JPH11242337A - Resist composition and pattern forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provid a high sensitivity and high resolution practical resist compsn. using a polymer having high transmittance to far UV of <=220 nm, in particular ArF excimer laser light and excellent in etching resistance and to provide a pattern forming method using the resist compsn. SOLUTION: This resist compsn. contains a polymer contg. monomeric units represented by formula as the constituent units, a photosensitive compsn. that generates an acid when exposed and a solvent capable of dissolving them. In the formula, X is a polycyclic hydrocarbon group that may have a substituent, Z is a spacer or a bonding radical and R is a substd. alkyl or alkenyl group having one or two protected hydroxyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resist composition used in the manufacture of semiconductor devices and the like, and a pattern forming method using the same.

[0002]

2. Description of the Related Art Conventionally, novolak resins, phenolic resins, polymers containing acrylic acid or methacrylic acid as components, and the like are known as alkali-soluble resins. And many polymers have been put to practical use. Particularly in the field of lithography technology, g-line (436 nm wavelength), i-line (365 nm wavelength) ultraviolet light, and recently an excimer laser (KrF excimer laser;
248 nm, ArF excimer laser; wavelength 193 nm) has been used, and as a base polymer of a resist material corresponding to these light sources, a novolak resin is mainly used for a resist for g-line and i-line, and a phenol resin is mainly used for a KrF resist. In any of them, a phenolic hydroxyl group (pKa
About 12).

On the other hand, as a base polymer used in an ArF resist material currently under development, an acrylic acid derivative or methacrylic acid derivative resin is mainly used (for example,
JP-A-7-199467, JP-A-8-82925, JP-A-7
-234511). The reason is that conventionally used resins containing aromatic rings have low transparency in the far ultraviolet region,
This is because at 193 nm, which is the wavelength of the ArF excimer laser beam, it becomes completely opaque. However, the resist material using the acrylic acid or methacrylic acid resin as a base has a high acidity (pKa of about 5) due to the carboxylic acid group being a soluble group, and is not compatible with a conventional polymer having a phenolic hydroxyl group as a soluble group. Since the dissolution rate during alkali development is extremely high, the existing alkaline developer, 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, when used without dilution, may cause film peeling during fine pattern formation, or Since it dissolves to the unexposed portion, there is a disadvantage that a good pattern cannot be obtained. In addition, the above-mentioned 2.38% TMAH is the mainstream of the alkali developing solution currently used in the actual production line of semiconductor devices, and i-line resist and KrF resist or KrF resist and Ar
In a production line where resist materials of each generation are mixed, such as F resist, it is very difficult to dilute and use the developing solution.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and has high transparency to far ultraviolet light having a wavelength of 220 nm or less, particularly ArF excimer laser light.
An object of the present invention is to provide a novel resist composition capable of obtaining a resist film having excellent etching resistance and the like and a pattern forming method using the same.

[0005]

The present invention provides a compound represented by the general formula [1]
a]

[0006]

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(Wherein X represents a polycyclic hydrocarbon group which may have a substituent, Z represents a spacer or a bond, and R represents a substituted alkyl having one or two protected hydroxyl groups. A resist composition comprising a polymer comprising a monomer unit represented by the following formula: or a alkenyl group as a constituent unit, a photosensitive compound capable of generating an acid upon exposure, and a solvent capable of dissolving the compound. Invention.

[0008] The present invention also relates to (1) a step of applying the resist composition described above on a substrate, and (2) a step of exposing the resist composition to light of 220 nm or less through a mask after a heat treatment;
(3) a step of performing a heat treatment as necessary and then developing with a developer.

That is, the present inventors have conducted intensive studies to achieve the above object, and as a result, a resist film having high light transmittance in a wavelength region of 220 nm or less and having high etching resistance by using this as a resist material. Is obtained, a novel polymer comprising a monomer unit represented by the above general formula [1a] as a constitutional unit, and a photosensitive compound capable of generating an acid upon exposure to the polymer and a solvent capable of dissolving the same. The present invention has reached a chemically amplified resist material comprising the same, and has completed the present invention.

In the general formula [1a], represented by X
As the polycyclic hydrocarbon group which may have a substituent,
Examples include groups represented by the following general formulas [2a] to [4a].

[0011]

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(Wherein, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group, a cyano group, an alkyloxycarbonyl group or a carbamoyl group, and represents 0 or 1.)

[0013]

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(Wherein, R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, an alkyl group, a cyano group, an alkyloxycarbonyl group or a carbamoyl group.)

[0015]

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In the above formula, the alkyl group represented by R ^{16 to} R ¹⁹ may be linear, branched or cyclic, and includes, for example, an alkyl group having 1 to 20 carbon atoms. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group,
Neopentyl group, tert-pentyl group, 3,3-dimethylbutyl group, 1,1-dimethylbutyl group, 1-methylpentyl group, n
-Hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Examples include a hexadecyl group, an octadecyl group, a 2-ethylhexyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. The alkyloxycarbonyl group may be linear, branched or cyclic. Examples of the linear or branched alkyloxycarbonyl group include, for example, an alkyloxycarbonyl group having 2 to 19 carbon atoms, specifically, a methyloxycarbonyl group,
Ethyloxycarbonyl, propyloxycarbonyl, butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, tert-butyloxycarbonyl Group, 2-ethylhexyloxycarbonyl group and the like. Further, as the cyclic alkyloxycarbonyl group, the ring may be monocyclic or polycyclic, and examples thereof include an alicyclic alkyloxycarbonyl group having 6 to 14 carbon atoms. Specific examples include a cyclohexyloxycarbonyl group and tricyclodecacarbonyl. Nyloxycarbonyl group, adamantyloxycarbonyl group, norbornyloxycarbonyl group, bicyclo [3.2.1] octenyloxycarbonyl group, bicyclo [2.2.2] octyloxycarbonyloxycarbonyl group, menthyloxycarbonyl group, isobornyl An oxycarbonyl group;

In the general formula [1a],
The substituted alkyl group or alkenyl group having one or two protected hydroxyl groups may be linear, branched or cyclic, for example, a group represented by the following general formula [5] or [6], etc. Is mentioned.

[0018]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group or an aliphatic polycyclic hydrocarbon group, and R ¹ and R ² are bonded to each other. Each may form an aliphatic ring together with an adjacent carbon atom, and R ³ represents an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkyloxycarbonyl group or an alkylsilyl group.)

[0020]

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(Wherein R ⁴ represents an alkyl group; R ¹ and R
² and R ³ are the same as above. R ³ and R ⁴ may combine to form a methylene chain which may have a substituent or an aliphatic ring which may have a substituent. )

In the general formulas [5] and [6], the alkyl group represented by R ¹ and R ² may be linear, branched or cyclic, and has, for example, 1 to 12 carbon atoms. Is an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, se
c-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 3,3-dimethylbutyl group,
1,1-dimethylbutyl group, 1-methylpentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, Examples include a cyclohexyl group and a 2-cyclohexylethyl group. Further, as the substituted alkyl group, at least one of the hydrogen atoms of the above alkyl group is, for example, a cyano group, a hydroxyl group,
For example, halogen atoms such as fluorine, chlorine, bromine and iodine, for example, those having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentyloxy and hexyloxy groups. An alkyl group having a substituent having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, substituted with a functional group such as a lower alkoxy group,
Specifically, cyanoalkyl groups such as a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, a cyanopentyl group, a cyanohexyl group, and a cyanoheptyl group;
For example, a hydroxyalkyl group such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group,
For example, chloromethyl, bromomethyl, trifluoromethyl, 2-chloroethyl, 3-chloropropyl,
Haloalkyl groups such as bromopropyl group, 3,3,3-trifluoropropyl group and perfluorooctyl group, for example, methoxymethyl group, methoxyethyl group, ethoxymethyl group,
Ethoxyethyl group, propoxymethyl group, 2-propoxymethyl group, propoxyethyl group, butoxymethyl group, te
and alkoxyalkyl groups such as rt-butoxymethyl group. Examples of the aliphatic polycyclic hydrocarbon group include an aliphatic polycyclic hydrocarbon group having 3 to 30, preferably 5 to 12 carbon atoms, and specifically, tricyclo [5.2.1.0 ^2.6 ]
Decanyl group, dicyclopentenyl group, adamantyl group,
Examples include a norbornyl group, an isobornyl group, a 2-methyl-2-adamantyl group, and a menthyl group. In general formulas [5] and [6], when R ¹ and R ² are bonded to each other to form an aliphatic ring together with an adjacent carbon atom, An aliphatic ring having 3 to 10 carbon atoms may be mentioned, and the ring may be monocyclic or polycyclic.
In the general formula [5], for example, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, a cyclodecene ring,
A 2-norbornene ring and the like, and in the general formula [6], for example, a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, a cyclodecane ring,
And a norbornane ring.

In the general formulas [5] and [6], the alkyl group represented by R ³ may be linear or branched and has, for example, 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. And specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group , Neopentyl group, tert-pentyl group, 3,3-dimethylbutyl group, 1,1-dimethylbutyl group,
1-methylpentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group,
Examples include an isooctyl group and a 2-ethylhexyl group.
The alkenyl group may be linear or branched, and includes, for example, an alkenyl group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specifically, an ethenyl group, a propenyl group, an isopropenyl group, Butenyl group, isobutenyl group,
Pentenyl, isopentenyl, hexenyl, isohexenyl, heptenyl, octenyl and the like. The hydroxyalkyl group may be linear or branched, and includes, for example, a hydroxyalkyl group having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, specifically, a hydroxyethyl group, a hydroxypropyl group, Examples include a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, and a hydroxyoctyl group. As the alkyloxycarbonyl group,
It may be linear, branched or cyclic, and includes, for example, an alkyloxycarbonyl group having 3 to 19 carbon atoms,
Specifically, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, tert -Butyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, cyclohexyloxycarbonyl group and the like. The alkyl group of the alkylsilyl group may be linear or branched and includes a lower alkyl group, for example, an alkyl group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, and an n-propyl group. ,
Isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 3,3-dimethylbutyl, 1,1-dimethyl Butyl group, 1-methylpentyl group, n-hexyl group, isohexyl group, and the like. Specific examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group,
Triisopropylsilyl group, tri-n-butylsilyl group,
Tripentylsilyl group, tri-n-hexylsilyl group, ter
Preferred examples include a trialkylsilyl group such as a t-butyldimethylsilyl group.

In the general formula [6], the alkyl group represented by R ⁴ may be linear or branched, for example, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl group, 3,3
-Dimethylbutyl group, 1,1-dimethylbutyl group, 1-methylpentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group and the like. Can be

In the case where R ³ and R ⁴ are bonded to form a methylene chain, the methylene chain may be, for example, a methylene chain having 1 to 3 carbon atoms, specifically, methylene, ethylene, trimethylene or the like. Further, when R ³ and R ⁴ are bonded to each other to form an aliphatic ring, the ring may be a monocyclic ring or a polycyclic ring, for example, an aliphatic ring having 3 to 10 carbon atoms. Specific examples include a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, a norbornane ring and the like. The methylene chain and the aliphatic ring may have, as a substituent, at least one alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Good.

Among the substituted alkyl groups or substituted alkenyl groups having one or two protected hydroxyl groups represented by R in the general formula [1], the following general formulas [7],
The group represented by [8] or [8 '] is particularly preferable.

[0027]

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[0028]

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[0029]

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(Wherein R ^{1 ′} represents a hydrogen atom, R ^{2 ′} and R ^{3 ′} represent a lower alkyl group having 1 to 4 carbon atoms, and R ^{1 ′} and R ^{2 ′} are bonded to each other. And each may form an aliphatic ring having 5 to 6 carbon atoms, that is, a cyclopentene ring or a cyclohexene ring, together with adjacent carbon atoms,
Y and Y ′ represent a group represented by the following formula [9] or the following general formula [10].

[0031]

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[0032]

Embedded image In the formula, R ^{4 ′} and R ^{5 ′} represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. ｝)

In addition, examples of the spacer represented by Z in the general formula [1] include a group represented by the following general formula [11].

[0034]

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(Wherein A ₂ represents a divalent hydrocarbon group which may have an oxygen atom, A ₁ and A ₃ each independently represent a lower alkylene group, m, p, q and r independently represents 0 or 1, provided that when m is 1, q represents 1, and at least one of m, p, q and r is 1.

In the general formula [11], examples of the divalent hydrocarbon group optionally having an oxygen atom represented by A ₂ include:
Examples include an alkylene group. The alkylene group may be linear, branched or cyclic, and includes, for example, an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and specifically, for example, a methylene group,
Ethylene group, propylene group, butylene group, 2-methylpropylene group, pentylene group, 2,2-dimethylpropylene group,
2-ethylpropylene group, hexylene group, heptylene group,
Octylene group, 2-ethylhexylene group, nonylene group, decylene group, cyclopropylene group, cyclopentylene group,
Examples include a cyclohexylene group, an adamantanediyl group, a tricyclo [5.2.1.0 ^2.6 ] decanediyl group, a norbornanediyl group, a methylnorbornanediyl group, an isobornanediyl group, and a decalindiyl group. In the case of having an oxygen atom, those having 1 to 3 oxygen atoms in the main chain and / or side chain of the divalent hydrocarbon group are mentioned. Is a methoxyethylethylene group, an ethoxyethylethylene group, a bornyloxyethylethylene group, a norbornyloxyethylethylene group,
Menthyl oxyethyl ethylene group, adamantyloxyethyl ethylene group, methoxyethoxyethyl ethylene group, ethoxyethoxyethyl ethylene group, isobornyl oxy ethoxyethyl ethylene group, menthyloxycarbonyl ethoxyethyl ethylene group, -O-CH ₂ - group, -O- CH ₂ CH ₂ - group, -CH ₂ -O-
CH ₂ - _{group, -CH 2 CH 2 -O-CH} 2 - _{group, -CH 2 CH 2 -O-CH} 2 CH 2 - group, -CH
₂ CH ₂ —O—CH ₂ CH ₂ —O—CH ₂ CH ₂ — groups and the like. A ₁ and A
_The lower alkylene group represented by ₃ may be linear or branched and includes, for example, an alkylene group having 1 to 6 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group, a butylene group, and 2 -Methylpropylene group, pentylene group, 2,2-dimethylpropylene group, 2-ethylpropylene group, hexylene group and the like.

Among these spacers represented by Z, those represented by the following general formula [12] are particularly preferred.

[0038]

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(Wherein m ′ and p ′ are each independently 0
Or represents 1. However, at least one of m ′ and p ′ is 1. )

The monomer unit represented by the above general formula [1a] according to the present invention has the general formula [1]

[0041]

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(Wherein X ′ has a polymerizable double bond,
Represents a polycyclic hydrocarbon group which may have a substituent;
And R are the same as above. )).

In the general formula [1], represented by X ′
Examples of the optionally substituted polycyclic hydrocarbon group having a polymerizable double bond include the following general formulas [2] to
And the aliphatic group represented by [4].

[0044]

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(In the formula, R ¹⁶ , R ¹⁷ and k are the same as described above.)

[0046]

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(In the formula, R ¹⁸ and R ¹⁹ are the same as described above.)

[0048]

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In the general formula [1], represented by X ′
Specific examples of the polycyclic hydrocarbon group having a polymerizable double bond and optionally having a substituent include, for example, bicyclo [2.
2.1] Hept-2-en-5-yl group, 1-methylbicyclo [2.2.
1] Hept-2-en-5-yl group, 5-methylbicyclo [2.2.1]
Hept-2-en-5-yl group, 7-methylbicyclo [2.2.1] hept-2-en-5-yl group, 1-ethylbicyclo [2.2.1] hept-2-en-5-yl group , 5-Ethylbicyclo [2.2.1] hept-
2-en-5-yl group, 5-isopropylbicyclo [2.2.1] hept-2-en-5-yl group, 5-pentylbicyclo [2.2.1] hept-2-en-5-yl group, 5 -Heptylbicyclo [2.2.1] hept-2-en-5-yl group, 5- (2-ethylhexyl) bicyclo
[2.2.1] Hept-2-en-6-yl group, 7-octylbicyclo
[2.2.1] Hept-2-en-5-yl group, 1-nonylbicyclo [2.
2.1] Hept-2-en-5-yl group, 5-nonylbicyclo [2.2.
1] Hept-2-en-5-yl group, 5-dodecylbicyclo [2.2.
1] Hept-2-en-5-yl group, 5-pentadecylbicyclo
[2.2.1] Hept-2-en-5-yl group, 5,5-dimethylbicyclo [2.2.1] hept-2-en-6-yl group, 1,4-diisopropylbicyclo [2.2.1] hept 2-en-5-yl group, 5,5-diisopropylbicyclo [2.2.1] hept-2-en-6-yl group,
5,5-dibutylbicyclo [2.2.1] hept-2-en-6-yl group, 5,5-dihexylbicyclo [2.2.1] hept-2-ene-6-
Yl group, 5-methyl-5-ethylbicyclo [2.2.1] hept-2-
Ene-6-yl group, 5,5-didecylbicyclo [2.2.1] hept-2
-Ene-6-yl group, 5,6-dimethylbicyclo [2.2.1] hept-
2-en-5-yl group, 5-methyl-6-ethylbicyclo [2.2.1]
Hept-2-en-5-yl group, 5,6-dipropylbicyclo [2.
2.1] Hept-2-en-5-yl group, 5,6-diisopropylbicyclo [2.2.1] hept-2-en-5-yl group, 5,6-dipentylbicyclo [2.2.1] hept-2- Ene-5-yl group, 5,6-di (2-ethylhexyl) bicyclo [2.2.1] hept-2-en-5-yl group, 5,6-didodecylbicyclo [2.2.1] hept-2- En-5-
Yl group, 5,5,6-trimethylbicyclo [2.2.1] hept-2-en-6-yl group, 5-cyclobutylbicyclo [2.2.1] hept-2
-Ene-5-yl group, 5,6-dicyclopentylbicyclo [2.2.
1] Hept-2-en-5-yl group, 5-methylcyclopentylbicyclo [2.2.1] hept-2-en-5-yl group, 5-isopropylcyclopentylbicyclo [2.2.1] hept-2-ene- 5-yl group, 5-cyclohexylbicyclo [2.2.1] hept-2-ene
Bicyclic hydrocarbon group such as -5-yl group, for example, tricyclo [5.
2.1.0 ^2.6 ] dec-8-en-3-yl group, tricyclo [5.2.1.0
^2.6 ] Dec-8-en-4-yl group, 3-methyltricyclo [5.2.
1.0 ^2.6 ] dec-8-en-4-yl group, 3-ethyltricyclo [5.
2.1.0 ^2.6 ] Deca-8-en-4-yl group, 3,5-dimethyltricyclo [5.2.1.0 ^2.6 ] Tricyclic hydrocarbon group such as deca-8-en-4-yl group, for example, tetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] Dodeca
And a 4-cyclic hydrocarbon group such as a -3-en-8-yl group.

Specific examples of the monomer represented by the above general formula [1] according to the present invention include, for example,

[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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And the like.

The production of the monomer represented by the above general formula [1] according to the present invention may be carried out, for example, as follows. That is, for example, the general formula [13]

[0061]

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(Wherein R ¹ , R ² , X ′ and Z are the same as described above) and an orthocarboxylic acid ester, if necessary, in a suitable solvent in the presence of an acid catalyst. Can be obtained.

Examples of the orthocarboxylic acid esters include methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate and the like.

The amount of the orthocarboxylic acid ester to be used is not particularly limited, but is appropriately selected usually from the range of 1 to 30 times, preferably from 1 to 10 times the mol of the compound represented by the general formula [13]. .

Examples of the acid catalyst include organic acids (or salts thereof) such as camphorsulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid, oxalic acid, and pyridinium chloride; and inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. Acids include, for example, Lewis acids such as aluminum chloride and boron trifluoride diethyl ether complex (BF ₃ .Et ₂₀ ).

The amount of the acid catalyst used is not particularly limited, but is appropriately selected usually from 0.1 to 20 mol%, preferably from 1 to 10 mol%, based on the compound represented by the general formula [13].

The reaction solvent used if necessary includes, for example, hydrocarbons such as toluene, xylene, benzene, cyclohexane, n-hexane and n-octane, for example, methylene chloride, dichloroethane, trichloroethylene, carbon tetrachloride, chloroform and the like. Halogenated hydrocarbons such as methyl acetate, ethyl acetate, n-butyl acetate,
Esters such as methyl propionate, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, for example, dimethyl ether, diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxane, etc. Ethers,
N-methylpyrrolidone, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide and the like. These may be used alone or in combination of two or more.

The reaction temperature is not particularly limited, but is usually 0 to
It is appropriately selected from the range of 150 ° C, preferably 20 to 80 ° C.

The reaction time is determined by the general formula [1]
Although it varies depending on the reaction conditions such as the type and concentration of the compound shown in [3], it is usually appropriately selected from the range of 0.5 to 10 hours.

The monomer represented by the above general formula [1] according to the present invention can also be obtained by the following production method. That is, for example, if the compound represented by the general formula [13] and a diol are required, they can be obtained by reacting in a suitable solvent in the presence of an acid catalyst.

Examples of the diols include ethylene glycol, propylene glycol, 2,2-dimethylpropanediol, 1,3-butanediol, 1,4-butanediol,
Diethylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, triethylene glycol, 2-butyl-2-ethyl-1,3-propanediol , 1,2-
Cyclohexanediol, 1,3-cyclohexanediol and the like can be mentioned.

The amount of the diols to be used is not particularly limited, but is usually from 1 to 1 relative to the compound represented by the formula [13].
It is appropriately selected from the range of 20-fold molar, preferably 3 to 10-fold molar.

Examples of the acid catalyst include organic acids (or salts thereof) such as camphorsulfonic acid, p-toluenesulfonic acid and pyridinium p-toluenesulfonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid. Can be

The amount of the acid catalyst used is not particularly limited, but is appropriately selected usually in the range of 0.1 to 20 mol%, preferably 1 to 10 mol%, based on the compound represented by the general formula [13].

The reaction solvent used if necessary includes, for example, hydrocarbons such as toluene, xylene, benzene, cyclohexane, n-hexane and n-octane, for example, methylene chloride, dichloroethane, trichloroethylene, carbon tetrachloride, chloroform and the like. Halogenated hydrocarbons such as methyl acetate, ethyl acetate, n-butyl acetate,
Esters such as methyl propionate, for example, dimethyl ether, diethyl ether, diisopropyl ether,
Ethers such as dimethoxyethane, tetrahydrofuran and dioxane, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like. These may be used alone or in combination of two or more. Incidentally, these reaction solvents are preferably solvents capable of forming an azeotropic mixture with water and removing water from the reaction system.

The reaction temperature is not particularly limited, but is usually 0 to
The temperature is appropriately selected from the range of 150 ° C, preferably 20 to 130 ° C.

The reaction time is determined by the general formula [1]
The reaction time varies depending on the reaction conditions such as the type and concentration of the compound shown in [3], but it is usually appropriately selected from the range of 0.5 to 48 hours.

The post-treatment after the reaction may be carried out according to the post-treatment method usually performed in any of the above-mentioned production methods, and the obtained monomer represented by the above general formula [1] may be purified without particular purification. The crude product may be subjected to a polymerization reaction (that is, an unreacted compound represented by the above general formula [13] may be present), and distillation or column chromatography. After purifying by any purification method such as the above, it may be subjected to the next reaction.

As the compound represented by the above general formula [13], a commercially available product or a compound appropriately produced by a conventional method may be used.

When the monomer according to the present invention has an alkylsilyl group, the monomer according to the present invention having no alkylsilyl group obtained by any of the above-mentioned production methods and an alkylsilyl halide may be used. Can be obtained by reacting in a suitable solvent, if necessary, in the presence of a basic catalyst.

Examples of the alkylsilyl halide include chlorotrimethylsilane, chlorotriethylsilane, chlorodimethylethylsilane, chlorotripropylsilane, chlorotriisopropylsilane, chlorotributylsilane, chlorotrihexylsilane, butylchlorodimethylsilane and the like. .

Although the amount of the alkylsilyl halide to be used is not particularly limited, it is usually 1 to 20 moles, preferably 1 to 5 moles, per mole of the compound represented by the general formula [1] having no alkylsilyl group. Is selected as appropriate.

Examples of the basic catalyst include triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine, 1,5-diazabicyclo [4.3.0] non-5-ene, Organic amines such as 8-diazabicyclo [5.4.0] undec-7-ene, tri-n-butylamine and N-methylmorpholine, for example, metal hydrides such as sodium hydride, for example, n-butyllithium, tert-butyl And basic organic alkali metal compounds such as lithium.

The amount of the basic catalyst used is not particularly limited, but is usually 0.1 to 20 times, preferably 1 to 20 times, the molar amount of the compound represented by the general formula [1] having no alkylsilyl group.
It is appropriately selected from a range of 5 moles.

The reaction solvent used if necessary includes, for example, hydrocarbons such as toluene, xylene, benzene, cyclohexane, n-hexane and n-octane, for example, methylene chloride, dichloroethane, trichloroethylene, carbon tetrachloride, chloroform and the like. Halogenated hydrocarbons such as methyl acetate, ethyl acetate, n-butyl acetate,
Esters such as methyl propionate, for example, dimethyl ether, diethyl ether, diisopropyl ether,
Ethers such as dimethoxyethane, tetrahydrofuran and dioxane, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like. These may be used alone or in combination of two or more.

The reaction temperature is not particularly limited, but is usually 0 to
It is appropriately selected from the range of 150 ° C, preferably 20 to 80 ° C.

The reaction time varies depending on the reaction conditions such as the type and concentration of the compound represented by the general formula [1] having no alkylsilyl group to be reacted, but it is usually 0.5 to 48.
It is appropriately selected from a range of time.

The post-treatment after the reaction may be carried out in accordance with a usual post-treatment method. The obtained monomer represented by the above general formula [1] having an alkylsilyl group may be crudely purified without particular purification. The polymer may be subjected to a polymerization reaction as it is (that is, a state in which an unreacted compound represented by the general formula [13] or a monomer according to the present invention having no alkylsilyl group is present). After purification by any purification method such as distillation or column chromatography, and then subjecting it to the next reaction.

The polymer according to the present invention comprising the monomer unit represented by the general formula [1a] according to the present invention as a constituent unit includes one or more monomer units according to the present invention, or a monomer unit according to the present invention. Examples of the polymer include, as constituent units, one or more monomer units other than the monomer units according to the present invention (hereinafter, referred to as “other monomer units”).

Examples of the other monomer units include monomer units represented by the following general formulas [14a] and [15a].

[0091]

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[0092] In the formula, R ⁹ represents a hydrogen atom, a lower alkyl group or a halogen atom, R ¹⁰ represents a hydrogen atom, a lower alkyl group, a halogen atom, a carboxyl group, an alkyloxycarbonyl group or a formyl group, R ¹¹ Is a hydrogen atom,
Represents a lower alkyl group, a carboxyl group, an alkyloxycarbonyl group or a halogen atom, R ¹² represents an alkylene group or a bond which may have a double bond, R ¹³ represents a hydrogen atom, an alkyl group, a haloalkyl group, It represents an aliphatic heterocyclic group, a halogen atom, an alkyloxycarbonyl group, a hydroxyalkyloxycarbonyl group, an acyloxy group, a cyano group, a carboxyl group, a formyl group, a carbamoyl group or a hydroxyl group. In addition, the -CO-Q-CO- group ｛Q bonded by R ¹⁰ and R ¹³ is O or NR ¹⁴
(R ¹⁴ represents a hydrogen atom or a lower alkyl group.)｝ May be formed. ]

[0093]

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[Wherein, G ′ represents an aliphatic cyclic hydrocarbon group, and R ²⁰ and R ²¹ each independently represent a hydrogen atom, an alkyl group, a hydrophilic group or an alkyloxycarbonyl group. Further, R ²⁰ and R ²¹ may combine to form a dicarboximide (—CO—NH—CO—) group. ]

Among the monomer units represented by the general formula [14a], those represented by the following general formula [16] are particularly preferable.

[0096]

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(Wherein R ¹⁰ and R ¹³ are bonded together to form —CO—
Q—CO— group ｛Q is O or N—R ¹⁴ [R ¹⁴ represents a hydrogen atom or a lower alkyl group. ] May be formed. )

Of the monomer units represented by the general formula [15a], those represented by the following general formulas [17] to [19] are particularly preferable.

[0099]

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[0100]

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[0101]

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(In the formula, R ²⁰ , R ²¹ and k are the same as described above.)

Further, the polymer according to the present invention has the following general formula [1] derived from the compound represented by the general formula [13].
3a]

[0104]

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(Wherein R ¹ , R ² , X and Z are the same as described above) may be contained as a constitutional unit.

In the general formula [14a], R ⁹ , R ¹⁰ ,
Examples of the halogen atom represented by R ¹¹ and R ¹³ include fluorine, chlorine, bromine, iodine and the like. The lower alkyl group represented by R ⁹ , R ¹⁰ and R ¹¹ may be linear or branched, and includes, for example, an alkyl group having 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, ter
t-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 3,3-dimethylbutyl, 1,1-dimethylbutyl, 1-methylpentyl, n-butyl Examples include a hexyl group and an isohexyl group. The alkyloxycarbonyl group represented by R ¹⁰ , R ¹¹ and R ¹³ may be linear, branched or cyclic, and may have a double bond. Examples of the linear or branched alkyloxycarbonyl group include an alkyloxycarbonyl group having 2 to 19 carbon atoms, specifically, a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, and butyl. Oxycarbonyl group, pentyloxycarbonyl group,
Hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethenyloxycarbonyl group, propenyloxycarbonyl group, butenyloxycarbonyl group, tert-butyloxycarbonyl group, 2 -Ethylhexyloxycarbonyl group and the like. As the cyclic alkyloxycarbonyl group, the ring may be monocyclic or polycyclic.
To 14 alicyclic alkyloxycarbonyl groups,
Specifically, a cyclohexyloxycarbonyl group, a tricyclodecanyloxycarbonyl group, an adamantyloxycarbonyl group, a norbornyloxycarbonyl group, a bicyclo [3.2.1] octenyloxycarbonyl group, a bicyclo
[2.2.2] Examples include an octyloxycarbonyl group, a menthyloxycarbonyl group, and an isobornyloxycarbonyl group. The alkyl group represented by R ¹³ may be linear, branched or cyclic, and has, for example, 1 carbon atom.
To 20 alkyl groups, specifically, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-
Pentyl group, isopentyl group, neopentyl group, tert-
Pentyl, 3,3-dimethylbutyl, 1,1-dimethylbutyl, 1-methylpentyl, n-hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl , Hexadecyl group, octadecyl group, 2-ethylhexyl group, cyclopropyl group,
Examples include a cyclopentyl group and a cyclohexyl group.
Examples of the haloalkyl group include a haloalkyl group having 1 to 20 carbon atoms in which the above alkyl group is optionally halogenated (eg, fluorinated, chlorinated, brominated, iodized, etc.), and specifically, chloromethyl Group, bromomethyl group, trifluoromethyl group, 2-chloroethyl group, 3-chloropropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl group, 2-perfluorooctylethyl group, perfluorooctyl group , 1-chlorodecyl group, 1-chlorooctadecyl group and the like. As the aliphatic heterocyclic group, for example, a 5-membered or 6-membered aliphatic heterocyclic group is preferable, and contains 1 to 3 hetero atoms such as a nitrogen atom, an oxygen atom, and a sulfur atom as isomer atoms. And specific examples thereof include, for example, a pyrrolidyl-2-one group, a piperidino group, a morpholino group and the like. As the acyloxy group, for example, an acyloxy group having 2 to 18 carbon atoms derived from a carboxylic acid is preferable. Specifically, an acetyloxy group, a propionyloxy group, a butyryloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoyloxy group Octanoyloxy group, lauroyloxy group, stearoyloxy group, benzoyloxy group and the like. Examples of the hydroxyalkyloxycarbonyl group include a hydroxyalkyloxycarbonyl group having 2 to 19 carbon atoms in which a hydrogen atom of the alkyloxycarbonyl group is substituted with a hydroxyl group as described above, specifically, a hydroxymethyloxycarbonyl group, Hydroxyethyloxycarbonyl, hydroxypropyloxycarbonyl, hydroxybutyloxycarbonyl, hydroxypentyloxycarbonyl, hydroxyhexyloxycarbonyl, hydroxyheptyloxycarbonyl, hydroxyoctyloxycarbonyl, hydroxydodecyloxycarbonyl, hydroxyoctadecyl An oxycarbonyl group;
The alkylene group which may have a double bond represented by R ¹² may be linear or branched and includes, for example, an alkylene group having 1 to 10 carbon atoms. When one or more double bonds are present at the terminal of the alkylene group or at any position in the chain, preferably one or more double bonds are present.
Those having from 5 to 5, more preferably from 1 to 3, specifically, methylene, ethylene, propylene, butylene, 2-methylpropylene, pentylene, 2,2-dimethyl Propylene, 2-ethylpropylene, hexylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, ethenylene, propenylene, butenylene, pentenylene, hexenylene, butadienylene, etc. No.

In the general formula [14a], in a —CO—Q—CO— group formed by combining R ¹⁰ and R ¹³ ,
In Q, the lower alkyl group represented by R ¹⁴ includes:
It may be linear, branched or cyclic, and includes, for example, an alkyl group having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 3,3-dimethylbutyl group, 1,1-dimethylbutyl group, 1-methylpentyl group, Examples include an n-hexyl group, an isohexyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The other monomer units represented by the general formula [14a] are represented by the general formula [14]

[0109]

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(Wherein, R ^{9 to} R ¹³ are the same as described above). Specific examples of the monomer include alkenyl esters having 3 to 20 carbon atoms such as vinyl formate, vinyl acetate, vinyl propionate, and isopropenyl acetate, for example, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, and tetrachloroethylene. Halogen-containing ethylenically unsaturated compounds having 2 to 20 carbon atoms such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc.
Ethylenically unsaturated carboxylic acids having 3 to 20 carbon atoms such as citraconic acid, mesaconic acid, vinyl acetic acid and allyl acetic acid (these acids are in the form of salts such as alkali metal salts such as sodium and potassium and ammonium salts). For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate,
Stearyl methacrylate, vinyl methacrylate, allyl methacrylate, adamantyl methacrylate, tricyclodecanyl methacrylate, menthyl methacrylate, norbornyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, vinyl acrylate, adamantyl acrylate, tricyclodecanyl acrylate, menthyl acrylate, norbornyl acrylate, isobornyl acrylate, dimethyl itaconate, diethyl itaconate,
Dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, methyl crotonate, ethyl crotonate, vinyl crotonate, dimethyl citraconic acid, diethyl citraconic acid, dimethyl mesaconate, diethyl mesaconate, methyl 3-butenoate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate,
C4 to C20 ethylenically unsaturated carboxylic acid esters such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate and 2-hydroxypropyl acrylate, for example, acrylonitrile, methacrylonitrile C3-20 cyano-containing unsaturated compounds such as allyl cyanide, etc., e.g. C3-20 ethylenically unsaturated amide compounds such as acrylamide, methacrylamide, maleimide, etc., e.g. acrolein, crotonaldehyde, etc. C3 to C20 ethylenically unsaturated aldehydes such as vinylsulfonic acid and the like, and C2 to C20 ethylenically unsaturated sulfonic acids (for example, salts of these salts such as alkali metal salts such as sodium and potassium). May be in the form of)), for example, vinylamine, allyl C2-C20 ethylenically unsaturated aliphatic amines such as amines such as N-vinylpyrrolidone and vinylpiperidine; C5-C20 ethylenically unsaturated aliphatic heterocyclic amines such as allyl alcohol, Examples thereof include ethylenically unsaturated alcohols having 3 to 20 carbon atoms such as tyl alcohol, and diene compounds having 4 to 20 carbon atoms such as butadiene and isoprene.

The monomer unit represented by the general formula [15a] is represented by the general formula [15]

[0112]

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(Wherein G is a fat having a polymerizable double bond)
Represents an aromatic hydrocarbon group;²⁰And R ^{twenty one}Is the same as above
Same. )).

In the general formula [15a], the aliphatic cyclic hydrocarbon group represented by G ′ is the aliphatic ring having a polymerizable double bond represented by G in the general formula [15a]. Although derived from the formula hydrocarbon group, examples of the aliphatic cyclic hydrocarbon group having a polymerizable double bond include an aliphatic polycyclic hydrocarbon group having 7 to 12 carbon atoms. Specifically, those represented by the following formulas are preferred.

[0115]

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[0116]

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[0117]

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[0118]

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In the general formulas [15a] and [15],
The alkyloxycarbonyl group represented by R ²⁰ and R ²¹ may be linear or branched, and for example, has 2 to 2 carbon atoms.
9 alkyloxycarbonyl groups, specifically, methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyl Examples include an oxycarbonyl group, a tert-butyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, and the like. Examples of the hydrophilic group include a hydroxyalkyloxycarbonyl group, a cyano group, a formyl group, a hydroxyl group, a hydroxyalkyl group, a carboxyl group,
Carboxyalkyl group, a carbamoyl group, -CH ₂ OC
OCH ₂ COCH ₃ group, —CH ₂ OCOCH ₂ COC ₂ H
₅ groups, or a dicarboximide (—CO—NH—CO—) group formed by bonding R ²⁰ and R ²¹ . Examples of the hydroxyalkyloxycarbonyl group include a hydroxyalkyloxycarbonyl group having 3 to 9 carbon atoms in which a hydrogen atom of the alkyloxycarbonyl group is substituted with a hydroxyl group as described above. , Hydroxypropyloxycarbonyl group, hydroxybutyloxycarbonyl group, hydroxypentyloxycarbonyl group,
Examples include a hydroxyhexyloxycarbonyl group, a hydroxyheptyloxycarbonyl group, a hydroxyoctyloxycarbonyl group, and the like. The hydroxyalkyl group may be linear or branched, and includes, for example, a hydroxyalkyl group having 1 to 8 carbon atoms, specifically, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Group, hydroxypentyl group, hydroxyhexyl group, hydroxyheptyl group,
And a hydroxyoctyl group. The carboxyalkyl group may be linear or branched, and includes, for example, a carboxyalkyl group having 2 to 6 carbon atoms, specifically, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, And a carboxypentyl group.

Specific examples of the monomer represented by the general formula [15] include the following monomers.

[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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In producing the polymer according to the present invention, one or a combination of two or more of these monomers (hereinafter, referred to as “other monomers”) may be used in addition to the monomer according to the present invention. When the polymer according to the present invention is used as a resist material for ArF, these other monomers used in combination with the monomer according to the present invention have a group having a hydrophilic property in order to improve the substrate adhesion. A monomer is preferably used, and a monomer having a group having hydrophilicity and having a polycyclic hydrocarbon group is more preferably used.

Examples of the polymer according to the present invention include those represented by the following general formula [20].

[0137]

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(Where x + y + z = 1, 0.10 ≦ x ≦ 0.9
9, 0 ≦ y ≦ 0.90, 0 ≦ z ≦ 0.90, 0.01 ≦ y + z ≦ 0.90, and n represents the degree of polymerization. Other symbols are the same as above. )

Further, when the polymer according to the present invention contains the monomer unit represented by the above general formula [13a] as a constitutional unit, the polymer according to the present invention includes:
For example, those represented by the following general formula [20 ′] can be mentioned.

[0140]

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(Where x + y + z + z ′ = 1, 0.10 ≦ x
≤ 0.99, 0 ≤ y ≤ 0.90, 0 ≤ z ≤ 0.90, 0 ≤ z '≤ 0.50, 0.
01 ≦ y + z + z ′ ≦ 0.90, and n represents the degree of polymerization. Other symbols are the same as above. )

Among these polymers according to the present invention, more specifically, those represented by the following general formula [20 ″] are preferred.

[0143]

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(Where x + y + z = 1, 0.10 ≦ x ≦ 0.9
9, 0 ≦ y ≦ 0.90, 0 ≦ z ≦ 0.90, 0.01 ≦ y + z ≦ 0.90, n represents the degree of polymerization, R ^{20 ′} represents a hydrogen atom or a hydroxymethyl group, and Q is the same as above. Also,
R ′ represents the following general formula [7], [8] or [8 ′].

[0145]

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[0146]

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[0147]

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In the formula, R ^{1 ′} represents a hydrogen atom, R ^{2 ′} and R ^{3 ′} represent a lower alkyl group having 1 to 4 carbon atoms, and R ^{1 ′} and R ^{2 ′} are bonded to each other. To form a methylene chain having 3 to 4 carbon atoms, and Y and Y ′ represent a group represented by the following formula [9] or the following general formula [10].

[0149]

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[0150]

Embedded image [In the formula, R ^{4 ′} and R ^{5 ′} represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. ]｝)

Examples of the polymer according to the present invention include:
For example, a polymer having the following segments can be mentioned.

[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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The polymer according to the present invention can be easily obtained, for example, by the following method (a) or (b).

(A) Method-1 The monomer according to the present invention and, if necessary, another monomer are dissolved in an appropriate solvent in the presence of a catalytic amount of a radical polymerization initiator, and optionally under an inert gas atmosphere. 0.5 ~ at 20 ~ 150 ℃
The polymerization reaction is performed for 48 hours according to a conventional method. After the reaction, a post-treatment is carried out according to a conventional method for obtaining a polymer, whereby a polymer containing the desired monomer unit represented by the above general formula [1a] as a constituent unit can be obtained.

Examples of the radical polymerization initiator include azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (methyl 2-methylpropionate), 2 , 2'-azobis (2-methylbutyronitrile),
2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), azo-based polymerization initiators such as 4,4'-azobis (4-cyanopentanoic acid), for example, lauroyl peroxide, benzoyl peroxide, Examples include peroxide-based polymerization initiators such as bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxy-2-ethylhexanoate, and methyl ethyl ketone peroxide.

Examples of the reaction solvent include hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate and n-butyl acetate; for example, ethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and the like. , 4-dioxane, ethers such as 1,3-dioxolane, for example, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, alcohols such as tert-butanol, for example, methyl ethyl ketone, methyl isobutyl ketone, Organic solvents such as ketones such as cyclohexanone.

The inert gas used when the polymerization reaction is carried out in an inert gas atmosphere includes, for example, nitrogen gas, argon gas and the like.

(B) Method-2 The monomer of the present invention and, if necessary, other monomers are prepared in a suitable organic solvent in the presence of a catalytic amount of an organometallic catalyst, optionally in an inert gas atmosphere. The polymerization reaction is carried out at 78 to 50 ° C for 0.5 to 48 hours according to a conventional method. After the reaction, a post-treatment is carried out according to a conventional method for obtaining a polymer, whereby a polymer containing the desired monomer unit represented by the above general formula [1a] as a constituent unit can be obtained.

Examples of the organometallic catalyst include n-butyllithium, sec-butyllithium, tert-butyllithium,
Organic alkali metal compounds such as naphthalene sodium, naphthalene potassium and cumyl potassium, for example, [Pd (CH ₃ CN)
₄ ] [BF ₄ ] ₂ , [Pd (PhCN) ₄ ] [BF ₄ ] ₂ , [Pd (C (CH ₃ ) ₃ CN) ₄ ] [BF ₄ ]
₂ , [Pd (C ₅ H ₅ N) ₄ ] [BF ₄ ] ₂ , [Pd (CH ₃ CN) _4-n (PPh ₃ ) _n ] [B
And organic palladium compounds such as [F ₄ ] ₂ and [Pd (CH ₃ CN) _x (CO) _y ] [BF ₄ ] ₂ .

As the organic solvent, for example, ethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-
Ethers such as dioxane and 1,3-dioxolane; for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone; esters such as methyl acetate, ethyl acetate and n-butyl acetate; for example, benzene, toluene, xylene and the like Hydrocarbons, for example, nitro compounds such as nitromethane and nitroethane, and the like. These organic solvents are preferably used after drying.

The inert gas used when the polymerization reaction is carried out in an inert gas atmosphere includes, for example, nitrogen gas, argon gas and the like.

The concentration of the monomer according to the present invention and the other monomers during the polymerization reaction is not particularly limited in any of the methods 1 and 2, but the total of both is usually 5 to 95% by weight, preferably 10 to 10% by weight. It is appropriately selected so as to be in the range of ~ 90% by weight.

The molecular weight of the polymer according to the present invention comprising the monomer unit represented by the general formula [1a] as a constituent unit is not particularly limited, but is usually 1,000 to 300,000, preferably 1,500 to 50,000 as a weight average molecular weight. ,
More preferably, a thing of 1,500-30,000 is mentioned. The degree of polymerization (n) of the polymer is not particularly limited, but is usually 4 to 2,000, preferably 8 to 500, and more preferably 10 to 300.

The proportion of the monomer unit derived from the monomer according to the present invention in the copolymer obtained by polymerizing the monomer according to the present invention with another monomer is not particularly limited. Usually 99 ~
It is appropriately selected from the range of 10% by weight, preferably 95 to 20% by weight.

The proportion of the monomer units derived from other monomers is usually 1 to 90% by weight, preferably 5 to 90% by weight.
It is appropriately selected from the range of ~ 80% by weight.

The polymer according to the present invention thus obtained is a substituted alkyl group or a substituted alkyl group having one or two protected hydroxyl groups represented by the above-mentioned general formula [5] or [6]. It is characterized by having an alkenyl group.

By using the polymer according to the present invention as the resist material of the present invention, the protected hydroxyl group represented by the above general formula [5] or [6] in the polymer can be replaced with one.
Alternatively, a hydroxyl group formed by removing (deprotecting) a protective group of a substituted alkyl group or substituted alkenyl group having two by the action of an acid generated by exposure is a soluble group of a conventionally used novolak resin or phenol resin. Since it becomes a group having the same pKa (12 to 13) as the phenolic hydroxyl group, by introducing the group into the polymer according to the present invention, it is possible to use 2.38% of the existing alkali developing solution in the development processing after exposure. This has a remarkable effect in that a TMAH aqueous solution can be used, the dissolution rate can be easily controlled during alkali development, and a resist material having excellent dissolution characteristics can be provided. Therefore, a resist composition comprising the polymer according to the present invention, a photosensitive compound capable of generating an acid upon exposure, and a solvent capable of dissolving the same is useful as a next-generation exposure technology.
It can be used very effectively as a resist material for rF excimer laser.

In the resist composition of the present invention, the photosensitive compound that generates an acid upon exposure (hereinafter, abbreviated as an acid generator) is a photosensitive compound that generates an acid upon exposure. Any one may be used as long as it does not adversely affect the light transmittance, particularly, the light transmittance near 193 nm is good and the high transparency of the resist composition can be maintained, or the light transmittance near 193 nm is increased by exposure. Acid generators that can maintain high transparency of the resist composition are more preferred. Particularly preferred acid generators in the present invention include, for example, trimethylsulfonium.
Trifluoromethanesulfonate, triphenylsulfonium ・ trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium ・ trifluoromethanesulfonate, cyclopentylmethyl
(2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 2-oxocyclohexylmethyl (2
-Norbornyl) sulfonium salts such as sulfonium / trifluoromethanesulfonate, trifluoromethylsulfonyloxy-7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, trifluoromethylsulfonyloxybicyclo [2.2 .2] Carboximide compounds such as hept-5-ene-2,3-carboximide, trifluoromethylsulfonyloxysuccinimide, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis ( 1,1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyldiazomethane, tert-butylsulfonylmethylsulfonyldiazomethane, Cyclohe Diazodisulfone compounds such sill sulfonyl ethylsulfonyl diazomethane. Incidentally, the acid generator may be used those appropriately synthesized by even or a conventional method using a commercially available product.

The solvent used in the present invention may be any solvent as long as it can dissolve the polymer according to the present invention and the acid generator.
Those having no absorption around 00 nm are more preferably used. Specifically, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, acetic acid 2-
Ethoxyethyl, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclohexanone, methyl ethyl ketone , 2-heptanone, 1,4-dioxane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, and the like.

The resist composition of the present invention generally comprises the aforementioned 3
The components (the polymer, the acid generator and the solvent according to the present invention) are the main constituent components, and if necessary, an ultraviolet absorber [eg, 9-diazofluorene and its derivative, 1-diazo-2-
Tetralone, 2-diazo-1-tetralone, 9-diazo-10-phenanthrone, benzophenone, 9- (2-methoxyethoxy) methylanthracene, 9- (2-ethoxyethoxy) methylanthracene, 9- (4-methoxybutoxy) Methylanthracene, 9-anthracenemethyl acetate, benzophenone and the like can be mentioned. ] May be added.

Furthermore, sensitivity modifiers usually used in this field [for example, polyvinyl pyridine, poly (vinyl pyridine / methyl methacrylate), pyridine, piperidine, triethylamine, tri-n-propylamine, tri-
n-butylamine, trioctylamine, tribenzylamine, dicyclohexylamine, dicyclohexylmethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, N-methyl-2-pyrrolidone, and the like. . And a plasticizer [for example, diethyl phthalate, dibutyl phthalate, dipropyl phthalate and the like]. ], Organic acids [for example, salicylic acid, lactic acid, 2-hydroxynaphthalene-3-carboxylic acid, 2-nitrobenzoic acid,
Examples include phthalic acid, succinic acid, and malonic acid. ], And surfactants [for example, various commercially available nonionic surfactants, cationic surfactants, anionic surfactants and various fluorine-based surfactants} such as Florard (Sumitomo 3M)
(Trade name), F-Top (trade name of Tochem Products Co., Ltd.), Surflon (trade name of Asahi Glass Co., Ltd.), Fantagent (trade name of Neos Co., Ltd.), Mega Fac (Dainippon Ink Co., Ltd.) (Trade name), Unidyne (trade name of Daikin Industries, Ltd.) and the like. And the like. ] May be appropriately added to these.

A pattern can be formed using the resist composition of the present invention, for example, as follows. That is, the resist composition of the present invention is applied on a semiconductor substrate such as a silicon wafer so as to have a thickness of about 0.3 to 2.0 μm (0.1 to 0.5 μm when used as an upper layer of three layers).
m) in an oven at 70-130 ° C. for 10-30 minutes, or on a hot plate at 60-150 ° C., preferably 60-110 ° C. for 60-180 seconds. Next, a mask for forming a desired pattern is held over the resist film obtained as described above, and, for example, far ultraviolet light of 220 nm or less is irradiated so as to have an exposure amount of about 1 to 100 mJ / cm ² , 60-150 ° C on a hot plate, preferably 60-110
Bake at 60 ° C for 60-180 seconds. Further, using a developing solution such as a 0.1-5% aqueous solution of tetramethylammonium hydroxide (TMAH), a dipping method (dip) for about 0.5-3 minutes, and a paddle (pud).
A target pattern can be formed on the substrate by performing development using a conventional method such as a ddle) method or a spray method.

The mixing ratio of the polymer to the acid generator according to the present invention in the resist composition is 1 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the polymer.
Parts by weight. Further, the amount of the solvent in the resist composition of the present invention is an amount that does not hinder the application of a positive resist material obtained as a result of dissolving the polymer and the acid generator according to the present invention on a substrate. If so, it is not particularly limited, but usually 1 to 1 weight of the polymer.
20 weight, preferably in the range of 1.5 to 10 weight.

The developing solution used in the above-mentioned various pattern forming methods may be an alkali having a suitable concentration such that the difference in solubility between exposed and unexposed portions can be increased in accordance with the solubility of the resist material. An aqueous solution may be selected, and is usually appropriately selected from the range of 0.01 to 20%. Further, examples of the alkaline aqueous solution to be used include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline, triethanolamine, morpholine and 1-methylmorpholine. An aqueous solution containing an organic amine, for example, an inorganic alkali compound such as sodium hydroxide or potassium hydroxide, or the like can be given.

The semiconductor substrate includes, for example, a silicon wafer, polysilicon, a TiN substrate, a BPSG substrate and the like. It is preferable that these semiconductor substrates are treated with a substrate treating agent such as hexamethyldisilazane (HMDS).

The polymer according to the present invention can be prepared by, for example, a compound represented by the general formula [1a] having a substituted alkyl group or a substituted alkenyl group having one or two protected hydroxyl groups represented by the general formula [5] or [6]. In the case where this is used as a resist material, the pKa can be appropriately selected and set as compared with a conventional polymer used for the same kind of purpose, since the monomer unit represented by the formula (1) is included as a constituent unit. This makes it possible to control the dissolution rate during alkali development, and thus a good resist pattern can be obtained, so that a semiconductor device such as a semiconductor integrated circuit with a higher degree of integration can be manufactured. Is played.

The resist composition of the present invention can be prepared using a deep ultraviolet light,
It has been confirmed that an acid is also generated by rF excimer laser light and irradiation with an electron beam or soft X-ray, and a chemical amplification action is caused. Therefore, the resist composition of the present invention is a resist material capable of forming a pattern even by low-exposure deep ultraviolet light, KrF excimer laser light, and electron beam or soft X-ray irradiation utilizing chemical amplification.

The resist material of the present invention will be described in more detail with reference to a specific example.
An acid is generated in a portion exposed to F excimer laser light (λ = 193 nm) according to, for example, a photoreaction represented by the following [Equation 1], [Equation 2], or [Equation 3].

[0192]

(Equation 1)

[0193]

(Equation 2)

[0194]

(Equation 3)

When a heat treatment is carried out following the exposure step, a specific functional group of the polymer according to the present invention is deprotected by an acid according to the reaction of the following [Formula 4] or [Formula 5], becomes alkali-soluble, and becomes It elutes in the developer.

[0196]

(Equation 4)

[0197]

(Equation 5)

On the other hand, since no acid is generated in the unexposed portion, no chemical change occurs even when the heat treatment is performed. As described above, when a pattern is formed using the resist composition containing the polymer according to the present invention, a solubility difference occurs in an alkali developing solution between an exposed portion and an unexposed portion, and as a result, Thus, a positive pattern having good contrast is formed.

Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention is not limited by these. The acid generator used in the examples is described in, for example, JP-A-7-25846, TMChapm
an et al .; Synthesis, 1971, 591, TMChapman et al .; J. Org, Che
m., 38 , 3908 (1973).

[0200]

EXAMPLES Reference Example 1 FIG. Synthesis of 5-norbornene-2-methyl acetoacetate 5-norbornene-2-methanol (endo-exo mixture) 100.
30 g (807.7 mmol) was dissolved in 800 ml of toluene, and 0.82 g (8.1 mmol) of triethylamine was added thereto.
After 7.9 g (807.7 mmol) was added dropwise at 30 ° C. over 15 minutes, the mixture was stirred and reacted at the same temperature for 4 hours. After standing overnight, the reaction solution is 1N-
The mixture was washed four times with 260 ml of H ₂ SO _{4 and} 260 ml of water, and dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was distilled under reduced pressure through a Vigreux rectification tube to obtain 118.4 g of the desired slightly yellow oily 5-norbornene-2-methyl acetoacetate (yield: 70%).
%). 1H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.56, 1.17 (m, 1
H), 1.26 (d, 1H), 1.44 (d, 1H), 1.72-1.89 (m, 1
H), 2.28 (s, 3H), 2.40 (m, 1H), 2.83 (s, 1H), 2.8
8 (s, 1H), 3.47 (s, 2H), 3.74, 4.05 (dd, 1H), 3.92,
4.22 (dd, 1H), 5.00 (s, 0.1H, enolized double bond 10
%), 5.93-6.18 (m, 2H), 12.11 (s, 0.1H, 10% of enolized OH).

Reference Example 2 5-norbornene-2-methyl 3-
Synthesis of methoxy-2-butenoate 30 g (144.1 mmol) of 5-norbornene-2-methyl acetoacetate obtained in Reference Example 1 was mixed with 47 ml of methyl orthoformate (43 ml).
2.2 mmol) and added thereto camphorsulfonic acid 1.67
After charging g (7.20 mmol), the mixture was stirred and reacted at room temperature for 3.5 hours. After standing overnight, dilute the reaction solution with 120 ml of toluene,
The extract was washed successively with 60 ml of saturated aqueous sodium bicarbonate, 60 ml of water and 60 ml of saturated saline, and dried over anhydrous magnesium sulfate. After distilling off the solvent, the obtained crude product was distilled under reduced pressure to obtain 30.33 g (yield 94%) of 5-norbornene-2-methyl 3-methoxy-2-butenoate as an objective slightly yellow oil. Boiling point: 134-137 ° C / 4mmHg. 1H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.58, 1.17 (m, 1
H), 1.26 (d, 1H), 1.45 (d, 1H), 1.80-1.90 (m, 1
H), 2.29 (s, 3H), 2.38-2.43 (m, 1H), 2.82 (s, 1
H), 2.90 (s, 1H), 3.64 (s, 3H), 3.66, 4.00 (dd, 1
H), 3.86, 4.14 (dd, 1H), 5.03 (s, 1H), 5.95-6.17
(M, 2H).

Reference Example 3 5-norbornene-2-methyl 3
Synthesis of 5-ethoxy-2-butenoate 62-48 g (300 mmol) of 5-norbornene-2-methyl acetoacetate obtained in Reference Example 1 was mixed with 150 ml of ethyl orthoformate.
(900 mmol), and added thereto camphorsulfonic acid 3.48.
g (15 mmol) was added thereto, and the mixture was stirred and reacted at room temperature for 3.5 hours. After standing overnight, the reaction solution was diluted with 240 ml of toluene, washed successively with 120 ml of saturated aqueous sodium hydrogen carbonate, 120 ml of water and 120 ml of saturated saline, and dried over anhydrous magnesium sulfate. After evaporating the solvent, the obtained crude product was distilled under reduced pressure to obtain 33.56 g (yield: 47%) of 5-norbornene-2-methyl-3-ethoxy-2-butenoate as a desired slightly yellow oil. Boiling point: 128-132 ° C / 4mmHg. 1H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.57, 1.18 (m, 1
H), 1.27 (d, 1H), 1.35 (t, J = 6.96, 3H), 1.45 (d, 1
H), 1.80-1.90 (m, 1H), 2.29 (s, 3H), 2.36-2.43
(M, 1H), 2.82 (s, 1H), 2.90 (s, 1H), 3.83 (q, J = 6.
96, 2H), 3.51, 3.98 (dd, 1H), 3.65, 4.13 (dd, 1H),
5.00 (s, 1H), 5.94 to 6.17 (m, 2H).

Reference Example 4 5-norbornene-2-methyl 2,
Synthesis of 2- (2 ', 2'-dimethylpropylenedioxy) butanoate 52.07 g (250 mmol) of 5-norbornene-2-methyl acetoacetate obtained in the same manner as in Reference Example 1 was dissolved in toluene 25
0 ml, and 78.11 g (750 mmol) of 2,2-dimethyl-1,3-propanediol and 0.48 g (2.5 mmol) of p-toluenesulfonic acid monohydrate were added thereto. The mixture was refluxed for 4 hours while removing by-produced water. After completion of the reaction, the reaction solution was washed with saturated aqueous sodium bicarbonate 125 ml, water 125 ml, and saturated saline.
The mixture was sequentially washed with 125 ml and dried over anhydrous magnesium sulfate. After distilling off the solvent, the obtained crude product was distilled under reduced pressure to obtain 5-norbornene-2-methyl 2,2-
(2 ', 2'-dimethylpropylenedioxy) butanoate45.
86 g (62.3% yield) was obtained. Boiling point: 141-147 ° C / 3mmHg. 1H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.52-0.59, 1.12
1.18 (m, 1H), 0.94 (s, 3H), 1.01 (s, 3H), 1.25 (d,
1H), 1.45 (d, 1H), 1.46 (s, 3H), 1.79-1.88 (m, 1
H), 2.38-2.43 (m, 1H), 2.80 (d, 3H), 2.89 (s, 1
H), 3.48-4.13 (m, 6H), 5.92-6.17 (m, 2H).

Reference Example 5 5-norbornene-2-methyl 2,
Synthesis of 2- (2′-butyl-2′-ethylpropylenedioxy) butanoate 24.99 g (120 mmol) of 5-norbornene-2-methyl acetoacetate obtained in the same manner as in Reference Example 1 was dissolved in toluene 24
0 ml, and into this were added 28.85 g (180 mmol) of 2-butyl-2-ethyl-1,3-propanediol and 1.39 g (6 mmol) of dl-camphorsulfonic acid, and water produced as a by-product in a water separator was added. The mixture was subjected to a reflux reaction for 5 hours while removing. After completion of the reaction, the reaction solution was washed successively with 60 ml of saturated aqueous sodium hydrogen carbonate, 60 ml of water and 60 ml of saturated saline, and dried over anhydrous magnesium sulfate. After evaporating the solvent, the obtained crude product was purified by column chromatography [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent: n-hexane / ethyl acetate = 4/1] To obtain the desired slightly yellow oily 5-norbornene-2-methyl
32.95 g (78.3% yield) of 2,2- (2'-butyl-2'-ethylpropylenedioxy) butanoate was obtained. 1H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.53-0.60 (m, 1
H), 0.77-0.84 (m, 3H), 0.91 (t, J = 6.96, 3H), 1.11
1.51 (m, 10H), 1.54 (s, 3H), 1.79-1.88 (m, 1H), 2.
36-2.45 (m, 1H), 2.81-2.78 (m, 3H), 2.89 (s, 1H),
3.54-4.19 (m, 6H), 5.92-6.17 (m, 2H).

Reference Example 6 5-norbornene-2-methanol (endo-exo mixture) 0.40
g (3.2 mmol), maleic anhydride 2.98 g (30.4 mmol), 5-norbornene-2-methyl 3-methoxy-2 obtained in Reference Example 2.
A mixture of 10.31 g (46.4 mmol) of -butenoate and 44 ml of dry tetrahydrofuran (THF) was heated to 65 ° C., and then 0.53 g (3.2 mmol) of azobisisobutyronitrile was mixed.
Was added, and a polymerization reaction was carried out at the same temperature in a nitrogen stream for 16 hours. After completion of the reaction, the reaction solution was poured into 500 ml of n-hexane to precipitate a polymer. This is collected by filtration, dried and dried.
5.93 g (43% yield) were obtained. The composition ratio of 5-norbornene-2-methanol unit, maleic anhydride unit and 5-norbornene-2-methyl-3-methoxy-2-butenoate unit in the obtained polymer was about 0.16: 0.33: 0.
It was 50. GPC using polystyrene as standard
(Gel permeation chromatography, solvent: tetrahydrofuran), the weight average molecular weight (Mw) was found to be 20.
00, the degree of dispersion was 1.50.

Reference Example 7 In Reference Example 5, except that 5-norbornene-2-methyl 3-ethoxy-2-butenoate obtained in Reference Example 3 was used instead of 5-norbornene-2-methyl 3-methoxy-2-butenoate. A polymerization reaction was carried out in exactly the same manner as in Reference Example 6,
5.75 g (yield 40%) of the desired product was obtained. The composition ratio of the 5-norbornene-2-methanol unit, maleic anhydride unit and 5-norbornene-2-methyl 3-ethoxy-2-butenoate unit in the obtained polymer was about 0.16 by 1H-NMR measurement.
0.33: 0.50. GPC (solvent: tetrahydrofuran) measurement using polystyrene as a standard revealed that the weight average molecular weight (Mw) was 2300 and the dispersity was 1.48.

Reference Example 8 In Reference Example 6, 5-norbornene-2-methyl 2,2- (2 ', 2'-dimethyl obtained in Reference Example 4 was used instead of 5-norbornene-2-methyl 3-methoxy-2-butenoate. A polymerization reaction was carried out in exactly the same manner as in Reference Example 6 except that propylenedioxy) butanoate was used, to give 6.48 g of the desired product (yield 38
%). 5-norbornene-2-methanol unit, maleic anhydride unit and 5-norbornene of the polymer obtained
The composition ratio of -2-methyl 2,2- (2 ', 2'-dimethylpropylenedioxy) butanoate unit was about 0.1 from 1H-NMR measurement.
6: 0.33: 0.50. GPC (solvent: tetrahydrofuran) measurement using polystyrene as a standard revealed that the weight average molecular weight (Mw) was 2000 and the degree of dispersion was 1.50.

Reference Example 9 In Reference Example 6, 5-norbornene-2-methyl 2,2- (2′-butyl-2 ′) obtained in Reference Example 5 was used instead of 5-norbornene-2-methyl 3-methoxy-2-butenoate. A polymerization reaction was carried out in exactly the same manner as in Reference Example 6 except that (-ethylpropylenedioxy) butanoate was used.
34%). The resulting polymer 5-norbornene-2-
The composition ratio of methanol unit, maleic anhydride unit and 5-norbornene-2-methyl 2,2- (2′-butyl-2′-ethylpropylenedioxy) butanoate unit was about 0.16: 0.33: 0.50 by 1 H-NMR measurement. Met. GPC (solvent: tetrahydrofuran) measurement using polystyrene as a standard revealed that the weight average molecular weight (Mw) was 2500 and the dispersity was 1.29.

Reference Example 10 Under a nitrogen stream, 0.09 g (0.2 mmol) of [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ was suspended in 15 ml of nitromethane, and the 5-norbornene-2-methyl obtained in Reference Example 1 was added to the suspension. Acetoacetate 1.
25 g (6 mmol) of 5-norbornene-2 obtained in Reference Example 2
-Methyl 3-methoxy-2-butenoate 3.11g (14mmo
l) and a solution comprising 5 ml of nitromethane were added dropwise at room temperature over 5 minutes, and a polymerization reaction was carried out at room temperature for 16 hours. After completion of the reaction, the polymerization catalyst was removed by filtration, and the obtained mother liquor was poured into 200 ml of diisopropyl ether (IPE) to precipitate a polymer. This was collected by filtration and dried to obtain 1.98 g of the desired product (yield 45
%). 5-norbornene-2-methyl acetoacetate unit of the resulting polymer, 5-norbornene-2-methyl
The composition ratio of 3-methoxy-2-butenoate units is 1H-N
It was about 0.30: 0.70 from MR measurement. GPC (gel permeation chromatography, solvent: tetrahydrofuran) measurement using polystyrene as a standard showed that the weight average molecular weight (Mw) was 19200 and the dispersity was 2.27.

Embodiment 1 A resist composition having the following composition was prepared. (A) 3.0 g of the polymer obtained in Reference Example 5 (b) Acid generator 60 mg (triphenylsulfonium trifluoromethanesulfonate) (c) 15.6 g of ethylene glycol dimethyl ether

The resist composition having the above composition was used in an amount of 0.1 μm
The resulting filtrate was spin-coated on a silicon wafer and baked on a hot plate at 140 ° C. for 60 seconds to obtain a resist film having a thickness of 0.4 μm. Next, the formed wafer is allowed to stand still in a projection exposure experiment machine sufficiently purged with nitrogen, and ArF excimer laser light (λ
= 193 nm; NA 0.55). After exposure, the film was heated on a hot plate at 90 ° C. for 60 seconds, and a developing solution [2.38% TMAH aqueous solution. Liquid temperature 23 ° C. , And then rinsed with ultrapure water for 60 seconds to obtain a 0.17 μm (exposure amount: about 36 mJ / cm ² ) line and space pattern.

[0212]

As described above, the present invention provides a novel resist composition used in the production of semiconductor devices and the like and a pattern forming method using the same.
The resist composition of the present invention can be used very effectively as a resist material for ArF excimer laser, which is a promising next-generation exposure technology. Therefore, the present invention has great value for forming fine patterns in the semiconductor industry, for example.

Claims (4)

[Claims] 1. A compound of the general formula [1a] (Wherein, X represents a polycyclic hydrocarbon group which may have a substituent, Z represents a spacer or a bond, and R represents a substituted alkyl group or a substituted alkyl group having one or two protected hydroxyl groups. A resist composition comprising a polymer comprising a monomer unit represented by an alkenyl group) as a constituent unit, a photosensitive compound capable of generating an acid upon exposure, and a solvent capable of dissolving the same. 2. A substituted alkyl or alkenyl group having one or two protected hydroxyl groups represented by R in the general formula [1a] is represented by the general formula [5]: (Wherein R ^{1 and} R ² each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group or an aliphatic polycyclic hydrocarbon group, and R ¹ and R ² are bonded to each other; R ³ may be an aliphatic ring together with an adjacent carbon atom.
Represents an alkyl group, an alkenyl group, a hydroxyalkyl group,
Represents an alkyloxycarbonyl group or an alkylsilyl group. ) Or the general formula [6] (In the formula, R ⁴ represents an alkyl group, R ¹ , R ² and R ³ are the same as those described above. Further, a methylene chain or a substituted or unsubstituted methylene chain may be bonded to R ³ and R ⁴ . May form an aliphatic ring which may have a group).
The resist composition according to claim 1. 3. The polycyclic hydrocarbon group represented by X in the general formula [1a], which may have a substituent, is represented by the general formula [2a]: (Wherein, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group, a cyano group, an alkyloxycarbonyl group or a carbamoyl group, and k represents 0 or 1), and a general formula: [3a] embedded image (Wherein, R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, an alkyl group, a cyano group, an alkyloxycarbonyl group or a carbamoyl group), or a general formula [4
a] embedded image The resist composition according to claim 1, which is a group represented by the formula: 4. Exposing the resist composition according to claim 1 to a substrate, and (2) exposing with a light of 220 nm or less through a mask after a heat treatment. A pattern formation method comprising: a step of performing (3) a heat treatment as necessary and then developing using a developer.