JP2002278073A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition containing a specified polysiloxane, having high transparency to radiation of <=193 nm wavelength and excellent in dry etching resistance, sensitivity, resolution, developability, etc. SOLUTION: The radiation sensitive resin composition contains (a) a resin having at least one selected from the group comprising a structural unit (I) or a structural unit (II) of formula (1) and a structural unit (III) or a structural unit (IV) of formula (2) and made alkali-soluble when an acid dissociable group is dissociated and (b) a radiation sensitive acid generator. In the formulae, each R is H or methyl; R' is H, a monovalent (halogenated) hydrocarbon group, halogen or amino; X<1> and X<2> are each a monovalent organic group which is dissociated by an acid and generates H or H (but the case of X<1> =H is excluded); R" is H, methyl or trifluoromethyl; and (m) and (n) are each an integer of 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive resin composition containing a siloxane-based polymer having a specific norbornene-based alicyclic structure and suitable for fine processing using radiation such as far ultraviolet rays, electron beams, and X-rays. About things.

[0002]

2. Description of the Related Art In recent years, demands for higher density and higher integration of LSIs (highly integrated circuits) have been increasing, and accordingly, miniaturization of wiring patterns has been rapidly progressing. As one of means that can cope with such miniaturization of wiring patterns, there is a method of shortening the wavelength of exposure light used in a lithography process.
m) or i-rays (wavelength 365 nm)
rF excimer laser (wavelength 248 nm) or Ar
Far ultraviolet rays typified by F excimer laser (wavelength 193 nm), electron beams, X-rays, and the like have come to be used. By the way, novolak resins, poly (vinylphenol), and the like have been used as resin components in conventional resist compositions, but these materials contain an aromatic ring in the structure and have strong absorption at a wavelength of 193 nm. Therefore, for example, A
In a lithography process using an rF excimer laser, high sensitivity, high resolution, and high accuracy corresponding to a high aspect ratio cannot be obtained. Therefore, 193 nm or less, especially 1
There is a need for a resist resin component that is transparent to a wavelength of 57 nm and has a dry etching resistance equal to or higher than that of an aromatic ring. One such example is a siloxane-based polymer. MIT RRKunz et al. Have shown that polysiloxane-based polymers have excellent transparency at wavelengths of 193 nm or less, particularly at 157 nm. It is reported to be suitable for resist materials in lithography processes using wavelengths (J. Photopolym. Sci. Technol., Vol. 12, No. 4,
1999). It is also known that a polysiloxane-based polymer has excellent dry etching resistance, and in particular, a resist containing a polyorganopolysilsesquioxane having a ladder structure has high plasma resistance.

On the other hand, some resist materials using siloxane polymers have already been reported. That is,
JP-A-5-323611 discloses a polymer having an acid-dissociable group in a side chain in which an acid-dissociable group such as a carboxylic acid ester group and a phenol ether group is bonded to a silicon atom via one or more carbon atoms. Japanese Patent Application Laid-Open No. 8-160623 discloses a radiation-sensitive resin composition using siloxane, in which a polymer obtained by protecting a carboxyl group of poly (2-carboxyethylsiloxane) with an acid-dissociable group such as a t-butyl group is used. JP-A-11-60733 discloses a resist resin composition using a polyorganosilsesquioxane having an acid-dissociable ester group. However, resist materials using these conventional acid-dissociable group-containing siloxane-based polymers are not yet at a satisfactory level in terms of basic physical properties of the resist such as transparency to radiation, resolution, and developability. . Further, JP-A-11-302382 discloses a non-aromatic monocyclic or polycyclic hydrocarbon group having a carboxyl group or a bridged cyclic hydrocarbon group in a side chain, and A siloxane-based polymer in which at least a part of
A siloxane-based polymer in which a norbornyl group having a t-butoxycarbonyl group at a position is bonded to a silicon atom, and a resist material using the polymer are disclosed.
This resist material is a KrF excimer laser (wavelength 2).
48 nm) or ArF excimer laser (wavelength 19
3 nm), the pattern shape is good,
It is also said to be excellent in sensitivity, resolution, dry etching resistance and the like. However, Japanese Patent Application Laid-Open No. 11-302
Even if the siloxane-based polymer disclosed in Japanese Patent No. 382 is included, there are few types of siloxane-based polymers useful as a resin component of a resist material, and the siloxane-based polymer is used as a resin component to effectively respond to short-wavelength radiation and to perform advanced dry etching. Development of a radiation-sensitive resin composition having excellent basic properties as a resist while having resistance has become an important issue from the viewpoint of technical development capable of coping with the progress of miniaturization of semiconductor elements.

[0004]

An object of the present invention is to contain a siloxane-based polymer having a specific norbornene-based alicyclic structure, and to effectively respond to radiation such as far ultraviolet rays, electron beams, and X-rays. Wavelength 193 nm or less, especially wavelength 157
It is an object of the present invention to provide a radiation-sensitive resin composition having high transparency to radiation of nm and excellent in basic physical properties as a resist such as dry etching resistance, sensitivity, resolution, and developability.

[0005]

According to the present invention, the object is to provide (a) a structural unit (I) or a structural unit (II) represented by the following general formula (1) and a structural unit represented by the following general formula (2): An alkali-insoluble or alkali-insoluble polysiloxane having at least one structural unit selected from the group consisting of units (III) and structural units (IV),
A radiation-sensitive resin composition comprising a resin which becomes alkali-soluble when the acid-dissociable group is dissociated, and (b) a radiation-sensitive acid generator.

[0006]

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[In the general formula (1), each R independently represents a hydrogen atom or a methyl group, R ′ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, 2
X represents a monovalent halogenated hydrocarbon group, a halogen atom or a primary, secondary or tertiary amino group; X ¹ represents a monovalent organic group which is dissociated by an acid to generate a hydrogen atom;
Is an integer of 0 to 3. However, each silicon atom in the general formula (1) is bonded to the 2-position or 3-position of the bicyclo [2.2.1] heptane ring at the highest position. ]

[0008]

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[In the general formula (2), each R independently represents a hydrogen atom or a methyl group; R 'represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, 2
0 represents a monovalent halogenated hydrocarbon group, a halogen atom or a primary, secondary or tertiary amino group; R ″ represents a hydrogen atom, a methyl group or a trifluoromethyl group;
² represents a hydrogen atom or a monovalent organic group which is dissociated by an acid to generate a hydrogen atom, and n is an integer of 0 to 3. However,
Each silicon atom in the general formula (2) is a bicyclo at the top
[2.2.1] It is bonded to the 2- or 3-position of the heptane ring. ] Is achieved.

Hereinafter, the present invention will be described in detail. Polysiloxane (a) In the present invention, the component (a) comprises the structural unit (I) or the structural unit (II) represented by the general formula (1) and the structural unit (III) or the structural unit represented by the general formula (2) (IV)
A polysiloxane having at least one structural unit selected from the group consisting of: an alkali-insoluble or slightly alkali-soluble polysiloxane, which becomes alkali-soluble when its acid-dissociable group is dissociated (hereinafter referred to as “polysiloxane ( B))).

In the general formulas (1) and (2), R in the structural unit (I), R in the structural unit (II), R in the structural unit (III), and the structural unit (I
R in V) may be the same or different from each other.

Next, in the structural unit (II) of the general formula (1) and the structural unit (IV) of the general formula (2), as the monovalent hydrocarbon group having 1 to 20 carbon atoms for R ′, for example, , Methyl, ethyl, n-propyl, i-propyl, n
-Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n A linear or branched alkyl group such as a nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group; cyclobutyl group,
Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; phenyl group, o-tolyl group, m-tolyl group, p-
Aromatic hydrocarbon groups such as tolyl group, benzyl group, phenethyl group, 1-naphthyl group and 2-naphthyl group; norbornyl group, tricyclodecanyl group, tetracyclodecanyl group,
And a bridged hydrocarbon group such as an adamantyl group.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms for R ′ include, for example, the aforementioned 1 to 2 carbon atoms.
A group in which a monovalent hydrocarbon group of 0 is substituted with one or more or one or more halogen atoms, preferably a fluorine atom, more specifically, a pentafluoroethyl group, 3,3,3,
2,2-pentafluoro-n-propyl group, perfluoro-i-propyl group, pentafluorophenyl group, o-
Trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoromethylphenyl group,
2,6-bis (trifluoromethyl) phenyl group, 3,
5-bis (trifluoromethyl) phenyl group, 2,4
6-tris (trifluoromethyl) phenyl group, 3,
4,5-tris (trifluoromethyl) phenyl group, perfluoronorbonyl group, the following formula (3)

[0014]

Embedded image (In the formula, each Rf independently represents a hydrogen atom or a fluorine atom, and at least one Rf is a fluorine atom, and j is an integer of 0 to 4.) Can be mentioned.

Among these monovalent halogenated hydrocarbon groups, a trifluoromethyl group, a pentafluoroethyl group,
3,3,3,2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, , 4-difluorophenyl group, 2,5-difluorophenyl group, 2,6
-Difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-triphenyl group Fluorophenyl group, 2,4
6-trifluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorobenzyl group, pentafluorophenethyl group, o-trifluoromethylphenyl group, m-trifluoromethylphenyl group, p-trifluoromethylphenyl Group, 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-tris As the (trifluoromethyl) phenyl group and the group represented by the formula (3), a pentafluorobenzyl group, a pentafluorophenethyl group, and the like are preferable.

Examples of the halogen atom for R ′ include a fluorine atom, a chlorine atom, and a bromine atom. Of these halogen atoms, a chlorine atom is preferred. Examples of the secondary or tertiary amino group for R ′ include a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, a cyclopentylamino group, and a cyclohexylamino. Group, phenylamino group, benzylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-i-propylamino group, di-n-butylamino group, dicyclopentylamino group, dicyclohexylamino group, Examples thereof include a diphenylamino group and a dibenzylamino group. As the amino group for R ′, an amino group, a dimethylamino group, a diethylamino group, a dicyclopentylamino group, a dicyclohexylamino group, a diphenylamino group, and the like are preferable.

R ′ in the structural units (II) and (IV) is particularly preferably a methyl group, an ethyl group, a cyclohexyl group, a pentafluoroethyl group, a chlorine atom, a dimethylamino group and the like. R ′ in the structural unit (II) and R ′ in the structural unit (IV) may be the same or different from each other. As R ″ in the general formula (2), a hydrogen atom, a methyl group, and a trifluoromethyl group are all preferable. R ″ in the structural unit (III) and R ″ in the structural unit (IV) may be the same or different from each other.

Next, in the structural unit (I) and the structural unit (II) of the general formula (1), the monovalent organic group which dissociates with an acid of X ¹ to generate a hydrogen atom includes the following formula (a) (Hereinafter, referred to as “acid dissociable group (a)”).

[0019]

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[In the formula (a), R ′ ″ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. Or a derivative thereof, or any two R ″ ′ s are mutually bonded to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which they are bonded. Wherein the remaining R ′ ″ is a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or a derivative thereof. ]

In the formula (a), R ″ ′ has 1 to 4 carbon atoms.
Examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t- Butyl group and the like.
Also, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ″ ″ and a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms formed by bonding any two R ′ ″ to each other. Examples of the cyclic hydrocarbon group include, for example, alicyclics derived from cycloalkanes such as norbornane, tricyclodecane, tetracyclodecane, adamantane, and cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. A group consisting of a group; a group consisting of these alicyclic groups
Examples thereof include a group substituted with one or more alkyl groups having 1 to 4 carbon atoms. R ′ ″ in the general formula (1)
Is particularly preferably a methyl group.

In the structural units (III) and (IV) of the general formula (2), a monovalent organic group which is dissociated by an acid of X ² to generate a hydrogen atom (hereinafter referred to as “acid-dissociable group ( b))) include, for example, a tertiary alkyl group, a group that forms an acetal group together with an oxygen atom to which X ² is bonded (hereinafter, referred to as an “acetal forming group”);
Examples include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group (excluding a tertiary alkyl group), a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a cyclic acid dissociable group. Can be.

In the acid dissociable group (b), the tertiary alkyl group includes, for example, t-butyl group, 1,1-dimethylpropyl group, 1-methyl-1-ethylpropyl group,
1,1-dimethylbutyl group, 1-methyl-1-ethylbutyl group, 1,1-dimethylpentyl group, 1-methyl-1
-Ethylpentyl group, 1,1-dimethylhexyl group,
Examples thereof include a 1,1-dimethylheptyl group and a 1,1-dimethyloctyl group. Examples of the acetal-forming group include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, a t-butoxymethyl group,
-Pentyloxymethyl group, n-hexyloxymethyl group, cyclopentyloxymethyl group, cyclohexyloxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-i-propoxyethyl group , 1-n-butoxyethyl group, 1-t-butoxyethyl group, 1-n-pentyloxyethyl group, 1
-N-hexyloxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1
-Methoxypropyl group, 1-ethoxypropyl group, (cyclohexyl) (methoxy) methyl group, (cyclohexyl)
(Ethoxy) methyl group, (cyclohexyl) (n-propoxy) methyl group, (cyclohexyl) (i-propoxy)
Methyl group, (cyclohexyl) (cyclohexyloxy)
Examples include a methyl group.

Examples of the substituted methyl group include, for example, phenacyl group, p-bromophenacyl group, p-methoxyphenacyl group, p-methylthiophenacyl group, α-
Methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, p
-Bromobenzyl group, p-nitrobenzyl group, p-methoxybenzyl group, p-methylthiobenzyl group, p-ethoxybenzyl group, p-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n -Propoxycarbonylmethyl group, i-
Examples thereof include a propoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, and a t-butoxycarbonylmethyl group. Examples of the 1-substituted ethyl group include 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, n-propoxycarbonylethyl group, 1-i-
Examples thereof include a propoxycarbonylethyl group, a 1-n-butoxycarbonylethyl group, and a 1-t-butoxycarbonylethyl group.

Further, as the 1-branched alkyl group,
For example, an i-propyl group, a sec-butyl group, a 1-methylbutyl group and the like can be mentioned. Examples of the silyl group include trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, i-propyldimethylsilyl, and methyldi-i.
-Propylsilyl group, tri-i-propylsilyl group, t
-Butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group and the like. Examples of the germyl group include a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an i-propyldimethylgermyl group, a methyldi-i-propylgermyl group, and a trimethylgermyl group. -I-propylgermyl group, t-butyldimethylgermyl group, methyldi-t
-Butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group and the like.
Further, as the alkoxycarbonyl group, for example,
Examples include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, and a t-butoxycarbonyl group.

Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauryloyl group, a myristoyl group, a palmitoyl group, a stearoyl group, an oxalyl group. Group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoil group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group,
Fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, tenoyl group, nicotinoyl group, isonicotinoyl group , P-toluenesulfonyl group, mesyl group and the like. Further, examples of the cyclic acid dissociable group include a 3-oxocyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 3-bromotetrahydropyranyl group, -Methoxytetrahydropyranyl group, 2-oxo-4-methyl-4-tetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group,
Examples thereof include a 3-tetrahydrothiophene-1,1-dioxide group.

X ² in the general formula (2) is a hydrogen atom, or an acid-dissociable group (b) such as a t-butyl group or a t-butyl group.
Butoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, methoxymethyl, ethoxymethyl, 1-methoxyethyl, 1-ethoxyethyl and the like are preferred. X ¹ in the structural unit (I), X in the X ¹ in the structural unit (II), dissociated by acid X ² in the structural unit (III) 1 monovalent organic groups formed hydrogen atom and the structural unit, (IV) ^The monovalent organic groups that are dissociated by the ^two acids to generate a hydrogen atom may be the same or different from each other.

Further, m in the structural unit (I) and m in the structural unit (II) are each 0 or 1
Is particularly preferable, and n in the structural unit (III) and n in the structural unit (IV) are each preferably 0 or 1. M in the structural unit (I), m in the structural unit (II), and n in the structural unit (III)
And n in the structural unit (IV) may be the same or different from each other.

Preferred specific examples of the structural unit (I) include structural units represented by the following formula (I-1) or (I-2).

[0030]

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Preferred specific examples of the structural unit (II) include structural units represented by the following formulas (II-1) to (II-8).

[0032]

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[0033]

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Preferred examples of the structural unit (III) include structural units represented by the following formulas (III-1-1) to (III-1-12); To (III-2-12).

[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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[0040]

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[0041]

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[0042]

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Among these structural units (III), the compounds represented by the formulas (III-1-2), (III-1-3), (III-1-5) and (III-1-
6), Formula (III-1-8), Formula (III-1-9), Formula (III-2-2), Formula (III-2-3), Formula (III-2-5), Formula (III-2-5) III-2-6), Formula (III-2-
The structural unit represented by 8) or the formula (III-2-9) is preferable.

Preferred specific examples of the structural unit (IV) include structural units represented by the following formulas (IV-1-1) to (IV-1-48); To (IV-2-48).

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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Among these structural units (IV), in particular, the formulas (IV-1-14), (IV-1-15), (IV-1-17) and (IV-1-1)
8), Formula (IV-1-20), Formula (IV-1-21), Formula (IV-1-26), Formula (IV-1-27), Formula (IV-1-29), Formula (IV-1-29) IV-1-30), Formula (IV-1-3
2), Formula (IV-1-33), Formula (IV-2-14), Formula (IV-2-15), Formula (IV-2-17), Formula (IV-2-18), Formula (IV-2-18) IV-2-20), Formula (IV-2-2
1), Formula (IV-2-26), Formula (IV-2-27), Formula (IV-2-29), Formula (IV-2-30), Formula (IV-2-32) or Formula (IV-2-32) The structural unit represented by IV-2-33) is preferred. In the polysiloxane (a), the structural unit (I), the structural unit (II), and the structural unit (III)
And each of the structural units (IV) may be present alone or in combination of two or more.

Examples of the condensing component providing the structural unit (I) include a silane compound (i) represented by the following general formula (4) or a linear or cyclic oligomer obtained by partially condensing the silane compound. Examples of the condensation component that provides the structural unit (II) include a silane compound (ii) represented by the following general formula (4) or a linear or cyclic oligomer obtained by partially condensing the silane compound. Examples of the condensing component that provides the unit (III) include a silane compound (iii) represented by the following general formula (5) or a linear or cyclic oligomer obtained by partially condensing the silane compound. Examples of the condensing component that provides (IV) include a silane compound (iv) represented by the following general formula (5) or a straight chain obtained by partially condensing the silane compound. Ku can be mentioned the cyclic oligomers.

[0079]

Embedded image [In the general formula (4), R, R ′, X ¹ and m are
R, R ′, X ¹ and m in the general formula (1), respectively
And Y is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or the following formula (6)

[0080]

Embedded image (Wherein each Y ′ is independently a hydrogen atom, a carbon atom 1)
A monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, and k represents 1 to 1
It is an integer of 0. ). ]

[0081]

Embedded image [In the general formula (5), R, R ′, R ″, X ² and n are each R, R ′, R ″,
Have the same meaning as X ² and n, Y is a monovalent hydrocarbon group, a group represented by a monovalent halogenated hydrocarbon group or the formula of 1 to 20 carbon atoms (6) of 1 to 20 carbon atoms Show. ]

The “linear oligomer in which the silane compound is partially condensed” refers to two Si—O in each silane compound.
By condensation between the Y groups, a dimer to dimer, preferably 2 to 10 mer,
To a pentamer, and the term "cyclic oligomer in which a silane compound is partially condensed" refers to an oligomer which is condensed between two Si-OY groups in each silane compound, and is usually 3 to 10 Oligomer, preferably an oligomer which forms a trimer, preferably a trimer to a pentamer. As Y in the silane compounds (i) to (iv), a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and the like are preferable.

The silane compound (i) and the silane compound (ii) may be, for example, a norbornene (that is, bicyclo [2.2.1] hept-2-ene) derivative corresponding to each silane compound and a corresponding hydrosilyl compound. Can be synthesized according to a conventional method for hydrosilylation in the presence of a hydrosilylation catalyst, in the absence of a solvent, or in an appropriate solvent.

When X ² is a hydrogen atom, for example, the silane compound (iii) and the silane compound (iv) are prepared by subjecting a norbornene derivative corresponding to each silane compound and a corresponding hydrosilane compound to a conventional hydrosilylation reaction. The reaction can be carried out in the presence of a hydrosilylation catalyst, in the absence of a solvent, or in a suitable solvent. When X ² is an acid dissociable group (b), it can be synthesized by, for example, the following methods. The silane compound X ² is t- butoxycarbonyl group (iii) and the silane compound (iv) is a silane compound X ² is a hydrogen atom (iii) or X ² is a silane compound are hydrogen atoms (iv) in the A method for esterifying a hydroxyl group with di-t-butyl dicarbonate in the presence of a catalytic amount of 4-dimethylaminopyridine; the silane compound (iii) and the silane compound (iv) wherein X ² is a t-butyl group a compound obtained by converting the silane compound X ² is a hydrogen atom (iii) or X ² is a silane compound which is a hydrogen atom a hydroxyl group in (iv) sodium oxide group, a t- butyl chloride, removal by a conventional method A method in which a sodium chloride reaction is carried out or a compound obtained by converting a hydroxyl group in a silane compound (i) to (iv) into an acid anhydride group and t-butyl alcohol are condensed by a conventional method. The silane compound X ² is tetrahydropyranyl group (iii) and the silane compound (iv) is a hydroxyl group in the silane compound X ² is a hydrogen atom (iii) or X ² is a silane compound which is a hydrogen atom (iv) Is 2,3-dihydro-
A method of subjecting 4H-pyran to an addition reaction by a conventional method; a silane compound (iii) wherein X ² is an acetal-forming group
And the silane compound (iv) method, the silane compound X ² is a hydrogen atom (iii) or X ² is a silane compound which is a hydrogen atom a hydroxyl group in (iv), and the corresponding vinyl ether, to an addition reaction by a conventional method .

Further, the polysiloxane (a) may have one or more structural units other than the structural units (I) to (IV) (hereinafter, referred to as “other structural units”). Examples of the condensing component that provides another structural unit include a silane compound represented by the following general formula (7) (hereinafter, referred to as “silane compound (7)”) and a silane represented by the following general formula (8) A silane compound having an acid-dissociable group such as a compound (hereinafter, referred to as “silane compound (8)”)

[0086]

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[0087] In [Formula (7) and the general formula (8), A represents a monovalent organic group having an oxygen atom, each R ¹
Are independently of each other a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms or a linear chain having 1 to 10 carbon atoms,
A branched or cyclic halogenated alkyl group;
² is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched halogenated alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic group having 6 to 20 carbon atoms. It represents a hydrocarbon group or a monovalent halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms. ];

A silane compound represented by the following general formula (9) (hereinafter referred to as “silane compound (9)”) and a silane compound represented by the following general formula (10) (hereinafter referred to as “silane compound (10)”) ") And a silane compound represented by the following general formula (11) (hereinafter, referred to as" silane compound (11) ").

[0089]

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[In the general formulas (9) to (11), each R
¹ shows independently of each other a straight, branched or cyclic alkyl group or a straight, a halogenated alkyl group branched or cyclic, each R ³ Are independently of each other a hydrogen atom, a hydroxyl group, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an optionally substituted 1 to 20 carbon atom Linear, branched or cyclic alkoxyl group, acetoxy group which may be substituted,
It represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted. However, each R ³ does not include A in the general formulas (7) and (8). And the like. Further, each of these silane compounds (7) to (11) may be partially or entirely used as a partial condensate. The term "partially condensed product" as used herein refers to a compound which is condensed between two Si-OR 'groups in each silane compound,
Linear oligomers forming 10 to 10-mers, preferably 2 to 5-mers, or two Si-
It means a cyclic oligomer which is condensed between OR 'groups to form a 3- to 10-mer, preferably a 3- to 5-mer.

Hereinafter, these silane compounds (7) to (1)
1) will be described sequentially. In the general formulas (7) and (8), the monovalent organic group having an oxygen atom of A is preferably a carboxyl group, a phenolic hydroxyl group or an organic group having an alcoholic hydroxyl group, or dissociated by an acid. Is a carboxyl group, a linear or branched alkyl group having 1 to 20 carbon atoms having an acid-dissociable group generating a phenolic hydroxyl group or an alcoholic hydroxyl group,
Examples thereof include a monovalent alicyclic hydrocarbon group having 4 to 30 carbon atoms having the acid dissociable group. A is preferably, for example, a group represented by the following general formula (12) or (13).

[0092]

Embedded image [In the general formulas (12) and (13), P represents a single bond, a methylene group, a difluoromethylene group,
-20 linear, branched or cyclic alkylene groups,
A linear, branched or cyclic fluoroalkylene group having 2 to 20 carbon atoms, a divalent aromatic group having 6 to 20 carbon atoms or a divalent alicyclic group having 3 to 20 carbon atoms; A monovalent organic group which is dissociated by a hydrogen atom or an acid to generate a hydrogen atom. ]

In the general formulas (12) and (13), examples of the linear, branched or cyclic alkylene group having 2 to 20 carbon atoms of P include, for example, ethylene group, propylene group, trimethylene group and tetramethylene group. Examples of the methylene group include a linear, branched or cyclic fluoroalkylene group having 2 to 20 carbon atoms, for example, a tetrafluoroethylene group, a hexafluoropropylene group,
Hexafluorotrimethylene group, octafluorotetramethylene group and the like can be mentioned.
Examples of the valent aromatic group include a phenylene group, a naphthylene group, a perfluorophenylene group, a perfluoronaphthylene group, and the like.As the divalent alicyclic group having 3 to 20 carbon atoms, Examples include divalent hydrocarbon groups having a norbornene skeleton, tricyclodecane skeleton, or adamantane skeleton, and halides of these groups. In the general formulas (12) and (13), P represents a single bond, a methylene group, a trifluoromethylene group, a divalent hydrocarbon group having a norbornene skeleton, a halide thereof, or a divalent carbon group having an adamantane skeleton. Hydrogen groups and their halides are preferred.

Examples of the monovalent organic group which is dissociated by an acid of Z to generate a hydrogen atom include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
i-butyl group, sec-butyl group, t-butyl group, n-
Linear groups such as pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, and cyclooctyl; Branched or cyclic alkyl group; phenoxycarbonyl group, 4-t
Aryloxycarbonyl groups such as -butylphenyl group and 1-naphthyl group; aralkyl groups such as benzyl group, 4-t-butylbenzyl group, phenethyl group and 4-t-butylphenethyl group; t-butoxycarbonyl group and methoxycarbonyl Group, ethoxycarbonyl group, i-propoxycarbonyl group, 9-fluorenylmethylcarbonyl group, 2,
2,2-trichloroethylcarbonyl group, 2- (trimethylsilyl) ethylcarbonyl group, i-butylcarbonyl group, vinylcarbonyl group, allylcarbonyl group, benzylcarbonyl group, 4-ethoxy-1-naphthylcarbonyl group, methyldithiocarbonyl group Organic carbonyl groups such as;

Methoxymethyl, ethoxymethyl, methylthiomethyl, t-butylthiomethyl, (phenyldimethylsilyl) methoxymethyl, benzyloxymethyl, t-butoxymethyl, siloxymethyl,
-Methoxyethoxymethyl group, 2,2,2-trichloroethoxymethyl group, bis (2-chloroethoxy) methyl group, 2- (trimethylsilyl) ethoxymethyl group, 1-
Methoxycyclohexyl group, tetrahydropyranyl group,
4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1-
Methyl-1-methoxyethyl group, 1-methyl-1-benzyloxyethyl group, 1- (2-chloroethoxy) ethyl group, 1-methyl-1-benzyloxy-2-fluoroethyl group, 2,2,2- Organic groups such as trichloroethyl group, 2-trimethylsilylethyl group and 2- (phenylselenyl) ethyl group which form an acetal group by bonding to an oxygen atom in the general formula (14); trimethylsilyl group, triethylsilyl group, Tri-i-propylsilyl group, dimethyl-
i-propylsilyl group, diethyl-i-propylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, tribenzylsilyl group, tri-p-xylylsilyl group, triphenylsilyl group, Examples thereof include organic silyl groups such as a diphenylmethylsilyl group and a t-butylmethoxyphenylsilyl group.

Among the monovalent organic groups that dissociate with these acids to generate hydrogen atoms, t-butyl, methoxymethyl, ethoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-methoxyethyl, A 1-ethoxyethyl group, a t-butyldimethylsilyl group and the like are preferable. Note that A in the general formula (7) and A in the general formula (8) may be the same or different from each other.

In the general formulas (7) and (8), examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms for R ¹ include a methyl group, an ethyl group, and an n-type alkyl group. -Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, n
-Octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group and the like.Examples of the linear, branched or cyclic halogenated alkyl group having 1 to 10 carbon atoms include: Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group,
Examples thereof include a dichloromethyl group and a trifluoromethyl group. R ¹ in the general formulas (7) and (8) represents a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group and the like are preferable. Note that the R ¹ in R ¹ of the general formula in the formula (7) (8) may be the same or different from each other.

In formula (8), examples of the linear or branched alkyl group having 1 to 20 carbon atoms for R ² include a methyl group, an ethyl group, an n-propyl group and an i-type group.
-Propyl group, n-butyl group, i-butyl group, sec-
Butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like;
Examples of the straight-chain or branched halogenated alkyl group of 0 include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, and a heptafluoro-i-propyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include:
Examples thereof include a phenyl group, an α-naphthyl group, a β-naphthyl group, a benzyl group, a phenethyl group, and the like.
Examples of the 20 monovalent halogenated aromatic hydrocarbon group include a perfluorophenyl group, a perfluorobenzyl group, a perfluorophenethyl group, a 2- (perfluorophenyl) hexafluoro-n-propyl group, and a 3- ( Perfluorophenyl) hexafluoro-n-propyl group. As R ² in the general formula (8), a methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluorophenethyl group,
-(Perfluorophenyl) hexafluoro-n-propyl group and the like are preferable.

Next, in the general formulas (9) to (11),
Examples of the linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms and the linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms represented by R ¹ include a group represented by the general formula (7): And groups corresponding to R ¹ in the general formula (8). General formula (9)
As R ¹ in (11), a methyl group, an ethyl group,
Preferred are an n-propyl group, an i-propyl group, an n-butyl group and the like. In addition, R ¹ in the general formula (9) and the general formula (1
R ^{1 in} formula (0) and R in general formula (11)
¹ may be the same or different, and each of these R ^1, R ¹ and formula in the formula (7) (8)
R ¹ may be the same or different from each other.

Further, examples of the halogen atom for R ³ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may be substituted for R ³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and an n-propyl group. -Butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl Group,
Cyclohexyl, trifluoromethyl, pentafluoroethyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 4-hydroxycyclohexyl, methoxymethyl, 2-methoxyethyl A 3-methoxypropyl group, a 4-methoxybutyl group, a 4-methoxycyclohexyl group, an acetoxymethyl group, a 2-acetoxyethyl group,
3-acetoxypropyl group, 4-acetoxybutyl group,
4-acetoxycyclohexyl group, mercaptomethyl group, 2-mercaptoethyl group, 3-mercaptopropyl group, 4-mercaptobutyl group, 4-mercaptocyclohexyl group, cyanomethyl group, 2-cyanoethyl group, 3-
Cyanopropyl group, 4-cyanocyclohexyl group, 3-
Examples thereof include a glycidoxypropyl group, a 2- (3,4-epoxy) cyclohexyl group, a 2- (3,4-epoxy) cyclohexylethyl group, and a 3-morpholinopropyl group.

The optionally substituted linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms for R ³ includes, for example, methoxy, ethoxy, n-propoxy, i-propoxy and the like. Group, n-butoxy group, i-
Butoxy group, sec-butoxy group, t-butoxy group, cyclohexyloxy group, fluoromethoxy group, chloromethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 3-chloropropoxy group, 3-bromopropoxy group, 3 -Glycidoxypropoxy group, 4-fluorocyclohexyloxy group, 3,4-epoxycyclohexyloxy group and the like. Examples of the optionally substituted acetoxy group for R ³ include an acetoxy group, a trifluoroacetoxy group, a chloroacetoxy group, and a bromoacetoxy group.

Examples of the optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms for R ³ include, for example, phenyl group, α-naphthyl group, benzyl group, phenethyl group,
-Fluorophenyl group, 3-fluorophenyl group, 4-
Fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group , 2-acetoxyphenyl, 3-acetoxyphenyl, 4-acetoxyphenyl, 2-trimethylsiloxyphenyl, 3-trimethylsiloxyphenyl, 4-trimethylsiloxyphenyl, 2-fluorobenzyl, 3-fluorobenzyl Group, 4-fluorobenzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, 2-hydroxybenzyl group, 3-hydroxybenzyl group, 4-hydroxybenzyl group, 2-methoxybenzyl group, 3-methoxybenzyl group, 4-methoxybenzyl group, 2-a Toxibenzyl group, 3-acetoxybenzyl group, 4-acetoxybenzyl group, 2-trimethylsiloxybenzyl group, 3-trimethylsiloxybenzyl group, 4-trimethylsiloxybenzyl group, perfluorophenethyl group, 3- (perfluorophenyl) hexa Examples thereof include a fluoro-n-propyl group.

R ³ in the general formulas (9) to (11) represents a methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluorophenethyl group,
-(Perfluorophenyl) hexafluoro-n-propyl group and the like are preferable. R ³ in the general formula (9), R ³ is in the R ³ and the formula in the formula (10) (11) may be the same or different from each other.

The silane compounds (7) to (11) can be used alone or in admixture of two or more, or two or more of them can be used in combination. The molecular weight and glass transition temperature (Tg) of the resulting polysiloxane (a) can be controlled by selecting
Transparency at a wavelength of 93 nm or less, especially 157 nm, can be further improved.

The polysiloxane (a) is obtained by converting a silane compound (i) and / or a silane compound (ii) or a partial condensate of these silane compounds, and optionally a silane compound (7) to (11) or a silane compound thereof. Together with the partial condensate of formula (I) in the presence of an acidic catalyst or a basic catalyst, in the absence of a solvent or in a solvent, by polycondensation according to a conventional method.

Hereinafter, the polycondensation method for producing the polysiloxane (a) will be described. Among the acidic catalysts, examples of the inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, and aluminum chloride. Examples of the organic acids include formic acid Acetic acid, n-propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, acetic anhydride, maleic anhydride, citric acid, benzenesulfonic acid , P-toluenesulfonic acid, methanesulfonic acid and the like.
These acidic catalysts can be used alone or in combination of two or more.

Among the above basic catalysts, examples of the inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, and the like.
Potassium carbonate and the like can be mentioned.

Further, as the organic bases, for example, n-
Linear, branched or cyclic monoalkylamines such as hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine; di-n-butylamine, di-n-pentyl Amines, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, linear or branched such as dicyclohexylamine Cyclic dialkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine,
Straight-chain such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, and tricyclohexylamine;
Branched or cyclic trialkylamines;

Aniline, N-methylaniline, N, N-
Aromatic amines such as dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine; ethylenediamine, N, N, N ',
N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 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
] Diamines such as benzene;

Imidazole, benzimidazole, 4-
Imidazoles such as methylimidazole and 4-methyl-2-phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-
Pyridines such as ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline and acridine; piperazine , 1- (2-hydroxyethyl) piperazine and the like, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine,
1,4-dimethylpiperazine, 1,4-diazabicyclo
[2.2.2] Other nitrogen-containing heterocyclic compounds such as octane can be exemplified. These basic catalysts can be used alone or in combination of two or more.

Among the above acidic and basic catalysts, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, acetic anhydride, maleic anhydride, triethylamine, tri-n-propylamine, tri-n -Butylamine, pyridine and the like are preferred. The used amount of the acidic catalyst or the basic catalyst is usually 0.01 to 10,000 parts by weight based on 100 parts by weight of the total amount of the silane compound.

The solvent used in the polycondensation reaction includes
For example, 2-butanone, 2-pentanone, 3-methyl-
Linear or branched such as 2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone Ketones; cyclopentanone, 3-methylcyclopentanone, cyclohexanone,
Cyclic ketones such as 2-methylcyclohexanone, 2,6-dimethylcyclohexanone and isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate;
Propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-se
propylene glycol monoalkyl ether acetates such as c-butyl ether acetate and propylene glycol mono-t-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- 2-hydroxypropionate
2 such as butyl and t-butyl 2-hydroxypropionate;
-Alkyl hydroxypropionates; methyl 3-methoxypropionate, ethyl 3-methoxypropionate,
Alkyl 3-alkoxypropionates such as methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate;

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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-
Alcohols such as propyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether and diethylene glycol di-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; Ethylene glycol monoalkyl ether acetates such as ethylene glycol mono-n-propyl ether acetate; aromatic hydrocarbons such as toluene and xylene;

Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate,
Methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, acetic acid In addition to other esters such as ethyl, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-
Dimethylacetamide, benzylethyl ether, di-
n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
γ-butyrolactone, ethylene carbonate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more. The amount of the solvent used is usually 2,000 parts by weight or less based on 100 parts by weight of the total amount of the silane compound.

The polycondensation reaction for producing the polysiloxane (a) is carried out without solvent, or with 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-hexanone,
Methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone, cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-
It is preferably carried out in a solvent such as 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.

In the polycondensation reaction, water can be added to the reaction system. The amount of water added in this case is usually 10, 10 parts by weight based on 100 parts by weight of the total amount of the silane compound.
000 parts by weight or less. Further, at the time of polycondensation for producing the polysiloxane (1), hexamethyldisiloxane can be added to control the molecular weight of the obtained polymer and improve the stability of the obtained polymer. The amount of hexamethyldisiloxane added is
Usually, 50 parts with respect to 100 parts by weight of the total amount of the silane compound.
0 parts by weight or less, preferably 50 parts by weight or less. In this case, if the addition amount of hexamethyldisiloxane exceeds 500 parts by weight, the molecular weight of the obtained polymer tends to decrease, and the glass transition temperature (Tg) tends to decrease. The reaction temperature in the polycondensation reaction is usually -50 to +300
° C, preferably 20 to 100 ° C, and the reaction time is usually about 1 minute to 100 hours. The polysiloxane (a) is a silane compound (i), a silane compound (iii),
When a silane compound (7), a silane compound (9), or a partial condensate thereof is used, it usually has a partial ladder structure.

In the polysiloxane (a), the total content of the structural units (I) to (IV) is usually from 1 to 100 mol%, preferably from 5 to 10 mol%, based on all the structural units.
0 mol%, particularly preferably 10 to 100 mol%,
The total content of the structural units (I) and (III) is usually 1 to 100 mol%, preferably 10 to 100 mol%, particularly preferably 30 to 100 mol%, based on all structural units. The total content of the structural unit (II) and the structural unit (IV) is usually from 0 to 100 mol%, preferably from 0 to 50 mol%, particularly preferably from 0 to 1 mol%, based on all the structural units.
0 mol%, and in the structural units (III) and (IV), the content of the unit in which X ² is a hydrogen atom is preferably 95 mol% or less, and particularly preferably 90 mol% or less. . The content of other structural units is usually 99 mol% or less, preferably 95 mol% or less, particularly preferably 90 mol% or less, based on all structural units, and is preferably a structural unit having an acid dissociable group. The total content of
Usually, 1 to 100 mol%, preferably 5 to 90 mol%, particularly preferably 10 to 80 mol%, based on all structural units.
It is. In addition, the total content of bifunctional structural units with respect to polycondensation is usually 90 mol% or less, preferably 80 mol% or less, particularly preferably 50 mol% or less, based on all structural units. The total content of the trifunctional structural units is usually 1 to 100 mol%, preferably 20 to 100 mol%, particularly preferably 50 to 100 mol%, based on all structural units. The total content of structural units is usually 5
0 mol% or less, preferably 20 mol% or less.

The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) of polysiloxane (a) measured by gel permeation chromatography (GPC).
Is from 500 to 1,000,000, preferably from 500 to 1,000,000
500,000, particularly preferably 1,000 to 100,
000. In this case, when Mw is less than 500, the glass transition temperature of the obtained polymer tends to decrease,
On the other hand, when it exceeds 1,000,000, the solubility of the obtained polymer in a solvent tends to decrease. The glass transition temperature (Tg) of the polysiloxane (a) is usually-
The temperature is 50 to + 500 ° C, preferably 0 to 300 ° C. In this case, when the glass transition temperature (Tg) is less than -50 ° C,
When it is used as a resist material, pattern formation tends to be difficult. On the other hand, when the temperature exceeds 500 ° C., the solubility of the obtained polymer in a solvent tends to decrease. In the present invention, the polysiloxane (a) can be used alone or as a mixture of two or more. Further, in the present invention, other polysiloxanes can be used in combination with the polysiloxane (a). Examples of the other polysiloxane include polysiloxanes obtained by polycondensing one or more of the silane compounds (7) to (11) or partial condensates of these silane compounds. In this case, the proportion of the other polysiloxane used is usually 95% by weight or less, preferably 90% by weight or less, based on the total of the polysiloxane (a) and the other polysiloxane.

Acid Generator (B) In the present invention, (B) is a radiation-sensitive acid generator that generates an acid upon exposure (hereinafter, referred to as “acid generator (B)”).
The acid dissociable group present in the polysiloxane (a) is dissociated by the action of the acid, and as a result, the exposed portion of the resist film becomes easily soluble in an alkali developing solution,
It has the function of forming a positive resist pattern. Examples of such an acid generator (b) include, for example,
Onium salts, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds and the like can be mentioned. Examples of these acid generators (b) include the following.

Onium salt: Examples of the onium salt include an iodonium salt, a sulfonium salt (including a tetrahydrothiophenium salt), a phosphonium salt, a diazonium salt, a pyridinium salt and the like. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium heptadecafluoro-n-octanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyl Iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-
t-butylphenyl) iodonium nonafluoro-n-
Butanesulfonate, bis (4-t-butylphenyl)
Iodonium heptadecafluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-
Butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium naphthalene sulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium heptadecafluoro-n-octanesulfonate,
Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium salicylate, 4-
Hydroxyphenyl / phenyl / methylsulfonium
p-toluenesulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonium trifluoromethanesulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl-2-oxocyclohexylmethylsulfoniumheptadecafluoro-n-
Octanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium nonafluoro-n-butanesulfonate,
Dicyclohexyl-2-oxocyclohexylsulfonium heptadecafluoro-n-octanesulfonate,
2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium nonafluoro-n-butanesulfonate, 2-oxocyclohexyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4
-Hydroxyphenyl benzyl methylsulfonium p-toluenesulfonate,

1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate,
Naphthyldimethylsulfonium heptadecafluoro-n
-Octanesulfonate, 1-naphthyldiethylsulfoniumtrifluoromethanesulfonate, 1-naphthyldiethylsulfoniumnonafluoro-n-butanesulfonate, 1-naphthyldiethylsulfoniumheptadecafluoro-n-octanesulfonate, 4-cyano-1
-Naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-cyano-1-
Naphthyl diethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate,

4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-
1-naphthyldimethylsulfonium nonafluoro-n-
Butanesulfonate, 4-nitro-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1
-Naphthyl diethylsulfonium nonafluoro-n-butanesulfonate, 4-nitro-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-
Naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethyl Sulfonium nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-
1-naphthyldimethylsulfonium nonafluoro-n-
Butanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate , 4-hydroxy-1-
Naphthyldiethylsulfonium heptadecafluoro-n
-Octane sulfonate,

4-Hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4
-Methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4- (1-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4- (2-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-methoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t-butoxycarbonyloxy-
1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium Trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiophenium Nonafluoro-n-butanesulfonate and the like can be mentioned.

Halogen-containing compound: Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include phenylbis (trichloromethyl) -s-triazine and 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. Specific examples of preferred diazoketones include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphtho of 2,3,4,4'-tetrahydroxybenzophenone. Quinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-
5-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, and the like. Can be.

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like. Sulfonic acid compound: Examples of the sulfonic acid compound include alkylsulfonic acid esters, alkylsulfonic acid imides, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, tris (trifluoromethanesulfonate) of pyrogallol, nitrobenzyl-
9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.
1] hept-5-ene-2,3-dicarbodiimide, N
-Hydroxysuccinimide trifluoromethanesulfonate and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

Of these acid generators (b), diphenyliodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n -Butanesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium salitium , Cyclohexyl-2-oxocyclohexylmethylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexyl Sill trifluoromethanesulfonate, 2-oxo-cyclohexyl dimethyl sulfonium trifluoromethane sulfonate, 4-
Hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo [2. 2.
1] hept-5-ene-2,3-dicarbodiimide, N
-Hydroxysuccinimide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate and the like are preferable.

In the present invention, the acid generators (b) can be used alone or as a mixture of two or more. The amount of the acid generator (b) used is from 10% of polysiloxane (b) from the viewpoint of securing the sensitivity and developability as a resist.
The amount is usually 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight with respect to 0 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 if it exceeds 10 parts by weight, transparency to radiation decreases, and Tends to be difficult to obtain.

Various Additives The radiation-sensitive resin composition of the present invention controls the diffusion phenomenon of the acid generated from the acid generator (b) in the resist film by exposure, and suppresses undesired chemical reactions in the unexposed area. It is preferred to add an acid diffusion controlling agent having an action of acting. By blending such an acid diffusion controller, the storage stability of the obtained composition is further improved, the resolution as a resist is further improved, and the delay time (PED) from exposure to development processing is reduced. The line width change of the resist pattern due to fluctuations can be suppressed,
A composition with excellent process stability is obtained. As the acid diffusion controller, a nitrogen-containing organic compound whose basicity is not changed by exposure or heat treatment during a resist pattern forming step is preferable. Such nitrogen-containing organic compounds include:
For example, the following general formula (16)

[0130]

Embedded image [In the general formula (14), each R ⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. ]

(Hereinafter, referred to as “nitrogen-containing compound (α)”), a compound having two nitrogen atoms in the same molecule (hereinafter, referred to as “nitrogen-containing compound (β)”),
Examples thereof include polymers having three or more nitrogen atoms (hereinafter, referred to as “nitrogen-containing compound (γ)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

Examples of the nitrogen-containing compound (α) include, for example, n
Mono (cyclo) alkylamines such as hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine;
Di-n-butylamine, di-n-pentylamine, di-
n-hexylamine, di-n-heptylamine, di-n
Di (cyclo) alkylamines such as -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-n-nonylamine, tri-n
Tri (cyclo) alkylamines such as decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine and tricyclohexylamine; aniline, N-
Examples thereof include aromatic amines such as methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, and naphthylamine.

Examples of the nitrogen-containing compound (β) include ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4 -Aminophenyl) propane, 2- (4-aminophenyl) -2-
(3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-
Methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like. Examples of the nitrogen-containing compound (γ) include polyethyleneimine, polyallylamine, and 2-dimethylaminoethylacrylamide polymers.

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

Among these nitrogen-containing organic compounds, a nitrogen-containing compound (α) and a nitrogen-containing heterocyclic compound are preferable.
Among the nitrogen-containing compounds (α), tri (cyclo) alkylamines are particularly preferable, and among the nitrogen-containing heterocyclic compounds, pyridines and piperazines are particularly preferable. The acid diffusion controllers can be used alone or in combination of two or more. The amount of the acid diffusion controller is 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 polysiloxane (a). In this case, the compounding amount of the acid diffusion controller is 1
If the amount exceeds 5 parts by weight, the sensitivity as a resist and the developability of an exposed portion tend to decrease. If the amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional fidelity as a resist may be reduced depending on the process conditions.

Further, the radiation-sensitive resin composition of the present invention may contain a surfactant having an effect of improving coatability, 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 and 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 amount of the surfactant is as follows: polysiloxane (a) and acid generator (b)
Is usually 2 parts by weight or less based on 100 parts by weight in total. In addition, examples of the additives other than the above include an antihalation agent, an adhesion aid, a storage stabilizer, and an antifoaming agent.

Preparation of Composition Solution The radiation-sensitive resin composition of the present invention is usually used such that the total solid content is usually 1 to 25% by weight, preferably 2 to 15% 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 in combination of two or more. Among them, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates , Alkyl 2-hydroxypropionates and alkyl 3-alkoxypropionates are preferred.

Method for Forming Resist Pattern In the radiation-sensitive resin composition of the present invention, an acid is generated from the acid generator (b) upon exposure, and the acid dissociation in the polysiloxane (a) is caused by the action of the acid. The group dissociates,
For example, a carboxyl group is generated. As a result, the solubility of the exposed portion of the resist in an alkali developing solution is increased, and the exposed portion is dissolved and removed by the alkali developing solution to obtain a positive resist pattern. 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. The radiation used at that time is far ultraviolet,
Various radiations such as an electron beam and an X-ray can be used, but a KrF excimer laser (wavelength: 248 nm), Ar
Far ultraviolet rays represented by an F excimer laser (wavelength 193 nm) or an F ₂ excimer laser (wavelength 157 nm) are preferable. In the present invention, it is preferable to perform a heat treatment (hereinafter, referred to as “PEB”) after the exposure.
By this PEB, the dissociation reaction of the acid dissociable group in the polysiloxane (a) proceeds smoothly. The heating conditions for PEB are:
Depending on the composition of the resist composition, it is usually 3
It is 0-200 ° C, preferably 50-170 ° 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, a predetermined resist pattern is formed by developing the exposed resist film. Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine. , Triethylamine,
Methyl diethylamine, ethyl dimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4. An alkaline aqueous solution in which at least one alkaline compound such as 3.0] -5-nonene is dissolved. 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 developer comprising the alkaline aqueous solution. Examples of the organic solvent include acetone, 2-butanone,
4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6-
Ketones such as dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, i
Alcohols such as -propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; ethyl acetate And esters such as n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone, and dimethylformamide. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is preferably 100% by volume or less based on the alkaline aqueous solution.
In this case, if the amount of the organic solvent used exceeds 100% by volume, the developability may be reduced and the undeveloped portion of the exposed portion may be increased. In addition, an appropriate amount of a surfactant or the like can be added to a developer composed of an alkaline aqueous solution. In addition,
After development with a developer composed of an alkaline aqueous solution, it is generally washed with water and dried.

[0143]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples. <Synthesis of Monomer> Synthesis Example 1 46.5 g of triethoxysilane and 5-t-butoxycarbonylbicyclo [2.2.1] hept-2 were placed in a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer. -En 4
2.0g was added, After stirring at room temperature, was added a 0.2 molar i- propyl alcohol solution 1.0 ml of chloroplatinic acid (H ₂ PtCl _6), to initiate the reaction, 140
The mixture was heated at reflux at 24 ° C. for 24 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered by suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product.
Thereafter, the crude product was purified by distillation under reduced pressure at 0.4 mmHg and 155 ° C. to obtain 54 g of a compound.

About this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), infrared absorption spectrum (I
R) and mass spectrum (FABMS), the measured values are as follows, where R is a hydrogen atom and X ¹ is t
A silane compound (i) having a butyl group, Y being an ethyl group and m being 0 (hereinafter, referred to as “silane compound (i-1)”). In addition, this compound was a mixture of a compound in which a triethoxysilyl group was bonded to the 2-position of the bicyclo [2.2.1] heptane ring and a compound in which the compound was bonded to the 3-position of the bicyclo [2.2.1] heptane ring. σH: 3.8 ppm (ethoxy group), 1.4 ppm
(T-butyl group). σC: 175 ppm (carbonyl group), 80 ppm
(T-butoxy group), 59 ppm (ethoxy group), 28
ppm (t-butyl group), 19 ppm (methyl group). σSi: -48 ppm. IR: 2879 cm ^-1 (ethoxy group), 1726 cm
^-1 (ester group), 1155 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). FABMS: m / z = 3
59 (M ⁺⁺ 1).

Synthesis Example 2 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 76.0 g of triethoxysilane, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene (100 g), and the mixture was stirred at room temperature. Then, 5.0 ml of a 0.2 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added to start the reaction. The mixture was heated and refluxed at 150 ° C. for 75 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered by suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was subjected to silica gel column chromatography to obtain 53 g of a compound as an n-hexane fraction.

About this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), infrared absorption spectrum (I
R) and mass spectrum (FABMS), the measured values are as follows, where R is a hydrogen atom and X ¹ is t
A silane compound (i) having a butyl group, Y being an ethyl group and m being 1 (hereinafter, referred to as “silane compound (i-2)”). In this compound, the triethoxysilyl group was tetracyclo [4.4.0.1 ^2,5 . [ ^7,10 ] dodecane ring was a mixture of approximately equal amounts of the compound bonded to the 3-position and the compound bonded to the 4-position. σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group), 1.4 ppm (t-butyl group). σC: 175 ppm (carbonyl group), 80 ppm
(T-butoxy group), 59 ppm (ethoxy group), 28
ppm (t-butyl group), 19 ppm (methyl group). σSi: -48 ppm. IR: 2885 cm ^-1 (ethoxy group), 1726 cm
^-1 (ester group), 1153 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). FABMS: m / z = 425 (M ⁺⁺ 1).

Synthesis Example 3 38.8 g of triethoxysilane and 5- [2-hydroxy-2,2-di (trifluoromethyl)] bicyclo were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. [2.2.1] hept-2-ene 43.2 g was added,
After stirring at room temperature, 0.2 ml of chloroplatinic acid (H ₂ PtCl ₆ ) was added.
The reaction was started by adding 0.1 ml of a molar i-propyl alcohol solution, and the mixture was heated and refluxed at 100 ° C. for 30 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered by suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the crude product was
Purification was performed by distillation under reduced pressure at mmHg and 105 ° C. to obtain 59.8 g of a compound.

About this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), ¹⁹ F-NMR When the spectrum (chemical shift “σF”), infrared absorption spectrum (IR), and mass spectrum (FABMS) were measured, the measured values were as follows, where R was a hydrogen atom and R ″ was a trifluoromethyl group. , X ² is a hydrogen atom, Y is an ethyl group, and n is 0 (hereinafter referred to as “silane compound (iii-
1) ". ). In addition, this compound was a mixture of a compound in which a triethoxysilyl group was bonded to the 2-position of the bicyclo [2.2.1] heptane ring and a compound in which the compound was bonded to the 3-position of the bicyclo [2.2.1] heptane ring. σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group). σC: 123 ppm (trifluoromethyl group), 59
ppm (ethoxy group), 18 ppm (methyl group). σSi: -48 ppm. ? F: -76 to -79 ppm. IR: 3400 cm ^-1 (hydroxyl group), 2878 cm
^-1 (methoxy group), 1215 cm ^-1 (CF bond), 1
082 cm ^-1 (siloxane group). FABMS: m / z = 439 (M ⁺⁺ 1).

Synthesis Example 4 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 3.0 g of the silane compound (iii-1) obtained in Synthesis Example 3 and 10 ml of tetrahydrofuran were added. When the temperature of the reaction solution reached 5 ° C. or lower, 16.7 mg of 4-dimethylaminopyridine was added.
After addition of 1.64 di-t-butyl dicarbonate.
g in 5 ml of tetrahydrofuran was added dropwise over 15 minutes. After stirring for 1 hour after the completion of the dropwise addition, the reaction solution was returned to room temperature and further stirred for 5 hours.
Thereafter, 50 ml of n-hexane was added to the reaction solution, and the mixture was transferred to a separating funnel. The organic layer was washed three times with ice water. Thereafter, the organic layer was poured into a beaker, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was subjected to silica gel chromatography to obtain 3.5 g of a compound from the n-hexane fraction.

About this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), ¹⁹ F-NMR When the spectrum (chemical shift “σF”), infrared absorption spectrum (IR), and mass spectrum (FABMS) were measured, the measured values were as follows, where R was a hydrogen atom and R ″ was a trifluoromethyl group. , X ² is a t-butoxycarbonyl group, Y is an ethyl group, and n is 0, and was identified as a compound substituted with a silane compound (iii) (hereinafter referred to as “silane compound (iii-2)”). σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group), 1.5 ppm (t-butyl group). σC: 149 ppm (carbonate group), 122 pp
m (trifluoromethyl group), 85 ppm (t-butoxy group), 59 ppm (ethoxy group), 28 ppm (t-
Butyl group), 18 ppm (methyl group). σSi: -48 ppm. ? F: -72.7 to -73.3 ppm. IR: 3400 cm ^-1 (hydroxyl group), 2879 cm
^-1 (methoxy group), 1774 cm ^-1 (carbonate group), 1221 cm ^-1 (CF bond), 1082 cm ^-1
(Siloxane group). FABMS: m / z = 539 (M ⁺⁺ 1).

Synthesis Example 5 In a three-necked flask equipped with a stirrer, a cold flow cooler, and a thermometer, 365 g of triethoxysilane and 2.2 g of bicyclo [2.2.
1] After adding 200 g of hept-2-ene and stirring at room temperature, 4.0 ml of a 0.2 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added to start the reaction, The mixture was heated under reflux at 160 ° C. for 90 hours. afterwards,
After returning the reaction solution to room temperature and diluting with n-hexane,
Suction filtration on celite, further distilling off the solvent under reduced pressure,
A crude product was obtained. Thereafter, the crude product was purified by distillation under reduced pressure at 3.0 mmHg and 82 ° C. to obtain 252 g of a compound. For this compound, ¹ H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (I
When R) was measured, the measured values were as follows and were identified as a silane compound represented by the following formula (v) (hereinafter, referred to as "silane compound (v)"). The triethoxysilyl group in this compound is bicyclo [2.2.1].
It is bonded to the 2-position of the heptane ring. σH: 3.8 ppm (ethoxy group), 1.2 ppm (ethoxy group). IR: 2880 cm ^-1 (ethoxy group), 1080 cm ^-1
(Siloxane group).

[0152]

Embedded image

Synthesis Example 6 118 g of triethoxysilane and tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene 100g added, After stirring at room temperature, was added a 0.2 molar i- propyl alcohol solution 4.0 ml of chloroplatinic acid (H ₂ PtCl _6), the reaction It was started and heated to reflux at 160 ° C. for 90 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered by suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was purified by distillation under reduced pressure at 1.5 mmHg and 133 ° C. to obtain 68 g of a compound. For this compound, ¹ H
When the -NMR spectrum (chemical shift "? H") and infrared absorption spectrum (IR) were measured, the measured values were as follows, and the silane compound represented by the following formula (vi) (hereinafter, "silane compound ( vi) ”). The triethoxysilyl group in this compound was tetracyclo [4.4.0.1 ^2,5 . [ ^7,10 ] dodecane ring at the 3-position. σH: 3.8 ppm (ethoxy group), 1.2 ppm (ethoxy group). IR: 2880 cm ^-1 (ethoxy group), 1080 cm ^-1
(Siloxane group).

[0154]

Embedded image

<Synthesis of Polymer> Synthesis Example 7 8.34 g of silane compound (i-2) and 12.92 g of silane compound (iii-1) were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. 7. methyltriethoxysilane
75 g, 30 g of 4-methyl-2-pentanone, 1.75
After adding 7.20 g of a weight% oxalic acid aqueous solution and reacting with stirring at 80 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added thereto, followed by washing with water.After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure. 18.5 g of polymer were obtained. When the ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured,
It was as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group), 0.2 ppm (SiCH
₃ ). Mw: 2,300. This polymer is referred to as polysiloxane (a-1).

Synthesis Example 8 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 5.36 g of the silane compound (i-2), 7.39 g of the silane compound (iii-1), and methyltriethoxysilane 2.2
5 g, 15 g of 4-methyl-2-pentanone, 3.09 g of a 1.75% by weight aqueous oxalic acid solution were added, and while stirring,
After reacting at 80 ° C for 6 hours, the reaction vessel was cooled with ice,
The reaction was stopped. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added and washed with water.After repeatedly washing with water until the reaction solution became neutral,
The organic layer was distilled off under reduced pressure to obtain 8.33 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group), 0.2 ppm (SiCH
₃ ). Mw: 1,800. This polymer is referred to as polysiloxane (a-2).

Synthesis Example 9 3.84 g of the silane compound (i-2), 7.93 g of the silane compound (iii-1) and methyltriethoxysilane were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. 3.2
2 g, 15 g of 4-methyl-2-pentanone, 3.32 g of 1.75 wt% oxalic acid aqueous solution were added, and while stirring,
After reacting at 80 ° C for 6 hours, the reaction vessel was cooled with ice,
The reaction was stopped. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added and washed with water.After repeatedly washing with water until the reaction solution became neutral,
The organic layer was distilled off under reduced pressure to obtain 8.24 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group), 0.2 ppm (SiCH
₃ ). Mw: 2,200. This polymer is referred to as polysiloxane (a-3).

Synthesis Example 10 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 7.00 g of the silane compound (i-2), 14.47 g of the silane compound (iii-1) and 14.47 g of the silane compound (v ) 8.52
g, 30 g of 4-methyl-2-pentanone, 6.05 g of a 1.75% by weight aqueous solution of oxalic acid, and while stirring, add 8 g of oxalic acid.
After reacting at 0 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added and washed with water.After repeatedly washing with water until the reaction solution became neutral,
The organic layer was distilled off under reduced pressure to obtain 18.75 g of a polymer.
The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,400. This polymer is referred to as polysiloxane (a-4).

Synthesis Example 11 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 1.28 g of the silane compound (i-2), 2.20 g of the silane compound (iii-1), and ) 0.52 g,
4.0 g of 4-methyl-2-pentanone, 1.75% by weight
Add 0.74 g of oxalic acid aqueous solution, and stir,
After the reaction at 6 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, transfer the reaction solution to a separating funnel,
The aqueous layer was discarded, and ion-exchanged water was further added thereto for washing with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 2.46 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,400. This polymer is referred to as polysiloxane (a-5).

Synthesis Example 12 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 3.34 g of the silane compound (i-2), 8.62 g of the silane compound (iii-1), and silane compound (v) ) 3.05 g,
15 g of 4-methyl-2-pentanone, 2.88 g of a 1.75% by weight aqueous solution of oxalic acid were added, and the mixture was stirred at 80 ° C.
After 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added thereto, followed by washing with water.After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure. 9.90 g of polymer were obtained. For this polymer, a ¹ H-NMR spectrum (chemical shift “σ
H ") and Mw were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,200. This polymer is referred to as polysiloxane (a-6).

Synthesis Example 13 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 1.5 g of the silane compound (iii-2) and 4-methyl-2-
After adding 1.5 g of pentanone and 0.20 g of a 1.75% by weight aqueous solution of oxalic acid, the mixture was reacted at 80 ° C. for 5 hours while stirring, and then the reaction vessel was cooled with ice to stop the reaction.
After that, transfer the reaction solution to a separating funnel, discard the aqueous layer,
Further, ion-exchanged water was added and the mixture was washed with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 1.01 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.5
ppm (t-butoxycarbonyl group). Mw: 7,500. This polymer is referred to as polysiloxane (a-7).

Synthesis Example 14 1.98 g of a silane compound (iii-1), 1.62 g of 2-t-butoxycarbonylethyltriethoxysilane, and methyl were placed in a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer. 2.41 g of triethoxysilane, 4-methyl-2-
After adding 6.0 g of pentanone and 1.65 g of a 1.75% by weight aqueous solution of oxalic acid, the mixture was reacted at 80 ° C. for 6 hours with stirring, and then the reaction vessel was cooled with ice to stop the reaction.
After that, transfer the reaction solution to a separating funnel, discard the aqueous layer,
Further, ion-exchanged water was added and the mixture was washed with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 3.17 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.5
ppm (t-butoxycarbonyl group), 0.2 ppm
(SiCH ₃ group). Mw: 2,500. This polymer is referred to as polysiloxane (a-8).

Synthesis Example 15 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 0.85 g of the silane compound (i-2), 2.63 g of the silane compound (iii-1), and the silane compound (v ) 0.52 g,
4.0 g of 4-methyl-2-pentanone, 1.75% by weight
Add 0.73 g of oxalic acid aqueous solution, and stir,
After the reaction at 6 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, transfer the reaction solution to a separating funnel,
The aqueous layer was discarded, and ion-exchanged water was added to wash with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 2.63 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,500. This polymer is referred to as polysiloxane (a-9).

Synthesis Example 16 0.85 g of the silane compound (i-2), 2.18 g of the silane compound (iii-1), and the silane compound (vi) were placed in a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer. ) 0.97 g,
4.0 g of 4-methyl-2-pentanone, 1.75% by weight
Add 0.73 g of oxalic acid aqueous solution, and stir,
After the reaction at 6 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, transfer the reaction solution to a separating funnel,
The aqueous layer was discarded, and ion-exchanged water was further added thereto, followed by washing with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 2.27 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,300. This polymer is referred to as polysiloxane (a-10).

Synthesis Example 17 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 0.82 g of the silane compound (i-2), 2.55 g of the silane compound (iii-1) and 2.5 g of the silane compound (vi ) 0.63 g,
4.0 g of 4-methyl-2-pentanone, 1.75% by weight
Add 0.71 g of oxalic acid aqueous solution, and stir
After the reaction at 6 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, transfer the reaction solution to a separating funnel,
The aqueous layer was discarded, and ion-exchanged water was further added thereto, followed by washing with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 2.25 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,500. This polymer is referred to as polysiloxane (a-11).

Synthesis Example 18 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 0.86 g of the silane compound (i-1), 1.58 g of the silane compound (iii-1) and 1.5 g of the silane compound (v ) 1.55 g,
4.0 g of 4-methyl-2-pentanone, 1.75% by weight
Add 0.88 g of oxalic acid aqueous solution, and stir,
After the reaction at 6 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, transfer the reaction solution to a separating funnel,
The aqueous layer was discarded, and ion-exchanged water was further added thereto for washing with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 2.31 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,000. This polymer is referred to as polysiloxane (a-12).

Synthesis Example 19 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 0.82 g of the silane compound (i-1), 2.00 g of the silane compound (iii-1), and silane compound (v ) 1.18 g,
4.0 g of 4-methyl-2-pentanone, 1.75% by weight
Add 0.84 g of oxalic acid aqueous solution, and stir with 80
After the reaction at 6 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, transfer the reaction solution to a separating funnel,
The aqueous layer was discarded, and ion-exchanged water was added to wash with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 2.26 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,100. This polymer is referred to as polysiloxane (a-13).

Synthesis Example 20 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 0.76 g of the silane compound (i-1), 1.86 g of the silane compound (iii-1), and the silane compound (v ) 1.38 g,
4.0 g of 4-methyl-2-pentanone, 1.75% by weight
Add 0.78 g of oxalic acid aqueous solution, and stir,
After the reaction at 6 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, transfer the reaction solution to a separating funnel,
The aqueous layer was discarded, and ion-exchanged water was further added for washing with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 2.22 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,200. This polymer is referred to as polysiloxane (a-14).

Synthesis Example 21 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 0.74 g of the silane compound (i-1), 2.26 g of the silane compound (iii-1), and the silane compound (vi) ) 1.00 g,
4.0 g of 4-methyl-2-pentanone, 1.75% by weight
Add 0.76 g of oxalic acid aqueous solution, and stir,
After the reaction at 6 ° C. for 6 hours, the reaction vessel was cooled with ice to stop the reaction. After that, transfer the reaction solution to a separating funnel,
The aqueous layer was discarded, and ion-exchanged water was further added to wash with water. After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure to obtain 2.38 g of a polymer. The ¹ H-NMR spectrum (chemical shift “σH”) and Mw of this polymer were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups), 1.4
ppm (t-butyl group). Mw: 1,300. This polymer is designated as polysiloxane (a-15).

Comparative Synthesis Example 1 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 20 g of 2-t-butoxycarbonylethyltriethoxysilane, 60 g of 4-methyl-2-pentanone, and 1.
After adding 4.09 g of a 75% by weight aqueous oxalic acid solution and reacting at 80 ° C. for 6 hours with stirring, the reaction vessel was cooled with ice to stop the reaction. After that, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added thereto, followed by washing with water.After repeatedly washing with water until the reaction solution became neutral, the organic layer was distilled off under reduced pressure. A polymer was obtained. The ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this polymer were measured. The results were as follows. σH: 1.5 ppm (t-butoxycarbonyl group). IR: 3400 cm ^-1 (hydroxyl group), 1703 cm ^-1 (carbonyl group), 1130 cm ^-1 (siloxane group), 10
80 cm ^-1 (siloxane group). Mw: 2,700. This polymer is used as a comparative polysiloxane.

[0171]

Example 1 (Evaluation of Radiation Transmittance) Wavelengths of 157 nm and 193 nm were measured for each of the 1,000-mm-thick films formed from the polysiloxanes (a-1) to (a-15) and the comparative polysiloxane. Was measured for radiation transmittance. Table 1 shows the measurement results.

[0172]

[Table 1]

As is evident from Table 1, the polysiloxane (a) of the present invention has a polysiloxane structure as its basic skeleton, so that the radiation transmittance at a wavelength of 193 nm is as high as or higher than that of the comparative polysiloxane. Indicates the value. On the other hand, at a wavelength of 157 nm, the radiation transmittance of the comparative polysiloxane is 30%, whereas all of the polysiloxanes (a-1) to (a-15) are higher than the comparative polysiloxane. Has radiation transmittance. Although the radiation transmittance at a wavelength of 157 nm is generally considered to decrease due to the relative increase in the proportion of the hydrocarbon structure in the polysiloxane, the polysiloxane (a) of the present invention has a relatively low proportion of the hydrocarbon structure. Despite the large number, and even when the partial structure in the polysiloxane changes, the radiation transmittance at a wavelength of 157 nm is at a high level.

Example 2 (Evaluation of resolution by ArF excimer laser) Polysiloxane (a-7) and polysiloxane (a
8), 100 parts by weight of each, 1 part by weight of triphenylsulfonium trifluoromethanesulfonate, 0.02 part by weight of tri-n-octylamine and 90 parts of 2-heptanone
0 parts by weight were uniformly mixed to prepare a composition solution. Next, each composition solution was applied on a silicon wafer by spin coating, and heat-treated on a hot plate kept at 130 ° C. for 90 seconds to form a resist film having a thickness of 100 nm. After that, each resist film was exposed to light by changing the amount of exposure with an ArF excimer laser (wavelength: 193 nm), and was heated on a hot plate kept at 110 ° C. for 90 seconds, and then 2.38% by weight. Development was performed with an aqueous solution of tetramethylammonium hydroxide to form a resist pattern. As a result of observing each of the obtained resist patterns with a scanning electron microscope, the resolution was reduced to 0.30 μm in the case of polysiloxane (a-7) and 0.15 μm in the case of polysiloxane (a-8). Had been resolved until.

Example 3 (Evaluation of dry etching resistance) Polysiloxane (a-3) and polysiloxane (a
4) and polystyrene (Mw = 16,000) for comparison.
0), 100 parts by weight of each, triphenylsulfonium nonafluoro-n-butanesulfonate 1 part by weight, tri-n
0.04 parts by weight of octylamine and 900 parts by weight of 2-heptanone were uniformly mixed to prepare a composition solution. Next, each composition solution was applied on a silicon wafer by spin coating, and heat-treated on a hot plate maintained at 140 ° C. for 90 seconds to obtain a film thickness of 1,000 °.
Was formed. Each of the obtained resist films was subjected to etching tests under various conditions.
Table 2 shows the etching gas (single or mixture), the etching rate, and the relative ratio of the etching rate of polysiloxane (a-3) or polysiloxane (a-4) to polystyrene.

[0176]

[Table 2]

As is clear from Table 2, it was found that the radiation-sensitive resin composition of the present invention exhibited almost the same high dry etching resistance as polystyrene under all the etching conditions studied.

Example 4 (Evaluation of resolution by ArF excimer laser) 100 parts by weight of each of polysiloxanes (E1) to (E11), 1 part by weight of triphenylsulfonium nonafluoro-n-butanesulfonate, tri-n- 0.04 parts by weight of octylamine and 900 parts by weight of 2-heptanone were uniformly mixed to prepare a composition solution. Next, each composition solution was applied on a silicon wafer by spin coating, and heat-treated on a hot plate maintained at 140 ° C. for 90 seconds to form a resist film having a thickness of 1,000 °. Thereafter, each resist film was exposed to light with a different amount of exposure using an ArF excimer laser (wavelength: 193 nm).
After a heat treatment for 2 seconds, development was performed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide,
A resist pattern was formed. As a result of observing each obtained resist pattern with a scanning electron microscope, the resolution was as shown in Table 3.
It is clear that the radiation-sensitive resin composition of the present invention exhibits high resolution performance with respect to an ArF excimer laser.

[0179]

[Table 3]

Example 5 (Evaluation of resolution by F ₂ excimer laser) 100 parts by weight of each of polysiloxanes (a-1) to (a-4) and polysiloxane (a-6), triphenylsulfonium nonafluoro-n 1 part by weight of butanesulfonate, 0.04 part by weight of tri-n-octylamine and 2 parts by weight
-900 parts by weight of heptanone were uniformly mixed to prepare a composition solution. Next, each composition solution was applied on a silicon wafer by spin coating, and heat-treated on a hot plate maintained at 140 ° C. for 90 seconds to obtain a film thickness of 1,
A resist film of 2,000 mm was formed. Thereafter, each of the obtained resist films is exposed to light with a different exposure amount using an F ₂ excimer laser (wavelength: 157 nm), and is heated for 90 seconds on a hot plate maintained at 100 ° C., and then 2.38 The resist pattern was formed by developing with an aqueous solution of tetramethylammonium hydroxide in a weight%. As a result of observing each obtained resist pattern with a scanning electron microscope, the resolution is as shown in Table 4,
It has been clarified that the radiation-sensitive resin composition of the present invention exhibits high resolution performance with respect to an F ₂ excimer laser.

[0181]

[Table 4]

[0182]

The radiation-sensitive resin composition of the present invention effectively responds to radiations such as far ultraviolet rays, electron beams, and X-rays, and particularly has high transparency to radiation having a wavelength of 193 nm or less, especially 157 nm. Moreover, dry etching resistance, sensitivity,
It has excellent basic physical properties as a resist such as resolution and developability. Therefore, the radiation-sensitive resin composition can be extremely suitably used in the field of microfabrication such as LSI (highly integrated circuit) in which miniaturization is expected to progress more and more in the future.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Akihiro Hayashi 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Tsutomu Shimokawa 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR F term (for reference) 2H025 AA01 AA02 AA04 AA09 AB16 AB17 AC04 AC05 AC06 AD03 BE00 BE10 BG00 CB33 CB41 FA17 4J002 CP051 CP071 CP081 CP091 CP101 CP151 CP161 EB116 EB126 EQ016 EU186 EV216 EV246 EV266 EV296 EV306 FD206 GP03

Claims (1)

[Claims] (1) A structural unit (I) or a structural unit (II) represented by the following general formula (1) and the following general formula (2)
An alkali-insoluble or poorly alkali-soluble polysiloxane having at least one structural unit selected from the group consisting of the structural unit (III) and the structural unit (IV), wherein the acid-dissociable group is dissociated. A radiation-sensitive resin composition, comprising: a resin which becomes alkali-soluble in the composition; and (b) a radiation-sensitive acid generator. Embedded image [In the general formula (1), each R independently represents a hydrogen atom or a methyl group, and R ′ represents a hydrogen atom and has 1 to 1 carbon atoms.
20 monovalent hydrocarbon group, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or primary, shows a secondary or tertiary amino group, X ¹ is hydrogen is dissociated by acid Represents a monovalent organic group generating an atom, and m is an integer of 0 to 3. However, each silicon atom in the general formula (1) is bonded to the 2-position or 3-position of the bicyclo [2.2.1] heptane ring at the highest position. [Chemical formula 2] [In the general formula (2), each R independently represents a hydrogen atom or a methyl group, R ′ represents a hydrogen atom, and has 1 to 1 carbon atoms.
20 represents a monovalent hydrocarbon group, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom or a primary, secondary or tertiary amino group, and R ″ represents a hydrogen atom, a methyl group Or X represents a trifluoromethyl group, X ² represents a hydrogen atom or a monovalent organic group which generates a hydrogen atom by dissociation with an acid, and n is an integer of 0 to 3. However, each silicon atom in the general formula (2) is a bicyclo [2.2.1] at the top.
It is bonded to the 2- or 3-position of the heptane ring. ]