carbonyloxy group bonded to a main chain carbon atom is represented by the above formula (3-3) or (3-3). -4) an acrylic repeating unit wherein R ⁵ is a hydrogen atom; R ⁶ is a hydrogen atom and the carbonyloxy group bonded to the main chain carbon atom is represented by the formula (3- 3) or a methacrylic repeating unit bonded to the position shown in formula (3-4), wherein R ⁵ is a methyl group; a carbonyloxy group bonded to the main chain carbon atom, wherein R ⁶ is a methyl group Is bonded to the position shown in the formula (3-3) or the formula (3-4), and an acrylic repeating unit in which R ⁵ is a hydrogen atom; R ⁶ is a methyl group;
The carbonyloxy group bonded to the main chain carbon atom is bonded to the position shown in the above formula (3-3) or (3-4), and a methacrylic repeating unit in which R ⁶ is a methyl group. be able to.

In the present invention, the repeating unit (I-1)
Among the repeating unit (I-2) and the repeating unit (I-3), the repeating unit (I-1) and the repeating unit (I-2)
And particularly preferably a repeating unit (I-1). In the resin (A), the repeating unit (I-1), the repeating unit (I-2) and the repeating unit (I-3) may be present alone or in combination of two or more. The repeating unit (I-1), the repeating unit (I-2) and the repeating unit (I-3) are each a repeating unit derived from a corresponding (meth) acrylate.

Next, in the repeating unit (II), carbon monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms and any two of R ^8, is formed by combining mutually R ⁸ 4 ~ 20
Examples of the divalent alicyclic hydrocarbon group include oils derived from cycloalkanes such as norbornane, tricyclodecane, tetracyclododecane, and adamantane, and cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. A group consisting of an alicyclic ring; a group consisting of these alicyclic rings is, for example, a methyl group, an ethyl group,
Linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as -propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc. One or more kinds or groups substituted by one or more kinds can be mentioned. Among these monovalent or divalent alicyclic hydrocarbon groups, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane or adamantane, or a group consisting of these alicyclic rings A group substituted with the alkyl group is preferable.

The monovalent or divalent alicyclic hydrocarbon group derivatives include, for example, a hydroxyl group; a carboxyl group; an oxo group (ie, ＝ O group); a hydroxymethyl group, a 1-hydroxyethyl group. , 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. A hydroxyalkyl group having 1 to 4 carbon atoms; carbon such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc. An alkoxyl group of formulas 1 to 4; a cyano group;
Examples thereof include groups having one or more substituents such as a cyanoalkyl group having 2 to 5 carbon atoms such as a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, and a 4-cyanobutyl group. Among these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group,
Preferred are a cyano group, a cyanomethyl group and the like.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms for R ⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, -Methylpropyl group, 1-methylpropyl group, t
- and butyl group. Among these alkyl groups, a methyl group, an ethyl group and the like are particularly preferable.

The group —COOC in the repeating unit (II)
(R ⁸ ) ₃ is an acid dissociable group that dissociates by the action of an acid to form a carboxyl group. Hereinafter, this group is referred to as an acid dissociable group (i). Specific examples of preferred acid dissociable groups (i) include a t-butoxycarbonyl group and groups represented by the following formulas (i-1) to (i-49).

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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Of these acid dissociable groups (i), t-butoxycarbonyl group, formula (i-1), formula (i-2), formula (i-10), formula (i-11), Formula (i-13), Formula (i-14), Formula (i-16), Formula (i-17), Formula (i-34), Formula (i-35), Formula (i-40), Formula A group represented by the formula (i-41), the formula (i-48) or the formula (i-49) is preferable. In the resin (A), the repeating unit (I
I) may be present alone or in combination of two or more. The repeating unit (II) is a repeating unit derived from the corresponding (meth) acrylate.

The resin (A) comprises a repeating unit other than the repeating unit (I-1), the repeating unit (I-2), the repeating unit (I-3) and the repeating unit (II) (hereinafter referred to as "another repeating unit"). "). Examples of the polymerizable unsaturated monomer that provides another repeating unit include, for example, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and tetracyclodecane (meth) acrylate. (Meth) acrylic acid having a bridged hydrocarbon skeleton such as benzyl, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, 3-hydroxyadamantyl (meth) acrylate, or adamantylmethyl (meth) acrylate Esters; carboxynorbornyl (meth) acrylate,
Carboxytricyclodecanyl (meth) acrylate,
Carboxyl group-containing esters having a bridged hydrocarbon skeleton of an unsaturated carboxylic acid such as carboxytetracyclodecanyl (meth) acrylate;

Norbornene (ie, bicyclo [2.2.
1] hept-2-ene), 5-methylbicyclo [2.
2.1] Hept-2-ene, 5-ethylbicyclo [2.
2.1] Hept-2-ene, 5-n-propylbicyclo
[2.2.1] Hept-2-ene, 5-n-butylbicyclo [2.2.1] hept-2-ene, 5-n-pentylbicyclo [2.2.1] hept-2-ene , 5-n-
Hexylbicyclo [2.2.1] hept-2-ene, 5
-Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-methyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-Ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8-n-propyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-N-butyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene, 8-n-pentyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-n-hexyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodeca-3-ene, 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-hydroxymethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene,

8-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 ] dodeca-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 [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
8,9-tris (trifluoromethyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
8,9,9-tetrafluorotetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-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] dodeca-3-ene, 8,8,9- trifluoro-9-trifluoromethoxy tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8,8,9-Trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 .
[ ^1,7,10 ] dodec-3-ene, 8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-
Chloro-8,9,9-trifluorotetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-
Dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8- (2 ', 2', 2'-trifluoro-carboethoxy) tetracyclo [4.4.0.1 ^{2, 5.} [ ^17,10 ] dodec-3-ene, 8-methyl-8- (2 ', 2', 2 '
-Trifluorocarboethoxy) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-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 . 1 ^9,12. 0 ^8,13] pentadeca-3 other monofunctional monomer having a bridged hydrocarbon skeleton such as ene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) 4-methoxycyclohexyl acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, 2-cyclohexyloxycarbonylethyl (meth) acrylate, 2- (4-methoxycyclohexyl) oxycarbonylethyl (meth) acrylate No bridge-type hydrocarbon skeleton (me ) Acrylic acid esters;

Methyl α-hydroxymethyl acrylate,
α-hydroxymethyl acrylates such as ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, and n-butyl α-hydroxymethyl acrylate; (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile , Maleic nitrile, fumalonitrile, mesaconitrile, citraconitrile, itaconitrile, and other unsaturated nitrile compounds; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, Unsaturated amide compounds such as itaconamide; other compounds such as N- (meth) acryloylmorpholine, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine and vinylimidazole; Unsaturated carboxylic acids (anhydrides) such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, 4-carboxycyclohexyl (meth) acrylate Carboxyl-containing esters having no bridged hydrocarbon skeleton of unsaturated carboxylic acids such as

Α- (meth) acryloyloxy-β-methoxycarbonyl-γ-butyrolactone, α- (meth)
Acryloyloxy-β-ethoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-
n-propoxycarbonyl-γ-butyrolactone, α-
(Meth) acryloyloxy-β-i-propoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-n-butoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (2-
Methylpropoxy) carbonyl-γ-butyrolactone,
α- (meth) acryloyloxy-β- (1-methylpropoxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-t-butoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β -Cyclohexyloxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (4
-T-butylcyclohexyloxy) carbonyl-γ-
Butyrolactone, α- (meth) acryloyloxy-β
-Phenoxycarbonyl-γ-butyrolactone, α-
(Meth) acryloyloxy-β- (1-ethoxyethoxy) carbonyl-γ-butyrolactone, α- (meth)
Acryloyloxy-β- (1-cyclohexyloxyethoxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-t-butoxycarbonylmethoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-tetrahydrofuran Nyloxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-tetrahydropyranyloxycarbonyl-γ-butyrolactone,

Α-methoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-ethoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-n-propoxycarbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-I-propoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-n-butoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α- (2-methylpropoxy) carbonyl-
β- (meth) acryloyloxy-γ-butyrolactone, α- (1-methylpropoxy) carbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-T-butoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-cyclohexyloxycarbonyl-β- (meth) acryloyloxy-γ-
Butyrolactone, α- (4-t-butylcyclohexyloxy) carbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-phenoxycarbonyl-β
-(Meth) acryloyloxy-γ-butyrolactone,
α- (1-ethoxyethoxy) carbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-
(1-cyclohexyloxyethoxy) carbonyl-β
-(Meth) acryloyloxy-γ-butyrolactone,
α-t-butoxycarbonylmethoxycarbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
(Meth) acryloyloxy having an acid dissociable group such as -tetrahydrofuranyloxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-tetrahydropyranyloxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone Lactone compounds;

Α- (meth) acryloyloxy-β-fluoro-γ-butyrolactone, α- (meth) acryloyloxy-β-hydroxy-γ-butyrolactone, α-
(Meth) acryloyloxy-β-methyl-γ-butyrolactone, α- (meth) acryloyloxy-β-ethyl-γ-butyrolactone, α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone, α-
(Meth) acryloyloxy-β-methoxy-γ-butyrolactone, α-fluoro-β- (meth) acryloyloxy-γ-butyrolactone, α-hydroxy-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-Methyl-β- (meth) acryloyloxy-γ-butyrolactone, α-ethyl-β- (meth) acryloyloxy-γ-butyrolactone, α, α-dimethyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-Methoxy-β- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-δ-
(Meth) acryloyloxylactone compounds having no acid-dissociable group such as mevalonolactone; carboxyl groups of the unsaturated carboxylic acids or carboxyl group-containing esters having no bridged hydrocarbon skeleton of the unsaturated carboxylic acid A monofunctional monomer such as a compound converted to an acid dissociable group (i) described below,

1,2-adamantanediol di (meth)
Polyfunctional having a bridged hydrocarbon skeleton such as acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, and tricyclodecanyl dimethylol di (meth) acrylate Monomer;

Methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexane Diol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
Multifunctional monomer having no bridged hydrocarbon skeleton such as 1,4-bis (2-hydroxypropyl) benzenedi (meth) acrylate and 1,3-bis (2-hydroxypropyl) benzenedi (meth) acrylate Examples include polyfunctional monomers such as bodies.

In the resin (A), the repeating unit (I-
1), the repeating unit (I-2) and the repeating unit (I-
The total content of 3) is usually 1 for all repeating units.
It is 0 to 80 mol%, preferably 20 to 70 mol%, and more preferably 30 to 70 mol%. In this case, if the total content is less than 10 mol%, the developability as a resist and the adhesiveness to a substrate tend to decrease, while 8
If it exceeds 0 mol%, the resolution as a resist tends to decrease. The content of the repeating unit (II) is usually from 10 to 80 mol%, preferably from 20 to 70 mol%, more preferably from 20 to 60 mol%, based on all repeating units. In this case, the content of the repeating unit (II) is 1
If the amount is less than 0 mol%, the resolution as a resist tends to decrease. On the other hand, if the amount exceeds 80 mol%, the developability of the resist tends to decrease, and scum tends to occur. The content of other repeating units is usually 50 mol% or less, preferably 4 mol%, based on all repeating units.
0 mol% or less.

The resin (A) may be prepared, for example, by polymerizing an unsaturated monomer corresponding to each repeating unit with a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds. And, if necessary, polymerization in an appropriate solvent in the presence of a chain transfer agent. Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, Cycloalkanes such as norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; halogenated hydrocarbons such as chlorobutane, bromohexanes, dichloroethanes, hexamethylene dibromide and chlorobenzene; ethyl acetate , N-butyl acetate, i-butyl acetate,
Saturated carboxylic esters such as methyl propionate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone; and ethers such as tetrahydrofuran, dimethoxyethane and diethoxyethane. These solvents can be used alone or in combination of two or more. The reaction temperature in the polymerization is usually 40 to 120 ° C, preferably 50 to 90 ° C, and the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours.

The polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) of the resin (A) determined by gel permeation chromatography (GPC) is usually 3,000.
0 to 30,000, preferably 5,000 to 30,00
0, more preferably 5,000 to 20,000. In this case, if the Mw of the resin (A) is less than 3,000, the heat resistance of the resist tends to decrease, while if it exceeds 30,000, the developability of the resist tends to decrease. is there. In addition, the M of the resin (A)
w and gel permeation chromatography (GPC)
Number average molecular weight (hereinafter referred to as "Mn")
That. ) (Mw / Mn) is usually 1 to 5, preferably 1 to 3. Note that the resin (A) preferably has less impurities such as halogens and metals, and thereby can further improve sensitivity, resolution, process stability, pattern shape, and the like when used as a resist. As a method for purifying the resin (A), for example, chemical purification methods such as washing with water and liquid-liquid extraction, and these chemical purification methods and ultrafiltration,
Combination with a physical purification method such as centrifugation can be mentioned.

Acid Generator (B) The component (B) in the present invention is a radiation-sensitive acid generator compound which generates an acid upon exposure (hereinafter referred to as “acid generator (B)”).
That. ). Examples of the acid generator (B) include an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, and a sulfonic acid compound. Hereinafter, examples of these acid generators (B) will be described. Onium salt compound: Examples of the onium salt compound include an iodonium salt, a sulfonium salt (including a thiophenium salt), a phosphonium salt, a diazonium salt, and a pyridinium salt. Preferred onium salt compounds include, for example, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n- Butanesulfonate, triphenylsulfonium perfluoro-n-
Octanesulfonate, triphenylsulfonium 1
0-camphorsulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 1- (3,5-dimethyl-4- (Hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-
(3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 4-methylphenyl-1-tetrahydrothiophenium nonafluoro-n-butanesulfonate,
-Methylphenyl-1-tetrahydrothiophenium perfluoro-n-octanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-hydroxy-1-
Naphthyltetrahydrothiophenium perfluoro-n
-Octanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (1 -Naphthyl acetomethyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate; 1- (1-naphthylacetomethyl) tetrahydrothiophenium perfluoro-n-octanesulfonate;

Halogen-containing compound: Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Preferred halogen-containing compounds include, for example, phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl)-
(Trichloromethyl) -s- such as s-triazine and 1-naphthylbis (trichloromethyl) -s-triazine
Examples thereof include a triazine derivative 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. Preferred diazoketones include, for example, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5
Sulfonyl chloride, 1,2-naphthoquinonediazide of 2,3,4,4'-tetrahydroxybenzophenone-
4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2 −
Naphthoquinonediazide-5-sulfonic acid ester and the like can be mentioned.

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Preferred sulfone compounds include, for example, 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like. Sulfonic acid compound: Examples of the sulfonic acid compound include alkylsulfonic acid esters, alkylsulfonic acid imides, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Preferred sulfonic acid compounds include, for example, benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-
9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.
1] Hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.
1] Hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n-butanesulfonate, N-hydroxysuccinimide perfluoro- n-octanesulfonate, 1,8-
Examples thereof include naphthalenedicarboxylic acid imide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic acid imidnonafluoro-n-butanesulfonate, and 1,8-naphthalenedicarboxylic acid imide perfluoro-n-octanesulfonate.

Of these acid generators (B), diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4
-T-butylphenyl) iodonium nonafluoro-n
-Butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-
n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonium trifluoromethanesulfonate, dicyclohexyl.2
-Oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 4-n-
Butoxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiophenium perfluoro-n-octanesulfonate,

Trifluoromethanesulfonylbicyclo [
2.2.1] Hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [
2.2.1] Hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo
[2.2.1] Hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n-butanesulfonate, N-hydroxysuccinimide Perfluoro-n-octanesulfonate, 1,
8-Naphthalenedicarboxylic acid imide trifluoromethanesulfonate and the like are preferred. The acid generator (B) can be used alone or in combination of two or more.

The amount of the acid generator (B) used in the present invention is usually 0.1 to 100 parts by weight of the resin (A) from the viewpoint of securing the sensitivity and developability as a resist.
To 20 parts by weight, preferably 0.5 to 10 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 2
If the amount exceeds 0 parts by weight, the transparency to radiation decreases, and it tends to be difficult to obtain a rectangular resist pattern.

Polycyclic Compound (C) The component (C) in the present invention has the formula —COOR ⁹ [wherein:
R ⁹ is a hydrogen atom, a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms;
A linear or branched alkyl group, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or —CH ₂ COOR ¹⁰ (where R ¹⁰ is a hydrogen atom, substituted or unsubstituted) A linear or branched alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted 3 to 20 carbon atoms
Is a monovalent alicyclic hydrocarbon group. ). And a polycyclic compound having a molecular weight of 1,000 or less (hereinafter referred to as "polycyclic compound (C)").
In the polycyclic compound (C), when there are a plurality of groups represented by the formula —COOR ⁹ , each R ⁹ may be the same or different.

In the polycyclic compound (C), examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms for R ⁹ include a methyl group, an ethyl group, an n-propyl group and an i-type group.
-Propyl group, n-butyl group, 2-methylpropyl group,
1-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group Linear, branched or cyclic unsubstituted alkyl groups such as n-octadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group and cyclooctyl group; these unsubstituted alkyl groups are hydroxyl groups; carboxyl groups; Oxo group; hydroxymethyl group, hydroxyethyl group, 1-hydroxypropyl group,
A hydroxyalkyl group having 1 to 4 carbon atoms such as a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group; a methoxy group; An alkoxyl group having 1 to 4 carbon atoms such as an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a t-butoxy group; a cyanomethyl group; Examples thereof include groups having one or more substituents such as a cyanoalkyl group having 2 to 5 carbon atoms such as a cyanoethyl group, a 3-cyanopropyl group, and a 4-cyanobutyl group.

The substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms for R ⁹ includes, for example,
Norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane,
A group consisting of an unsubstituted alicyclic ring derived from cycloalkanes such as cyclohexane, cycloheptane and cyclooctane; a group consisting of these unsubstituted alicyclic rings is a hydroxyl group; a carboxyl group; an oxo group; Hydroxymethyl group, hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. A methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a t-butoxy group, etc. C1-C4 alkoxyl group; cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group A substituent such as a cyano alkyl group having 2 to 5 carbon atoms such as 4-cyanobutyl group can include one or more or one or more having groups.

R ^{10 is} a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms and a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. Is, for example, the corresponding groups exemplified for R ⁹ above.

R ⁹ in the polycyclic compound (C) is a hydrogen atom, a 1-methylpropyl group, a t-butyl group,
A 1-methylpropoxycarbonylmethyl group, a t-butoxycarbonylmethyl group and the like are preferable, and a t-butyl group and a t-butoxycarbonylmethyl group are particularly preferable. When R ⁹ in the polycyclic compound (C) is a 1-branched alkyl group or a substituted derivative thereof, R ⁹ dissociates in the presence of an acid. Further, dissociates in the presence of -CH ₂ COOR ¹⁰ itself R ⁹ are acid, or in which case R ¹⁰ is a 1-branched alkyl group or a substituted derivative dissociates in the presence of R ¹⁰ also acid. In these cases, —COOR ⁹ and —COO—CH ₂ COOR ¹⁰ in the polycyclic compound (C) form an acid dissociable group.

As the polycyclic compound (C), for example, a compound represented by the following general formula (4) (hereinafter referred to as “polycyclic compound (C4)”) and a compound represented by the following general formula (5) (Hereinafter referred to as “polycyclic compound (C5)”),
A compound represented by the following general formula (6) (hereinafter, referred to as “polycyclic compound (C6)”), a compound represented by the following general formula (7) (hereinafter, “polycyclic compound (C7)”) ), A compound represented by the following general formula (8)
It is referred to as "polycyclic compound (C8)". ), A compound represented by the following general formula (9) (hereinafter, referred to as “polycyclic compound (C
9) ". ) And the like.

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[0070]

Embedded image [In the general formula (5), Z represents an m-valent hydrocarbon group having a polycyclic carbon ring having a total number of ring-constituting carbon atoms of 6 to 20 or a derivative thereof, and m is an integer of 1 to 4. . ]

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[0072]

Embedded image [In the general formula (7), R ¹¹ and R ¹² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms. A hydroxyalkyl group, —OR ¹³ , wherein R ¹³ is a hydrogen atom,
A linear or branched alkyl group having 1 to 4 carbon atoms or —CH ₂ COOR ¹⁴ (where R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms)} or —CO 2
OR ¹⁵ ｛wherein R ¹⁵ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or —CH ₂ COOR ¹⁶
(However, R ¹⁶ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.｝ Is shown, and n and p are independently 0 to 0)
It is an integer of 2. ]

[0073]

Embedded image [In the general formula (8), R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰
Are each independently a hydrogen atom, a hydroxyl group,
4 linear or branched alkyl group or 1 carbon atom
Represents a straight-chain or branched alkoxyl group of 1 to 4. ]

[0074]

Embedded image [In the general formula (9), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a hydroxyl group;
^21, at least one of R ²² and R ²³ is a hydroxyl group. ]

As specific examples of the cyclic compound (C4),
Di-tert-butyl 1,2-adamantanedicarboxylate,
Di-t-butyl 1,3-adamantanedicarboxylate,
Di-t-butyl 1,4-adamantanedicarboxylate,
Di-t-butyl 2,2-adamantanedicarboxylate,
Di-t-butyl 2,4-adamantanedicarboxylate,
Di-t-butyl 2,9-adamantanedicarboxylate,
Di-tert-butoxycarbonylmethyl 1,2-adamantanedicarboxylate, di-tert-butoxycarbonylmethyl 1,3-adamantanedicarboxylate, di-tert-butoxycarbonylmethyl 1,4-adamantanedicarboxylate,
Di-tert-butoxycarbonylmethyl 2,2-adamantanedicarboxylate, di-tert-butoxycarbonylmethyl 2,4-adamantanedicarboxylate, di-tert-butoxycarbonylmethyl 2,9-adamantanedicarboxylate,

1-t-butoxycarbonyl-2-t-butoxycarbonylmethoxycarbonyladamantane, 1
-Tert-butoxycarbonyl-3-tert-butoxycarbonylmethoxycarbonyladamantane, 1-tert-butoxycarbonyl-4-tert-butoxycarbonylmethoxycarbonyladamantane, 2-tert-butoxycarbonyl-2
-T-butoxycarbonylmethoxycarbonyl adamantane, 2-t-butoxycarbonyl-4-t-butoxycarbonylmethoxycarbonyl adamantane, 2-t-
Butoxycarbonyl-9-t-butoxycarbonylmethoxycarbonyladamantane, 1-t-butoxycarbonylmethoxycarbonyl-2-t-butoxycarbonyladamantane, 1-t-butoxycarbonylmethoxycarbonyl-4-t-butoxycarbonyladamantane, and the like. Can be.

Among these polycyclic compounds (C4), di-tert-butyl 1,3-adamantanedicarboxylate, di-tert-butoxycarbonylmethyl 1,3-adamantanedicarboxylate and the like are particularly preferred.

The polycyclic compound (C4) is, for example, 1,3-
In the case of di-t-butyl adamantane dicarboxylate, 1,3-adamantane dicarboxylic acid is dissolved in tetrahydrofuran under a nitrogen atmosphere, and trifluoroacetic anhydride is added dropwise to this solution under ice-cooling, and the solution is added at room temperature. After stirring,
It can be synthesized by dropping a solution of t-butanol in tetrahydrofuran under ice-cooling, and stirring and reacting at room temperature overnight, for example. In the case of di-t-butoxycarbonylmethyl 1,3-adamantanedicarboxylate, reacting 1,3-adamantanedicarboxylic acid and t-butyl bromoacetate in tetrahydrofuran in the presence of a potassium carbonate catalyst. Can be synthesized by

Next, in the alicyclic compound (C5), Z
Examples of the m-valent hydrocarbon group having a polycyclic carbon ring having a total number of ring-constituting carbon atoms of 6 to 20 include norbornane, tricyclodecane, tetracyclododecane, adamantane and the following formula (ii): Groups derived from polycyclic carbocycles such as the groups represented;

[0080]

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These polycyclic carbocycles are, for example, methyl, ethyl, n-propyl, i-propyl, n-
Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like, and a group substituted with one or more linear or branched or cyclic alkyl groups having 1 to 8 carbon atoms. And the like. In polycyclic compound (C5), m pieces of group -OCOC ₂ H ₄ COOCH ₂ COOR ⁹ can be attached to the polycyclic carbocyclic rings in the m-valent hydrocarbon group or polycyclic carbon, It may be bonded to an alkyl group which substitutes a ring.

When the total number of ring-constituting carbon atoms of Z is from 6 to
Examples of the derivative of an m-valent hydrocarbon group having 20 polycyclic carbon rings include a hydroxyl group; a carboxyl group;
Oxo group; hydroxymethyl group, hydroxyethyl group,
C1-C4 hydroxy such as 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl; Alkyl group; an alkoxyl group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, and a t-butoxy group. A methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group,
An alkoxycarbonyl group having 2 to 5 carbon atoms such as -methylpropoxycarbonyl group, t-butoxycarbonyl group; methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group, n-propoxycarbonylmethoxycarbonyl group, i-propoxycarbonylmethoxycarbonyl group , N-butoxycarbonylmethoxycarbonyl group, 2-methylpropoxycarbonylmethoxycarbonyl group, 1-methylpropoxycarbonylmethoxycarbonyl group, t-butoxycarbonylmethoxycarbonyl group, etc. A group having one or more groups or one or more groups can be given. These substituents may be bonded to a polycyclic carbocycle in the above-mentioned n-valent hydrocarbon group, or may be bonded to an alkyl group substituting the polycyclic carbocycle.

Among the above substituents, a hydroxyl group, 1-
A methylpropoxycarbonylmethoxycarbonyl group, t
-Butoxycarbonylmethoxycarbonyl group and the like are preferable, and a hydroxyl group is particularly preferable. Further, m in the polycyclic compound (C5) is preferably 1 or 2. In addition, (1-branched alkoxy) -CO
When it has a CH ₂ —OCO group, between the 1-branched alkoxy group and COCH _2, and
Also between -COCH ₂ and OCO can be dissociated in the presence of an acid.

Specific examples of the polycyclic compound (C5) include
Examples include compounds represented by the following formulas (5-1) to (5-44).

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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Among these polycyclic compounds (C5), formulas (5-9), (5-10), (5-13), (5-14), (5-17), Compounds represented by formula (5-18), formula (5-21), formula (5-22), formula (5-24), formula (5-30) or formula (5-44) are preferable, In particular, compounds represented by the formulas (5-10), (5-17), (5-21), (5-24), (5-30) or (5-44) are preferred. preferable.

The polycyclic compound (C5) can be synthesized, for example, by reacting an alcohol having an alicyclic carbon ring with succinic anhydride, and further reacting the reaction product with t-butyl bromoacetate. Can be. More specifically, for example, the compound represented by the above formula (5-30) is prepared by reacting deoxycholic acid and succinic anhydride under reflux in a nitrogen atmosphere in n-butyl acetate. The obtained white solid is dissolved in n-butyl acetate and washed several times with water, then the solvent is distilled off, and then tetrahydrofuran, distilled water, potassium carbonate and t-butyl bromoacetate are added, and the mixture is reacted for several hours to synthesize. be able to.

Next, specific examples of the polycyclic compound (C6) include compounds represented by the following formulas (6-1) to (6-29).

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Among these polycyclic compounds (C6), compounds represented by the formula (6-18) or the formula (6-27) are particularly preferable.

Of the polycyclic compound (C6), the compound represented by the formula (6-1)
Is available, and the other polycyclic compound (C6) can be synthesized using the compound represented by the formula (6-1) as a starting material. For example, equation (6-18)
The compound represented by the formula can be synthesized by reacting the compound represented by the formula (6-1) with potassium t-butoxide at a high temperature in the presence of a catalyst such as thionyl chloride. The compound represented by (6-27) can be synthesized by reacting the compound represented by formula (6-1) with t-butyl bromoacetate in the presence of a catalyst such as potassium carbonate. .

Next, in the polycyclic compound (C7), R
^When n and p are 0, the bonding position of ¹¹ and R ¹² is
The position of a divalent carbonyloxy group or a divalent oxycarbonyl group connecting two carbon rings in the general formula (7) is represented by 2
In the case where-is in the 5- or 6-position and n and p are 1, a divalent carbonyloxy group or a divalent oxycarbonyl linking two carbon rings in the general formula (7) When the position of the group is the 3-position, the group is located at the 8-position or 9-position, and when n and p are 2, the general formula (7)
When the position of the divalent carbonyloxy group or the divalent oxycarbonyl group connecting the two carbocycles is the 3-position, it is at the 10-position or 11-position.

In the polycyclic compound (C7), examples of the linear or branched alkyl group having 1 to 4 carbon atoms for R ¹¹ and R ¹² include a methyl group, an ethyl group, an n-propyl group and an i-type group. -Propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. Also, R ¹¹ and R ¹² have 1 to 1 carbon atoms.
Examples of the linear or branched hydroxyalkyl group of 4 include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxybutyl group. , 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like.

Further, among -OR ¹³ of R ¹¹ and R ¹² ,
Examples of the group in which R ¹³ is a linear or branched alkyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group and a 2-methyl group. Examples include a propoxy group, a 1-methylpropoxy group, and a t-butoxy group. Also, R
¹¹ and out of -OR ¹³ in R ^12, R ¹³ is -CH ₂ COO
Examples of the group represented by R ¹⁴ include a carboxymethoxy group, a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group, an n-propoxycarbonylmethoxy group,
i-propoxycarbonylmethoxy group, n-butoxycarbonylmethoxy group, 2-methylpropoxycarbonylmethoxy group, 1-methylpropoxycarbonylmethoxy group, t-butoxycarbonylmethoxy group, n-pentyloxycarbonylmethoxy group, n-hexyloxycarbonyl Methoxy group, n-octyloxycarbonylmethoxy group, n-decyloxycarbonylmethoxy group, n-
Dodecyloxycarbonylmethoxy, n-tetradecyloxycarbonylmethoxy, n-hexadecyloxycarbonylmethoxy, n-octadecyloxycarbonylmethoxy, cyclopentyloxycarbonylmethoxy, cyclohexyloxycarbonylmethoxy, cyclooctyloxycarbonylmethoxy And linear, branched or cyclic alkoxycarbonylmethoxy groups.

In the -COOR ¹⁵ of R ¹¹ and R ¹² , R ¹⁵ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, n -Propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group , N-octyloxycarbonyl group,
n-decyloxycarbonyl group, n-dodecyloxycarbonyl group, n-tetradecyloxycarbonyl group, n
Linear, branched or cyclic unsubstituted such as -hexadecyloxycarbonyl group, n-octadecyloxycarbonyl group, n-eicosyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, cyclooctyloxycarbonyl group, etc. Alkoxycarbonyl group; an alkoxyl group in these unsubstituted alkoxycarbonyl groups is substituted with a substituent such as a hydroxyl group, a carboxyl group, an oxo group, a hydroxymethyl group, a linear or branched alkoxyl group having 1 to 4 carbon atoms; 1
Derivatives substituted by one or more species or one or more species can be mentioned.

The group in which R ¹⁵ is —CH ₂ COOR ¹⁶ among —COOR ¹⁵ of R ¹¹ and R ¹² is, for example, a carboxymethoxycarbonyl group, a methoxycarbonylmethoxycarbonyl group, an ethoxycarbonylmethoxycarbonyl group. N-propoxycarbonylmethoxycarbonyl group, i-propoxycarbonylmethoxycarbonyl group, n-butoxycarbonylmethoxycarbonyl group, 2-methylpropoxycarbonylmethoxycarbonyl group, 1-methylpropoxycarbonylmethoxycarbonyl group, t-butoxycarbonylmethoxycarbonyl group N-pentyloxycarbonylmethoxycarbonyl group, n-hexyloxycarbonylmethoxycarbonyl group, n-octyloxycarbonylmethoxycarbonyl group, n-decyloxy Carbonylmethoxycarbonyl group, n-dodecyloxycarbonylmethoxycarbonyl group, n-tetradecyloxycarbonylmethoxycarbonyl group, n-hexadecyloxycarbonylmethoxycarbonyl group, n-octadecyloxycarbonylmethoxycarbonyl group, cyclopentyloxycarbonylmethoxycarbonyl group, Examples thereof include a linear, branched or cyclic alkoxycarbonylmethoxycarbonyl group such as a cyclohexyloxycarbonylmethoxycarbonyl group and a cyclooctyloxycarbonylmethoxycarbonyl group.

R ¹¹ and R ¹² in the polycyclic compound (C7) are each a hydrogen atom, a hydroxymethyl group, a hydroxyl group, a t-butoxycarbonylmethoxy group, a t-butoxycarbonyl group, a t-butoxycarbonylmethoxycarbonyl Groups and the like are preferred. Further, as n and p in the polycyclic compound (C7),
0 or 1 is preferred.

As specific examples of the polycyclic compound (C7),
Examples include compounds represented by the following formulas (7-1) to (7-208).

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Of these polycyclic compounds (C7), formulas (7-9), (7-10), (7-12), (7-13), (7-14), Equation (7-16), Equation (7-25), Equation (7-26), Equation (7-28), Equation (7-33), Equation (7-34), Equation (7-36), Equation (7-41), Formula (7-42), Formula (7-44), Formula (7-45), Formula (7-46), Formula (7-48), Formula (7-49), Formula (7-49) 7-50), Equation (7-52), Equation (7-61), Equation (7-62), Equation (7-64), Equation (7-65), Equation (7-66), Equation (7 -68), Equation (7-77), Equation (7-78), Equation (7-80), Equation (7-85), Equation (7-86), Equation (7-88), Equation (7-78) 93), Formula (7-94), Formula (7-96), Formula (7-97), Formula (7-98), Formula (7-100), Formula (7-101),
Formula (7-102), Formula (7-104), Formula (7-113), Formula (7-1)
14), Formula (7-116), Formula (7-117), Formula (7-118), Formula (7-120), Formula (7-129), Formula (7-130), Formula (7-13)
2), equation (7-137), equation (7-138), equation (7-140), equation (7-145), equation (7-146), equation (7-148), equation (7-14)
9), equation (7-150), equation (7-152), equation (7-153), equation (7-154), equation (7-156), equation (7-165), equation (7-16)
6), Equation (7-168), Equation (7-169), Equation (7-170), Equation (7-172), Equation (7-181), Equation (7-182), Equation (7-18)
4), equation (7-189), equation (7-190), equation (7-192), equation (7-197), equation (7-198), equation (7-200), equation (7-20)
1), a compound represented by the formula (7-202), the formula (7-204), the formula (7-205), the formula (7-206) or the formula (7-208), and the like. 7-34), Equation (7-104), Equation (7-13)
2) or a compound represented by the formula (7-169) is preferred.

In the case of the compound represented by the formula (7-103), for example, the polycyclic compound (C7) is subjected to a Diels-Alder reaction between dicyclopentadiene and allyl acetate,
After the addition reaction of the obtained reaction product with formic acid, in tetrahydrofuran, in the presence of triethylamine and 4-dimethylaminopyridine, reacted with a hymic acid, and further reacted with formic acid to the reaction product, Thereafter, it can be synthesized by hydrolysis with an aqueous solution of potassium hydroxide.

Next, in the polycyclic compound (C8), R
Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ include a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group,
A t-butyl group and the like can be mentioned. Also, R ¹⁷ , R
Examples of the linear or branched alkoxyl group having 1 to 4 carbon atoms of ¹⁸ , R ¹⁹ and R ²⁰ include a methoxy group,
Ethoxy, n-propoxy, i-propoxy, n
-Butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group and the like.
R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^{20 in the} polycyclic compound (C8) are a hydrogen atom, a hydroxyl group, a methyl group,
Ethyl, methoxy, ethoxy and the like are preferred.

Specific examples of the polycyclic compound (C8) include
Tetrahydroabietic acid, methyl tetrahydroabietic acid, ethyl tetrahydroabietic acid, n-propyl tetrahydroabietic acid, i-propyl tetrahydroabietic acid, n-butyl tetrahydroabietic acid, 2-methylpropyl tetrahydroabietic acid, 1-methylpropyl tetrahydroabietic acid , Tetrahydroabietic acid such as t-butyl tetrahydroabietic acid, cyclopentyl tetrahydroabietic acid, cyclohexyl tetrahydroabietic acid, and alkyl esters thereof;

Methoxycarbonylmethyl tetrahydroabietic acid, ethoxycarbonylmethyl tetrahydroabietic acid, n-propoxycarbonylmethyl tetrahydroabietic acid, i-propoxycarbonylmethyl tetrahydroabietic acid, n-tetrahydroabietic acid
-Butoxycarbonylmethyl, 2-methylpropoxycarbonylmethyl tetrahydroabietic acid, 1-methylpropoxycarbonylmethyl tetrahydroabietic acid, t-butoxycarbonylmethyl tetrahydroabietic acid, cyclopentyloxycarbonylmethyl tetrahydroabietic acid, cyclohexyloxycarbonylmethyl tetrahydroabietic acid, etc. Of alkoxycarbonylmethyl esters of tetrahydroabietic acid,
Examples include compounds represented by the following formulas (8-1) to (8-30).

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[0247]

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Of these polycyclic compounds (C8), particularly preferred are t-butyl tetrahydroabietic acid, t-butoxycarbonylmethyl tetrahydroabietic acid and the like.

For example, in the case of t-butyl tetrahydroabietic acid, the polycyclic compound (C8) is obtained by reacting tetrahydroabietic acid with potassium t-butoxide at a high temperature in the presence of a catalyst such as thionyl chloride. Can be synthesized and t-tetrahydroabietic acid
Butoxycarbonylmethyl can be synthesized by reacting tetrahydroabietic acid with t-butyl bromoacetate in the presence of a catalyst such as potassium carbonate.

Next, specific examples of the polycyclic compound (C9) include lithocholic acid, methyl lithocholic acid, ethyl lithocholic acid, n-propyl lithocholic acid, lithocholic acid i
-Propyl, n-butyl lithocholic acid, lithocholic acid 2
-Methylpropyl, 1-methylpropyl lithocholic acid,
T-butyl lithocholic acid, cyclopentyl lithocholic acid, cyclohexyl lithocholic acid, γ-butyrolactone lithocholic acid, mevalonic lactone lithocholic acid, methoxycarbonylmethyl lithocholic acid, ethoxycarbonylmethyl lithocholic acid, n-propoxycarbonylmethyl lithocholic acid, lithocholic acid i -Propoxycarbonylmethyl, n-butoxycarbonylmethyl lithocholic acid, 2-methylpropoxycarbonylmethyl lithocholic acid, 1-methylpropoxycarbonylmethyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, cyclopentyloxycarbonylmethyl lithocholic acid, cyclohexyloxy lithocholic acid Lithocholic acid such as carbonylmethyl or derivatives thereof;

Deoxycholic acid, methyl deoxycholate, ethyl deoxycholate, n-propyl deoxycholate, i-propyl deoxycholate, n-butyl deoxycholate, 2-methylpropyl deoxycholate, deoxycholate 1 -Methylpropyl, t-butyl deoxycholate, cyclopentyl deoxycholate,
Cyclohexyl deoxycholic acid, deoxycholic acid γ
-Butyrolactone, mevalonic lactone deoxycholate, methoxycarbonylmethyl deoxycholate, ethoxycarbonylmethyl deoxycholate, n-propoxycarbonylmethyl deoxycholate, i-propoxycarbonylmethyl deoxycholate, n-butoxycarbonyl deoxycholate Methyl, deoxycholic acid 2
Deoxycholic acid or derivatives thereof, such as -methylpropoxycarbonylmethyl, 1-methylpropoxycarbonylmethyl deoxycholate, t-butoxycarbonylmethyl deoxycholate, cyclopentyloxycarbonylmethyl deoxycholate, cyclohexyloxycarbonylmethyl deoxycholate;

Ursodeoxycholic acid, methyl ursodeoxycholic acid, ethyl ursodeoxycholic acid, n-propyl ursodeoxycholic acid, i-propyl ursodeoxycholic acid, n-butyl ursodeoxycholic acid, ursodeoxycholic acid 2- Methylpropyl, 1-methylpropyl ursodeoxycholate, t-butyl ursodeoxycholate, cyclopentyl ursodeoxycholate, cyclohexyl ursodeoxycholate, γ-butyrolactone ursodeoxycholic acid, mevalonic lactone ursodeoxycholate, urso Methoxycarbonylmethyl deoxycholate, ethoxycarbonylmethyl ursodeoxycholate, n-propoxycarbonylmethyl ursodeoxycholate, i-propoxy ursodeoxycholate Carbonyl-methyl, ursodeoxycholic acid n- butoxycarbonylmethyl, ursodeoxycholic acid 2-methyl-propoxycarbonyl methyl,
Ursodeoxycholic acids or derivatives thereof such as 1-methylpropoxycarbonylmethyl ursodeoxycholate, t-butoxycarbonylmethyl ursodeoxycholate, cyclopentyloxycarbonylmethyl ursodeoxycholate, cyclohexyloxycarbonylmethyl ursodeoxycholate;

Cholic acid, methyl cholate, ethyl cholate, n-propyl cholate, i-propyl cholate, n-butyl cholate, 2-methylpropyl cholate, 1-methylpropyl cholate, t-cholate Butyl, cyclopentyl cholate, cyclohexyl cholate, γ-butyrolactone cholate, mevalonic lactone cholate,
Methoxycarbonylmethyl cholate, ethoxycarbonylmethyl cholate, n-propoxycarbonylmethyl cholate, i-propoxycarbonylmethyl cholate, n-butoxycarbonylmethyl cholate, 2-methylpropoxycarbonylmethyl cholate, 1-methyl cholate Examples thereof include cholic acid such as propoxycarbonylmethyl, t-butoxycarbonylmethyl cholate, cyclopentyloxycarbonylmethyl cholate, and cyclohexyloxycarbonylmethyl cholate, and derivatives thereof.

Of these polycyclic compounds (C9), t-butyl lithocholic acid, γ-butyrolactone lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, t-butyl deoxycholate, γ-butyrolactone deoxycholate, deoxycholate T-butoxycarbonylmethyl cholate, t-butyl ursodeoxycholic acid, γ-butyrolactone ursodeoxycholic acid, t-butoxycarbonylmethyl ursodeoxycholate, t-butyl cholate, γ-butyrolactone cholate, t-cholate c- Butoxycarbonylmethyl and the like are preferred.

The polycyclic compound (C9) can be produced, for example, by converting the corresponding steroid carboxylic acid in the presence of potassium carbonate,
It can be synthesized by reacting with t-butyl bromoacetate or the like.

The polycyclic compound (C) in the present invention is preferably a polycyclic compound (C5), a polycyclic compound (C8), a polycyclic compound (C9), etc., and particularly preferably a polycyclic compound. (C9).

In the present invention, the polycyclic compound (C) is
They can be used alone or in combination of two or more. The amount of the polycyclic compound (C) used is 100 parts of the resin (A).
Usually, 1 to 20 parts by weight, preferably 1
To 15 parts by weight, particularly preferably 1 to 10 parts by weight.
In this case, if the amount of the polycyclic compound (C) is less than 1 part by weight, the effect of improving the line width of the line pattern due to the low density of the line and space pattern may be insufficient. On the other hand, when the amount exceeds 20 parts by weight, heat resistance and adhesion to a substrate tend to decrease.

The radiation-sensitive resin composition of the present invention has an effect of controlling the diffusion phenomenon of the acid generated from the acid generator (B) in the resist film due to exposure, and suppressing an undesired chemical reaction in the unexposed area. It is preferable to add an acid diffusion controller having the same. By blending such an acid diffusion controller, the storage stability of the obtained radiation-sensitive resin composition is further improved, and the resolution as a resist is further improved, and from exposure to heat treatment after exposure. It is possible to suppress a change in the line width of the resist pattern due to a change in the withdrawal time (PED), and to obtain a composition having extremely excellent process stability. 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 (10)

[0269]

Embedded image [In the general formula (10), R ²⁴ , R ²⁵ and R ²⁶ independently represent a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group or a substituted Alternatively, it represents an unsubstituted aralkyl group. ]

(Hereinafter, referred to as "nitrogen-containing compound (a)"), a compound having two nitrogen atoms in the same molecule (hereinafter, referred to as "nitrogen-containing compound (b)"),
Examples thereof include polyamino compounds and polymers having three or more nitrogen atoms (hereinafter collectively referred to as "nitrogen-containing compound (c)"), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. .

As the nitrogen-containing compound (A), for example, n
Monoalkylamines such as -hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine; di-n-butylamine, di-n-pentylamine, di-n-hexylamine Dialkylamines such as di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine and dicyclohexylamine; triethylamine, tri-n-propylamine, tri- n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine,
Tri-alkylamines such as tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, and tricyclohexylamine; bis (2-dimethylaminoethyl) ether;
Bis (dialkylaminoalkyl) ethers such as bis (2-diethylaminoethyl) ether; aniline,
N-methylaniline, N, N-dimethylaniline, 2-
Methylaniline, 3-methylaniline, 4-methylaniline, 2,6-di-t-butylaniline, 2,6-di-
Examples thereof include aromatic amines such as t-butyl-N-methylaniline, 2,6-di-t-butyl-N, N-dimethylaniline, 4-nitroaniline, diphenylamine, triphenylamine, and naphthylamine.

Examples of the nitrogen-containing compound (b) include, for example, 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 [1- (4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether and the like. it can. Examples of the nitrogen-containing compound (c) include polyethyleneimine, polyallylamine, and 2-dimethylaminoethylacrylamide polymers.

Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-
Adamantylamine, N, N-di-tert-butoxycarbonyl-1-adamantylamine, N, N-di-tert-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4 ′ -Diaminodiphenylmethane, N, N'-di-tert-butoxycarbonylhexamethylenediamine, N, N, N'N'-tetra-tert-butoxycarbonylhexamethylenediamine,
N, N'-di-tert-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-tert-butoxycarbonyl-1,8-diaminooctane, N, N'-di-tert-butoxycarbonyl- 1,9-diaminononane, N, N'-
Di-tert-butoxycarbonyl-1,10-diaminodecane, N, N′-di-tert-butoxycarbonyl-1,12
-Diaminododecane, N, N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt
-Butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, N
N-t-butoxycarbonyl group-containing amino compounds such as -t-butoxycarbonyl-2-phenylbenzimidazole, 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, 1,3-
Examples thereof include dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n-butylthiourea. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole; pyridine, -Methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, Pyridines such as -hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ': 6', 2 ''-terpyridine; piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine;
Pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4
-Dimethylpiperazine, 1,4-diazabicyclo [2.
2.2] octane and the like.

Of these nitrogen-containing organic compounds, a nitrogen-containing compound (a), an amide group-containing compound and a nitrogen-containing heterocyclic compound are preferable, and an Nt-butoxycarbonyl group-containing amino compound is particularly preferable. The acid diffusion controllers can be used alone or in combination of two or more. The compounding amount of the acid diffusion controller is usually 15 parts by weight or less, preferably 10 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the resin (A). in this case,
When the compounding 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.

The radiation-sensitive resin composition of the present invention may contain a surfactant having an effect of improving coating properties, developability and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene In addition to nonionic surfactants such as glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflow No. No. 75, the same No. 95
(Manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, E-top
F303, EF352 (Tochem Products Co., Ltd.)
), Megafax F171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florado FC430, F
C431 (manufactured by Sumitomo 3M Limited), Asahi Guard A
G710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, S
C-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) and the like. These surfactants can be used alone or in combination of two or more. The compounding amount of the surfactant is 1 in total of the resin (A) and the acid generator (B).
The amount is usually 2 parts by weight or less based on 00 parts by weight. Further, as additives other than the above, an antihalation agent,
Adhesion aids, storage stabilizers, defoamers and the like can be mentioned.

Preparation of Composition Solution The radiation-sensitive resin composition of the present invention is usually used such that the total solid content is usually 5 to 50% by weight, preferably 10 to 25% by weight. After dissolving in a solvent, the composition is prepared as a composition solution by filtering through, for example, a filter having a pore size of about 0.2 μm. As the solvent used for preparing the composition solution, for example, 2-
Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone,
Linear or branched ketones such as -methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; cyclopentanone, 3-methylcyclopentanone, cyclohexanone, -Methylcyclohexanone, 2,6-dimethylcyclohexanone,
Cyclic ketones such as 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 glycol mono-t-
Propylene glycol monoalkyl ether acetates such as butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate;
N-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, 2
Alkyl 2-hydroxypropionates such as t-butyl-hydroxypropionate; 3-alkoxypropion such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate In addition to alkyl acid salts,

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 mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, N-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, -N-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid,
Examples thereof include 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, and propylene carbonate.

These solvents can be used alone or as a mixture of two or more. Among them, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates are preferred. , Alkyl 2-hydroxypropionates, alkyl 3-alkoxypropionates, γ-butyrolactone and the like are preferred.

Method for Forming Resist Pattern The radiation-sensitive resin composition of the present invention is particularly useful as a chemically amplified resist. In the chemically amplified resist, an acid dissociable group in the resin (A) or the polycyclic compound (C) is dissociated by the action of an acid generated from the acid generator (B) upon exposure to form a carboxyl group. 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 by the alkali developing solution.
It is removed, and a positive resist pattern is obtained. When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution, by a suitable application means such as spin coating, casting coating, roll coating, for example, silicon wafer, coated with aluminum A resist film is formed by applying the resist film on a substrate such as a wafer which has been subjected to a heat treatment (hereinafter, referred to as “PB”) in some cases, and then the resist film is formed so as to form a predetermined resist pattern. Expose. As the radiation used at that time, visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam, etc. are appropriately selected and used depending on the type of the acid generator (B) used. ArF excimer laser (wavelength 1
93nm), KrF excimer laser (wavelength 248n)
m) or F ₂ excimer laser (wavelength 157 nm)
Is preferable. In the present invention,
After the exposure, heat treatment (hereinafter, referred to as “PEB”) is preferably performed. By this PEB, the dissociation reaction of the acid-dissociable group proceeds smoothly. The heating conditions for PEB vary depending on the composition of the radiation-sensitive resin composition.
To 200 ° C, preferably 50 to 170 ° C.

In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, for example,
As disclosed in Japanese Patent No. 12452 or the like, 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-5-18
As disclosed in Japanese Patent No. 8598 and the like, a protective film can be provided on a resist film, or these techniques can be used in combination. Next, by developing the exposed resist film using an alkaline developer,
A predetermined resist pattern is formed. Examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, Methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline,
1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-
An alkaline aqueous solution in which at least one alkaline compound such as 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 may be dissolved in the developer, which is not preferable.

Further, for example, an organic solvent can be added to the alkaline aqueous solution. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl i
Ketones such as -butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t- Butyl alcohol, cyclopentanol, cyclohexanol, 1,
Alcohols such as 4-hexanediol and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; ethyl acetate, n-butyl acetate and i-acetate
Esters such as amyl; 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 may be reduced and the undeveloped portion of the exposed portion may be increased. Further, an appropriate amount of a surfactant or the like can be added to the alkaline aqueous solution. After development with an alkali developing solution, it is generally washed with water and dried.

[0283]

Embodiments of the present invention will now be described more specifically with reference to the following examples. However, the present invention is not limited to these embodiments. Here, parts are by 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
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., using G3000HXL and G4000HXL. It was measured. Radiation transmittance: A 0.34 μm-thick resist film formed by applying the composition solution onto a quartz glass by spin coating and performing PB on a hot plate maintained at 90 ° C. for 60 seconds to measure the absorbance at a wavelength of 193 nm. , And the radiation transmittance was calculated and used as a measure of transparency in the far ultraviolet region.

Sensitivity: ARC25 (Brewer Science) having a thickness of 820 mm on the surface as a substrate
Silicone wafer with film (ARC25)
Alternatively, using a silicon wafer (SiON) on which a silicon oxynitride film prepared so as to exhibit an antireflection effect at a wavelength of 193 nm is applied, each composition solution is applied on each substrate by spin coating, and hot On a plate, a 0.34 μm-thick resist film formed by performing PB under the conditions shown in Table 2 was coated with an ArF excimer laser exposure device (Nikon Corporation) (lens numerical aperture: 0.2 mm).
Exposure wavelength: 193 nm) through a mask pattern. Thereafter, PEB was performed under the conditions shown in Table 2, and then developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds.
After washing with water and drying, a positive resist pattern was formed. At this time, an exposure amount for forming a line-and-space pattern (1L1S) having a line width of 160 nm in a one-to-one line width was defined as an optimum exposure amount (1L1S), and the optimum exposure amount (1L1S) was defined as a sensitivity. Dense / dense line width difference: When a line-and-space pattern (1L10S) having a line width of 160 nm is exposed at an optimum exposure amount (1L10S) for forming a line width of 1 to 10, a line-and-space pattern (160 nm) has a line width. The line width CD1 of the line pattern at 1L10S) and the line width CD2 of the line and space pattern (1L1.5S) with a line width of 160 nm are measured with a scanning electron microscope, and the difference between CD1 and CD2 is measured. (CD1-CD
2) was evaluated as the sparse / dense line width difference according to the following criteria. Good: CD1−CD2 <20 nm Poor: CD1−CD2 ≧ 20 nm Resolution: The minimum resist pattern dimension resolved at the optimum exposure (1L1S) was taken as the resolution.

Synthesis Example 1 Norbornane lactone methacrylate (methacrylic acid ester corresponding to repeating unit (I-1) in which X is a methylene group, R ¹ is a methyl group, and R ² is a hydrogen atom)
50 g and 2-methyl-2-adamantyl methacrylate 2
After dissolving 6.36 g and 1.15 g of methacrylic acid in 150 g of tetrahydrofuran under nitrogen substitution, 4.14 g of dimethyl azobisisopropionate and 1.36 g of n-dodecylmercaptan were mixed, and the mixture was heated at 70 ° C. Polymerized for 4 hours. Thereafter, the reaction solution was cooled, and methanol 1.
The resin was coagulated by dropping into 5 liters, and the coagulated resin was separated by filtration, washed, and dried by a vacuum dryer for 24 hours to obtain 45 g of a white powdery resin (yield: 90%).
% By weight). This resin had a Mw of 12,000, and as a result of composition analysis by ¹³ C-NMR, it was found that norbornane lactone methacrylate / 2-methyl-2 methacrylate was used.
The adamantyl / methacrylic acid copolymer molar ratio is 45.3;
/50.2/4.5. This resin is converted to resin (A-
1)

Synthesis Example 2 11.98 g of norbornane lactone methacrylate and 22.75 g of 2-methyl-2-adamantyl methacrylate
And 3-hydroxy-1-adamantyl methacrylate 1
5.29 g of tetrahydrofuran 1 under nitrogen substitution
After dissolving in 50 g, 3.97 g of dimethyl azobisisopropionate and 1.30 g of n-dodecylmercaptan
And polymerized at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled, and the resin was solidified by dropping into 1.5 liters of methanol. The solidified resin was separated by filtration, washed, and then dried in a vacuum drier for 24 hours to obtain a white powdery resin. 42 g (yield 84% by weight) were obtained. This resin had an Mw of 13,000, and as a result of compositional analysis by ¹³ C-NMR, the copolymer molar ratio of norbornane lactone methacrylate / 2-methyl-2-adamantyl methacrylate / 3-hydroxy-1-adamantyl methacrylate was found. 25.3 / 44.5 / 30.2. This resin is referred to as resin (A-2).

Synthesis Example 3 21.81 g of cyclohexyllactone methacrylate (methacrylic acid ester corresponding to the repeating unit (I-2) in which R ³ is a methyl group and R ⁴ is a hydrogen atom) and 2-methyl-2-adamantyl methacrylate After 27.01 g and 1.18 g of methacrylic acid were dissolved in 150 g of tetrahydrofuran under nitrogen substitution, 4.24 g of dimethyl azobisisopropionate and 1.39 g of n-dodecylmercaptan were mixed, and the mixture was heated at 70 ° C. Polymerized for 4 hours. Thereafter, the reaction solution was cooled, and the resin was solidified by dropping into 1.5 liters of methanol. The solidified resin was separated by filtration, washed, and then dried in a vacuum drier for 24 hours to obtain a white powdery resin. 44 g (88% by weight) were obtained. This resin has a Mw of 12,300 and a ¹³ C—N
As a result of composition analysis by MR, the molar ratio of norbornane lactone methacrylate / 2-methyl-2-adamantyl methacrylate / methacrylic acid copolymer was 45.2 / 49.8 /.
5.0. This resin is referred to as resin (A-3).

Synthesis Example 4 21.81 g of norbornane lactone methacrylate and 27.08 g of 2-ethyl-2-adamantyl methacrylate
And 1.11 g of methacrylic acid were dissolved in 150 g of tetrahydrofuran under nitrogen substitution, and 4.01 g of dimethyl azobisisopropionate and 1.31 g of n-dodecylmercaptan were mixed and polymerized at 70 ° C. for 4 hours. did. Thereafter, the reaction solution was cooled, and the resin was solidified by dropping into 1.5 liters of methanol. The solidified resin was separated by filtration, washed, and then dried in a vacuum drier for 24 hours to obtain a white powdery resin. 40 g (yield 80% by weight)
I got This resin has a Mw of 12,800 and a ¹³ C
As a result of composition analysis by NMR, the molar ratio of norbornane lactone methacrylate / 2-ethyl-2-adamantyl methacrylate / methacrylic acid copolymer was 44.3 / 50.
2 / 5.5. This resin is referred to as resin (A-4).

Synthesis Example 5 β-methacryloyloxy-γ-butyrolactone
0 g and 2-methyl-2-adamantyl methacrylate 2
9.0 g was dissolved in 50 g of tetrahydrofuran to make a uniform solution, and nitrogen gas was blown in for 30 minutes. Then, 2.4 g of azobisisobutyronitrile as a polymerization initiator was added, and
Stirred at 5 ° C. for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, diluted with 50 g of tetrahydrofuran, and diluted with n-
The resin was poured into 1,000 ml of hexane, and the precipitated resin was separated by filtration, washed, and dried to obtain the resin as a white powder. This resin has a Mw of 9,700 and has β-methacryloyloxy-γ-butyrolactone /
It was a copolymer having a 2-methyl-2-adamantyl methacrylate copolymer molar ratio of 50/50. This resin is referred to as resin (A-5).

Examples 1 to 6 and Comparative Examples 1 to 5 Various evaluations were made on each composition solution comprising the components shown in Table 1. Table 3 shows the evaluation results. The components other than the resins (A-1) to (A-5) in Table 1 are as follows. Acid generator (B) B-1: 4-n-butoxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate B-2: 4-n-butoxy-1-naphthyltetrahydrothiophenium perfluoro- n-octanesulfonate B-3: bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate B-4: nonafluoro-n-butanesulfonylbicyclo [
2.2.1] Hept-5-ene-2,3-dicarbodiimide polycyclic compound (C) C-1: t-butyl deoxycholate C-2: t-butoxycarbonylmethyl deoxycholate C-3 : T-butoxycarbonylmethyl lithocholic acid

Acid diffusion controller D-1: Nt-butoxycarbonyl-2-phenylbenzimidazole D-2: Nt-butoxycarbonyldicyclohexylamine D-3: 2,2 ': 6', 2 '' -Terpyridine solvent E-1: propylene glycol monomethyl ether acetate E-2: 2-heptanone E-3: γ-butyrolactone E-4: cyclohexanone

[0292]

[Table 1]

[0293]

[Table 2]

[0294]

[Table 3]

[0295]

The radiation-sensitive resin composition of the present invention can be used in the form of an actinic radiation such as an ArF excimer laser (wavelength 193n).
m), as a chemically amplified resist sensitive to far ultraviolet rays typified by KrF excimer laser (wavelength 248 nm) or F ₂ excimer laser (wavelength 157 nm), especially when the space width of the line and space pattern is wide. It is characterized in that a fine line pattern can be formed, and even in a pitch size up to a quasi-dense area (for example, about 1L1.5S), a large line width variation due to a proximity effect between lines is not exhibited. It has excellent properties, sensitivity, resolution, etc., and can be used very suitably in the manufacture of semiconductor devices that are expected to be further miniaturized in the future.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Ishii 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (72) Inventor Toru Kajita 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR In-house F-term (reference) 2H025 AA01 AA02 AA04 AB16 AC04 AC05 AC06 AC08 AD03 BE00 BE10 BG00 CB14 CB41 CB55 FA17 4J100 AL08P AL08Q BA03Q BA04Q BA05Q BA06Q BA11P BA11Q BA16Q BA40Q BC08Q BC09P CA58 BC05P

Claims (1)

[Claims] (A) at least one type of repeating unit selected from the group consisting of a repeating unit (I-1), a repeating unit (I-2) and a repeating unit (I-3) represented by the following general formula (1): And a repeating unit (II) represented by the following general formula (2), an alkali-insoluble or alkali-soluble resin showing alkali solubility by the action of an acid, (B) a radiation-sensitive acid generator, and (C) ) Formula -COOR ⁹ wherein R ⁹ is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted monovalent monovalent having 3 to 20 carbon atoms. Alicyclic hydrocarbon group or -CH
₂ COOR ¹⁰ (where R ¹⁰ is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted monovalent alicyclic having 3 to 20 carbon atoms) A hydrocarbon group). A radiation-sensitive resin composition comprising a polycyclic compound having a group represented by the following formula and having a molecular weight of 1,000 or less. Embedded image [In the general formula (1), R ¹ , R ³ and R ⁵ independently represent a hydrogen atom or a methyl group, and R ² , R ⁴ and R ⁶ independently represent a hydrogen atom or a carbon number of 1 to 4 X represents a methylene group, an oxygen atom or a sulfur atom, and a is an integer of 1 to 5. [Chemical formula 2] [In the general formula (2), R ⁷ represents a hydrogen atom or a methyl group, and each R ⁸ is independently a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, Represents a linear or branched alkyl group of 1 to 4, and at least one of R ⁸ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ⁸ are mutually bonded, Forming a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atom to which each is bonded, and the remaining R ⁸ is a linear or branched C 1 to C 4 hydrocarbon group; An alkyl group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof. ]