JPH1112325A - New monomer and polymer obtained by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new monomer useful for a polymer, having a high transmissivity for far ultraviolet rays, especially of ArF excimer laser, etc., and useful as resist compositions. SOLUTION: This monomer is represented by formula I (R<5> to R<7> are each H, an alkyl, etc.; Z is a spacer, etc.; R is a hydroxyalkyl), e.g. 2-(methacryloyloxy)ethyl :3-methoxy-butanoate). The monomer is obtained by reacting a cc>mpound represented by formula II (R<1> and R<2> are each H, etc.), with orthocarboxylic acid esters and an alcohol in a solvent and in the presence of a acid catalyst. For example, the copolymerizing reaction of the monomer with the other monomers is carried out in the presence of a catalytic amount of a radical polymerization initiator in a suitable solvent at 20-150 deg.C in an inert gas atmosphere for 0.5-20 hr according to 21 conventional method. Thereby, a polymer capable of providing 21 resist film excellent in etching resistance, etc., can be synthesized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymer useful for a resist composition used in the production of semiconductor devices and the like, and a novel monomer which can be a raw material of the polymer.

[0002]

2. Description of the Related Art Conventionally, novolak resins and polymers containing acrylic acid and methacrylic acid as components have been known as alkali-soluble resins, and they have been used as materials for the electronic industry such as photolithography and resist materials. Polymer has been put to practical use. Particularly in the field of lithography technology, g-rays (wavelength 436 nm) and i-rays (wavelength 365) are used as exposure light sources.
nm) ultraviolet light, and recently an excimer laser (KrF
Excimer laser; wavelength 248 nm, ArF excimer laser; wavelength 193 nm) are used. As a base polymer of a resist material corresponding to these light sources, a novolak resin is mainly used for g-line and i-line resists, and a phenol resin is mainly used for a KrF resist, and any of these functional groups can be developed with an alkali developing solution. Has _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 the resin having an aromatic ring used conventionally has 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) because the carboxylic acid group is a soluble group, and the conventional phenolic hydroxyl group is a soluble group. Since the dissolution rate during alkaline development is much faster than that of a polymer, the existing alkaline developer, 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH), will cause film peeling during fine pattern formation if used without dilution. In addition, there is a disadvantage that a good pattern cannot be obtained because of dissolution to the unexposed portion.

In addition, the alkaline developer currently used in the actual production line of the semiconductor device is the aforementioned 2.38% TM
AH is the mainstream, and it is very difficult to dilute and use the developer in a production line in which resist materials of each generation are mixed, such as i-line resist and KrF resist or KrF resist and ArF resist.

[0006]

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.
For example, when this is used as a polymer for a resist composition, a novel polymer which can provide a resist film having excellent etching resistance and the like, and acrylic acid and methacrylic acid derivatives which are novel monomers which can be used as a raw material monomer of the polymer The purpose is to provide.

[0007]

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

[0008]

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(Wherein, R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a cyano group, an alkyloxycarbonyl group or a carbamoyl group, Z represents a spacer or a bond, and R represents Wherein the terminal hydroxyl group represents a protected hydroxyalkyl group.)

Further, the present invention provides a compound represented by the general formula [1a]:

[0011]

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(Wherein R ⁵ , R ⁶ , R ⁷ , Z and R are the same as described above).

That is, the present inventors have conducted intensive studies to achieve the above object, and as a result, have high light transmittance in a wavelength region of 220 nm or less, and have high etching resistance when this is used as a resist material. A novel polymer comprising a monomer unit represented by the above general formula [1a] as a constitutional unit from which a resist film can be obtained has been found, and the present invention has been completed.

In the general formulas [1] and [1a],
The alkyl group represented by R ⁵ , R ⁶ and R ⁷ may be linear or branched and includes, for example, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-
Butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 3,3-dimethylbutyl, 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.

The alkyloxycarbonyl group may be linear, branched or cyclic, and includes, for example, an alkyloxycarbonyl group having 2 to 19 carbon atoms.
The cyclic alkyloxycarbonyl group may be monocyclic or polycyclic, and includes, for example, an alicyclic group having 6 to 14 carbon atoms. Specific examples of the alkyloxycarbonyl group include a methyloxycarbonyl group, an ethyloxycarbonyl group,
Propyloxycarbonyl, butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, tert-butyloxycarbonyl, 2-ethylhexyl Oxycarbonyl group, cyclohexyloxycarbonyl group, tricyclodecyloxycarbonyl group, tricycloundecyloxycarbonyl group, tricyclododecyloxycarbonyl group, tricyclotetradecyloxycarbonyl group, tetrahydropyranyloxycarbonyl group, adamantyloxycarbonyl group , A 2-methyl-2-adamantyloxycarbonyl group,
Norbornyloxycarbonyl group, bicyclo [3.2.1] octenyloxycarbonyl group, bicyclo [2.2.2] octyloxycarbonyl group, menthyloxycarbonyl group,
And an isobornyloxycarbonyl group.

Examples of the spacer represented by Z include a group represented by the following general formula [4].

[0017]

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(Wherein A ₂ represents a divalent hydrocarbon group optionally having an oxygen atom, A ₁ and A ₃ each independently represent a lower alkylene group, and m represents 0 or 1. And p, q
And r each independently represent 0 or 1. However, m is 1
In the case of q represents 1. )

In the general formula [4], examples of the divalent hydrocarbon group represented by A ₂ which may have an oxygen atom include those having 1 to 20 carbon atoms. Preferably, an alkylene group of 1 to 10 and a divalent aromatic group are exemplified. The alkylene group may be linear, branched or cyclic, 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. As the divalent aromatic group, for example, o-phenylene group, m-phenylene group, p-
Phenylene group, diphenylene group, p-xylene-α, α′-diyl group, —CH ₂ —C ₆ H ₄ — and the like.

In the case of having an oxygen atom, those having one or more, preferably 1 to 3 oxygen atoms in the divalent hydrocarbon group chain are mentioned. Specific examples include a methoxyethylethylene group, an ethoxyethylethylene group, a bornyloxyethylethylene group, a norbornyloxyethylethylene group, a menthyloxyethylethylene group, an adamantyloxyethylethylene group, a methoxyethoxyethylethylene group, and an ethoxyethoxy group. Ethylethylene group, bornyloxyethoxyethylethylene group, menthyloxyethoxyethylethylene group, -CH ₂
-O-CH _2- , -CH ₂ CH ₂ -O-CH _2- , -CH ₂ CH ₂ -O-CH ₂ CH _2- , -CH ₂ CH
_{2 -O-CH 2 CH 2 -O} -CH 2 CH 2 -, - CH 2 -OC 6 H 4 - , and the like.

The lower alkylene group represented by A ₁ and A ₃ may be linear or branched and has, for example, 1 to 1 carbon atoms.
6 alkylene groups, specifically, a methylene group,
Ethylene group, propylene group, butylene group, 2-methylpropylene group, pentylene group, 2,2-dimethylpropylene group,
Examples include a 2-ethylpropylene group and a hexylene group.

The hydroxyalkyl group in which the terminal hydroxyl group represented by R is protected may be linear, branched or cyclic, and may have a double bond. Examples include groups represented by the formula [2] or the general formula [3].

[0023]

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[0024] (wherein, R ¹ and R ² are independently a hydrogen atom, an alkyl group or an alicyclic hydrocarbon group which may have a substituent group, and in R ¹ and R ² It may form an aliphatic ring, and R ³ represents an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkyloxycarbonyl group or an alkylsilyl group.)

[0025]

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(Wherein R ⁴ represents an alkyl group; R ¹ , R
² and R ³ are the same as above. Note that R ³ and R ⁴ may form an aliphatic ring. )

In the general formulas [2] and [3], the alkyl group represented by R ¹ and R ² may be linear, branched or cyclic. 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.

As the alkyl group having a substituent, 1 to 17, preferably 1 to 10 hydrogen atoms of the above alkyl group are, for example, cyano group and hydroxyl group such as fluorine, chlorine, bromine and iodine. Halogen atoms such as methoxy, ethoxy, propoxy, 2-propoxy,
Examples thereof include those substituted with a lower alkoxy group having 1 to 6 carbon atoms such as a butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. Specific examples include a cyanomethyl group, a cyanoethyl group, and a cyanopropyl group. Group, cyanobutyl group, cyanopentyl group, cyanohexyl group, cyanoalkyl group such as cyanoheptyl group, for example, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxyheptyl And hydroxyalkyl groups such as hydroxyoctyl group, for example, chloromethyl group, bromomethyl group, trifluoromethyl group,
Haloalkyl groups such as chloroethyl group, 3-chloropropyl group, 3-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,
And alkoxyalkyl groups such as a propoxyethyl group, a butoxymethyl group and a tert-butoxymethyl group.

Examples of the alicyclic hydrocarbon group include an alicyclic hydrocarbon group having 3 to 30, preferably 5 to 12 carbon atoms. Specific examples include a tricyclo [5.2.1.0 ^2.6 ] decanyl group, Examples include a cyclopentenyl group, an adamantyl group, a norbornyl group, an isobornyl group, a 2-methyl-2-adamantyl group, and a menthyl group.

In the aliphatic ring formed by R ¹ and R ² , the ring may be monocyclic or polycyclic, for example, having 3 to 1 carbon atoms.
And those forming a ring with an alkylene chain of 0, and specific examples of the ring include a 2-norbornane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring,
Examples thereof include a cyclodecane ring, a 2-norbornene ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, and a cyclodecene ring.

The alkyl group represented by R ³ may be linear or branched, and includes, for example, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-
Butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 3,3-dimethylbutyl, 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.

The alkenyl group may be linear or branched and has, for example, 2 to 12 carbon atoms, preferably 2 carbon atoms.
And alkenyl groups of -8, and specifically include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, isohexenyl, heptenyl, octenyl and the like. No. As the hydroxyalkyl group,
It may be linear or branched, and includes, for example, a hydroxyalkyl group having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specifically, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl Group, hydroxyhexyl group, hydroxyheptyl group, hydroxyoctyl group and the like.

The alkyloxycarbonyl group may be linear, branched or cyclic, and includes, for example, an alkyloxycarbonyl group having 2 to 19 carbon atoms. Specifically, for example, an ethyloxycarbonyl group, propyl Oxycarbonyl group, butyloxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, tert-butyloxycarbonyl group, 2-ethylhexyloxy Examples include a carbonyl group and a cyclohexyloxycarbonyl group.

As the alkyl group of the alkylsilyl group,
It may be linear or branched and includes, for example, an alkyl group having 1 to 6 carbon atoms. Specifically, a methyl group, an ethyl group,
-Propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 3,3
-Dimethylbutyl group, 1,1-dimethylbutyl group, 1-methylpentyl group, n-hexyl group, isohexyl group and the like. As the alkylsilyl group, for example, a
18, preferably 1 to 9; specific examples include trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tripentylsilyl, and tri-n -
Examples include a trialkylsilyl group such as a hexylsilyl group and a tert-butyldimethylsilyl group.

In the general formula [3], 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

When R ³ and R ⁴ form an aliphatic ring, the ring may be monocyclic or polycyclic and has 2 to 1 carbon atoms.
Those which form a ring with 0, preferably 2 to 4 alkylene chains are mentioned. The alkylene chain may be linear or branched, and may have a hydroxyl group. Further, it may have a -O- group and / or a double bond at any position in the chain. Specific examples of these include ethylene group, propylene group, isopropyl group, isopropylidene group, butylene group, 2-methylpropylene group, pentylene group, 2,2-dimethylpropylene group, 2-ethylpropylene group, hexylene group , A 2-butyl-2-ethylpropylene group,
Ethenylene group, propenylene group, butenylene group, a vinylidene _{group, -CH 2 C (= CH 2} ) CH 2 -, 1- hydroxy ethylene group, 2
-Hydroxypropylene group, 2-hydroxybutylene group, 2
-Hydroxypentylene group, 3-hydroxypentylene group, 2-hydroxyhexylene group, 3-hydroxyhexylene group, -CH ₂ -O-CH _2- , -CH ₂ CH ₂ -O-CH ₂ -,- CH ₂ CH ₂ -O-CH ₂ CH
_2- and the like.

The monomer unit represented by the above general formula [1a] contained in the polymer of the present invention is represented by the above general formula [1]
Which is derived from a monomer represented by the following general formulas [1] -1, [1] -2,
Examples include those represented by [1] -3 and [1] -4.

[0038]

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[0039]

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[0040]

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[0041]

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(Wherein Q represents a divalent hydrocarbon group optionally having an oxygen atom, E represents a lower alkyl group,
X represents an alkyl group; G represents a lower alkylene group;
t shows the integer of 0-6. E ₁ and E _{2 each} represent a hydrogen atom, or E ₁ and E ₂ may form an aliphatic ring. )

In the above general formulas [1] -1 and [1] -2, the divalent hydrocarbon group of the divalent hydrocarbon group optionally having an oxygen atom represented by Q includes: For example, carbon number 1
-20, preferably 1-10 alkylene groups and divalent aromatic groups. The alkylene group may be linear, branched or cyclic, and specifically, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a 2-methylpropylene group, a pentylene group, and 2,2-dimethyl Propylene group, 2-ethylpropylene group, hexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, cyclopropylene group, cyclopentylene group, cyclohexylene group, adamantanediyl group, tricyclo [ 5.2.1.0 ^2.6 ] decanediyl group, norbornanediyl group, methylnorbornanediyl group, isobornanediyl group, decalindiyl group and the like.

Examples of the divalent aromatic group include o-phenylene group, m-phenylene group, p-phenylene group, diphenylene group, p-xylene-α, α′-diyl group, —CH ₂ —C ₆ H _4- and the like. When the divalent hydrocarbon group has an oxygen atom, those having one to three -O- groups in the chain forming the alkylene group are mentioned. Specifically, for example, -CH ₂ -O
_{-CH 2 -, - CH 2 CH} 2 -O-CH 2 -, - CH 2 -O-CH 2 CH 2 -, - CH 2 CH 2 -OC
H ₂ CH _2- , -CH ₂ -O-CH ₂ -O-CH _2- , -CH ₂ CH ₂ -O-CH ₂ -O-CH ₂ CH
_2- , -CH ₂ -O-CH ₂ -O-CH ₂ -O-CH _2- , -CH ₂ CH ₂ -O-CH ₂ -O-CH ₂ CH
₂ -O-CH ₂ CH _2- , -CH ₂ -O-CH (CH ₂ CH ₃ ) -CH _2- , -CH ₂ CH ₂ -O-CH
(CH ₃ ) -O-CH _2- ,

[0045]

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[0046]

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And the like. In the above general formulas [1] -1 and [1] -3, the lower alkyl group represented by E may be linear or branched, and includes, for example, an alkyl group having 1 to 6 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl , 3,3-dimethylbutyl group, 1,1-dimethylbutyl group, 1-
Examples include a methylpentyl group, an n-hexyl group, and an isohexyl group.

In the general formulas [1] -3 and [1] -4, the alkyl group represented by X may be linear, branched or cyclic, and has, for example, 1 to 20 carbon atoms, preferably Is an alkyl group of 1 to 15. Further, the cyclic alkyl group may be monocyclic or polycyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, 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, n-heptyl group,
Isoheptyl group, n-octyl group, isooctyl group, 2-
Ethylhexyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl, nonadecyl, icosyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-cyclohexylethyl, norbornyl, isobornyl, adamantyl Group, 2-methyl-2-adamantyl group, tetrahydropyranyl group, tricycloundecyl group, tricyclodecyl group,
Examples include a tricyclododecyl group, a tricyclotetradecyl group, a menthyl group, a bicyclo [3.2.1] octyl group, and a bicyclo [2.2.2] octyl group.

In the above general formulas [1] -2 and [1] -4, the lower alkylene group represented by G may be linear or branched, and may be an alkylene group having 1 to 6 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a 2-methylpropylene group, a pentylene group, a 2,2-dimethylpropylene group, a 2-ethylpropylene group, and a hexylene group.

In the above general formulas [1] -1 to [1] -4,
As the aliphatic ring formed by E ₁ and E ₂ , the ring may be monocyclic or polycyclic, and examples thereof include those having an alkylene chain having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms. Can be The alkylene chain may be linear or branched, and may have a double bond. Specific examples of these include ethylene group, propylene group, isopropyl group, isopropylidene group, butylene group, 2-methylpropylene group, pentylene group, 2,2-dimethylpropylene group, 2-ethylpropylene group, hexylene group , A 2-butyl-2-ethylpropylene group,
Examples include an ethenylene group, a propenylene group, a butenylene group, a vinylidene group, and —CH ₂ C (= CH ₂ ) CH ₂ —.

Specific examples of the general formula [1] -1 include, for example,

[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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Specific examples of the general formula [1] -2 include, for example,

[0058]

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[0059]

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[0060]

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[0061]

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Specific examples of the general formula [1] -3 include, for example,

[0063]

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[0064]

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Specific examples of the general formula [1] -4 include, for example,

[0066]

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[0067]

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And the like.

The monomer represented by the general formula [1] of the present invention is, for example, a compound represented by the general formula [5]

[0070]

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Wherein R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and Z
Is the same as above. Can be obtained by reacting the compound of the formula (1) with orthocarboxylic acid esters and, if necessary, alcohols in a suitable solvent, if necessary, in the presence of an acid catalyst.

Examples of the orthocarboxylic acid esters include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate and the like. The amount of orthocarboxylic acid esters used is
It is usually 1 to 30 moles, preferably 3 to 10 moles, based on the compound represented by the Formula [5].

As the alcohols, for example, those having 1 to 1 carbon atoms
12, preferably alcohols having 1 to 8 carbon atoms, specifically methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, n-pentanol, Isopentanol, neopentanol, tert-pentanol, 3,3-dimethylbutanol, 1,1-dimethylbutanol, 1-methylpentanol, n-hexanol,
Saturated alcohols such as isohexanol, n-heptanol, isoheptanol, n-octanol, isooctanol and 2-ethylhexanol, allyl alcohol,
3-buten-1-ol, 3-buten-2-ol, crotyl alcohol, 2-methyl-2-propen-1-ol, 2-methyl-3-
Buten-1-ol, 4-penten-1-ol, 4-penten-2
-Ol, 3-penten-2-ol, 1-hexen-3-ol, 3-hexen-1-ol, 3-methyl-1-penten-3-ol, 1-hepten-3-ol, 1- Octen-3-ol, 6-
And unsaturated alcohols such as methyl-5-hepten-2-ol. The amount of the alcohol to be used is generally 1 to 30 moles, preferably 1 to 10 moles, per 1 mole of the compound represented by the general formula [5].

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 to be used is generally 0.1 to 20 mol%, preferably 1 to 10 mol%, relative to the compound represented by the general formula [5].

The reaction solvent used if necessary includes, for example, hydrocarbons such as toluene, xylene, benzene, cyclohexane, n-hexane and n-octane, and halogenated hydrocarbons such as methylene chloride, dichloroethane and trichloroethylene. For example, esters such as methyl acetate, ethyl acetate, n-butyl acetate and methyl propionate; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol; Examples include ethers such as diethyl ether, diisopropyl ether, 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 usually 0 to 150 ° C., preferably 2 to 150 ° C.
0-80 ° C. The reaction time varies depending on the type and concentration of the compound to be reacted, but is usually 0.5 to 10 hours.

The monomer represented by the general formula [1] of the present invention can be obtained, for example, by adding the compound represented by the general formula [5] and a diol to a suitable solvent, if necessary, in the presence of an acid catalyst. It can also be obtained by reacting.

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 and the like. The amount of the diols to be used is generally 1 to 20-fold the molar amount of the compound represented by the general formula [5],
Preferably it is 3 to 10 times mol.

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 to be used is generally 0.1 to 20 mol%, preferably 1 to 10 mol%, relative to the compound represented by the general formula [5].

Examples of the reaction solvent used if necessary include hydrocarbons such as toluene, xylene, benzene, cyclohexane, n-hexane and n-octane, and halogenated hydrocarbons such as methylene chloride, dichloroethane and trichloroethylene. For example, esters such as methyl acetate, ethyl acetate, n-butyl acetate and methyl propionate; ethers such as dimethyl ether, diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran and dioxane; N-methylpyrrolidone; Examples include 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 usually 0 to 150 ° C., preferably 2 to 150 ° C.
0-130 ° C. The reaction time varies depending on the type and concentration of the compound to be reacted and the like, but is usually 0.5 to 48 hours.

In any of the above-mentioned methods, the obtained monomer represented by the general formula [1] may be directly subjected to a polymerization reaction without purification and / or isolation (that is, unreacted product). May be in a state in which the compound represented by the general formula [5] coexists.), And once purified and / or isolated by an arbitrary operation such as extraction and recrystallization, and then subjected to the next reaction. May be attached. The operation of the reaction other than the above, post-treatment, and the like may be performed according to those of the same kind of reaction that is usually performed.
As the compound represented by the general formula [5], a commercially available product or a compound produced by a conventional method may be used.

The monomer having an alkylsilyl group according to the present invention may be obtained by combining the monomer of the present invention obtained by any of the above-mentioned production methods with an alkylsilyl halide in a suitable solvent if necessary. By reacting in the presence of

Examples of the alkylsilyl halide include chlorotrimethylsilane, chlorotriethylsilane, chlorodimethylethylsilane, chlorotripropylsilane, chlorotriisopropylsilane, chlorotributylsilane, chlorotrihexylsilane, and butylchlorodimethylsilane. . The amount of the alkylsilyl halide to be used is generally 1- to 20-fold mol, preferably 1- to 5-fold mol, of the compound represented by the general formula [5].

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 alkali metal compounds such as lithium. The amount of basic catalyst used is
It is usually 0.1 to 20 times, preferably 1 to 5 times the mole of the compound represented by the formula [5].

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

The reaction temperature is generally 0 to 150 ° C., preferably 2 to 150 ° C.
0-80 ° C. The reaction time is determined by the general formula [5] to be reacted.
The reaction time is usually 0.5 to 48 hours, depending on the reaction conditions such as the type and concentration of the compound represented by

The obtained monomer represented by the general formula [1] may be directly subjected to a polymerization reaction without purification and / or isolation (that is, unreacted compound represented by the general formula [5]). The compound may be in the state of coexistence.), And once purified and / or isolated by any operation such as extraction and recrystallization, it may be subjected to the next reaction. The operation of the reaction other than the above, post-treatment, and the like may be performed according to those of the same kind of reaction that is usually performed.

The polymer of the present invention comprising the monomer unit represented by the general formula [1a] according to the present invention as a structural unit includes a homopolymer comprising the monomer unit represented by the general formula [1a] as a structural unit: General formula [1a]
A copolymer comprising two or more types of monomer units represented by the following formulas, and a monomer unit 1 represented by the general formula [1a]:
More than species and general formula [1b]

[0090]

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(Wherein, R ^{5 ′} , R ^{6 ′} , R ^{7 ′} and Z ′ have the same meanings as R ⁵ , R ⁶ , R ⁷ and Z in the general formula [1a], respectively. R 'represents a hydroxyalkyl group.)
And a copolymer comprising, as a constituent unit, one or more monomer units represented by the general formula [1a] and one or more monomer units represented by the general formula [1a]:

[0092]

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[0093] (wherein, 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, Aryl group,
Aliphatic heterocyclic group, aromatic heterocyclic group, halogen atom,
Alkyloxycarbonyl group, aralkyloxycarbonyl group, hydroxyalkyloxycarbonyl group, aryloxycarbonyl group, acyloxy group, cyano group,
Represents a carboxyl group, a formyl group, an amino group, a sulfonic acid group, a carbamoyl group or a hydroxyl group. Note that R
¹⁰ and R ¹³ combine to form -CO-O-CO- or -CO-
NH-CO- may be formed. And the like, as a constituent unit.

In the general formula [1b], examples of the hydroxyalkyl group represented by R ′ include the following general formula [2]
a].

[0095]

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(Wherein R ^{1 ′} and R ^{2 ′} have the same meanings as defined for R ¹ and R ² , respectively)

Specific examples of R ^{1 ′} , R ^{2 ′} , R ^{5 ′} , R ^{6 ′} , R ^{7 ′,} and Z ′ are R ¹ , R ² , R ⁵ , R ⁶ , R
⁷ and similar ones in Z.

In the general formula [6a], 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. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, ter
t-butyl group, sec-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 3,3-dimethylbutyl group, 1,1-dimethylbutyl group, 1-methylpentyl group, n-hexyl group And an isohexyl group.
Examples of the halogen atom represented by R ⁹ , R ¹⁰ , R ¹¹ and R ¹³ include fluorine, chlorine, bromine, iodine and the like.

The alkyloxycarbonyl group represented by R ¹⁰ , R ¹¹ and R ¹³ may be linear, branched or cyclic, and may have 1 to 3 double bonds. For example, an alkyloxycarbonyl group having 2 to 19 carbon atoms may be mentioned. In the case of a cyclic ring, the ring may be monocyclic or polycyclic, and examples thereof include those having 6 to 14 carbon atoms. Specific examples of the alkyloxycarbonyl group include a methyloxycarbonyl group, an ethyloxycarbonyl group,
Propyloxycarbonyl, butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, ethenyloxycarbonyl, propenyloxycarbonyl , Butenyloxycarbonyl group, tert-butyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, cyclohexyloxycarbonyl group, tricyclodecanyloxycarbonyl group, adamantyloxycarbonyl group, norbornyloxycarbonyl group, bicyclo [3.2. 1] octenyloxycarbonyl group, bicyclo [2.2.2] octyloxycarbonyl group, menthyloxycarbonyl group, isobornyloxycarbonyl group and the like. .

The alkyl group represented by R ¹³ may be linear, branched, or cyclic, and may have a double bond. Examples thereof include an alkyl group having 1 to 20 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, 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, hexadecyl group, octadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, pentenyl group,
Examples include a hexenyl group, a heptenyl group, and an octenyl group. Examples of the haloalkyl group include a haloalkyl group having 1 to 20 carbon atoms in which the above alkyl group is halogenated (for example, fluorinated, chlorinated, brominated, or iodinated). 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 aryl group, for example, a phenyl group,
Tolyl, xylyl, naphthyl, anthryl, 4-
Examples include an ethylphenyl group, a 4-methoxyphenyl group, a 4-vinylphenyl group, and a 4-chlorophenyl group. 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 aromatic heterocyclic group, for example, a 5-membered or 6-membered aromatic 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 a pyridyl group, an imidazolyl group, a thiazolyl group, a furanyl group, and a pyranyl group.

As the aralkyloxycarbonyl group,
For example, an aralkyloxycarbonyl group having 8 to 20 carbon atoms may be mentioned, and specifically, a benzyloxycarbonyl group,
And a phenethyloxycarbonyl group. As the acyloxy group, for example, a group having 2 to 2 carbon atoms derived from a carboxylic acid
Preferred are acyloxy groups of 18, specifically, acetyloxy, propionyloxy, butyryloxy,
Examples include a pentanoyloxy group, a hexanoyloxy group, a heptanoyloxy group, an octanoyloxy group, a lauroyloxy group, a stearoyloxy group, and a benzoyloxy group.

Examples of the hydroxyalkyloxycarbonyl group include a hydroxyalkyloxycarbonyl group having 2 to 18 carbon atoms in which a hydrogen atom of the above-described alkyloxycarbonyl group is substituted with a hydroxyl group. Group, hydroxyethyloxycarbonyl group, hydroxypropyloxycarbonyl group, hydroxybutyloxycarbonyl group,
Examples include a hydroxypentyloxycarbonyl group, a hydroxyhexyloxycarbonyl group, a hydroxyheptyloxycarbonyl group, a hydroxyoctyloxycarbonyl group, a hydroxydodecyloxycarbonyl group, and a hydroxyoctadecyloxycarbonyl group. Examples of the aryloxycarbonyl group include, for example, those having 7 to
15 aryloxycarbonyl groups are preferred, and specific examples include a phenyloxycarbonyl group and a naphthyloxycarbonyl group.

The alkylene group optionally having a double bond represented by R ¹² may be linear or branched,
For example, an alkylene group having 1 to 10 carbon atoms may be mentioned, and when the alkylene group has a double bond, one or more double bonds, preferably 1 to 2 at any position in the chain of the alkylene group.
Those having 5 or more preferably 1 to 3 are mentioned, and specifically, 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, ethenylene group, propenylene group, butenylene group, pentenylene group, hexenylene group, butadienylene group, and the like. Can be

The monomer unit represented by the general formula [6a] is represented by the general formula [6]

[0106]

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(Wherein, R ^{9 to} R ¹³ are the same as described above). Specific examples of the monomer include ethylenically unsaturated aromatic hydrocarbons having 8 to 20 carbon atoms such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene and divinylbenzene, for example, vinyl formate, C3-C20 alkenyl esters such as vinyl acetate, vinyl propionate, and isopropenyl acetate; for example, halogen-containing ethylenic compounds having 2 to 20 carbon atoms such as vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, and tetrachloroethylene; Unsaturated compounds such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid,
Citraconic acid, mesaconic acid, vinyl acetic acid, allyl acetic acid,
C3-20 ethylenically unsaturated carboxylic acids such as vinylbenzoic acid (these acids may be in the form of a salt such as an alkali metal salt such as sodium or potassium or an ammonium salt), for example. Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, vinyl methacrylate, allyl methacrylate, phenyl methacrylate, benzyl methacrylate, adamantyl methacrylate, Tricyclodecanyl methacrylate, menthyl methacrylate, norbornyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, acrylic acid Tearyl, vinyl acrylate, adamantyl acrylate, tricyclodecanyl acrylate, menthyl acrylate, norbornyl acrylate, isobornyl acrylate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl maleate, dimethyl fumarate, fumarate Diethyl citrate, methyl crotonate, ethyl crotonate, vinyl crotonate, dimethyl citraconic acid, diethyl citrate, dimethyl mesaconate, diethyl mesaconate, methyl 3-butenoate,
2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate,
C4-20 ethylenically unsaturated carboxylic esters such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate and 2-hydroxypropyl acrylate, for example carbons such as acrylonitrile, methacrylonitrile, allyl cyanide A cyanoethylenically unsaturated compound having 3 to 20 carbon atoms such as acrylamide, methacrylamide and maleimide; and a C3 to 20 ethylenically unsaturated amide compound such as acrolein and crotonaldehyde. Ethylenically unsaturated aldehydes, for example, ethylenically unsaturated sulfonic acids having 2 to 20 carbon atoms such as vinyl sulfonic acid and 4-vinylbenzene sulfonic acid (these acids include salts of salts such as alkali metal salts such as sodium and potassium). It may be in the form of a form.), For example, vinylamine, allylamine Of carbon atoms 2-20 ethylenically unsaturated aliphatic amines, for example, ethylenically unsaturated aromatic amines having 8 to 20 carbon atoms such as vinyl aniline, for example N
5-5-2 carbon atoms such as vinylpyrrolidone and vinylpiperidine
0 ethylenically unsaturated aliphatic heterocyclic amines such as vinylpyridine, 1-vinylimidazole, etc.
To 20 ethylenically unsaturated aromatic heterocyclic amines such as allyl alcohol and crotyl alcohol; and C3 to C20 ethylenically unsaturated alcohols; and C8 to C20 ethylene such as 4-vinylphenol. C4 of unsaturated unsaturated phenols such as butadiene and isoprene
To 20 diene compounds.

When the polymer of the present invention is used as a resist material, it is a copolymer having the general formula [1a] and the general formula [1b] as structural units, and the general formula [1]
b] other monomer units represented by R ^{5 ′} , R ^{6 ′} and R
^{7 ′} and Z ′ are respectively R ⁵ , R ⁶ and R in the general formula [1a].
Binary copolymers identical to ⁷ and Z, and the general formula [1
a], [1b] and [6a] as constituent units, wherein R ^{5 ′} , R ^{6 ′} , R ^{7 ′} and Z ′ of other monomer units represented by the general formula [1b] are each a general unit The same as R ⁵ , R ⁶ , R ⁷ and Z in the formula [1a],
And one or two monomer units represented by the general formula [6a]:
Particularly preferred are tertiary or quaternary copolymers containing species.

When the polymer of the present invention is used as a resist material for ArF, monomers other than the monomer of the present invention which are polymerized in combination with the monomer of the present invention preferably do not contain an aromatic group. Specific examples of the polymer of the present invention include, for example, polymers having the following combinations of segments.

[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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The polymer of the present invention can be obtained, for example, by any of the following methods (a) and (b).

(A) Method-1 The monomer of 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. The polymerization reaction is carried out at -150 ° C for 0.5-20 hours according to a conventional method. After the reaction, a post-treatment is carried out according to a conventional method for obtaining a polymer to obtain a compound represented by the general formula [1a]:
Can be obtained as a target polymer comprising the monomer unit represented by the formula (1) as a constitutional unit.

Examples of the radical polymerization initiator include azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (methyl 2-methylpropionate), , 2'-azobis (2-methylbutyronitrile),
Azo-based polymerization initiators such as 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) such as lauroyl peroxide, benzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, Peroxide-based polymerization initiators such as tert-butylperoxy-2-ethylhexanoate and the like can be mentioned.

Examples of the reaction solvent include hydrocarbons such as benzene, toluene, and xylene; esters such as ethyl acetate and n-butyl acetate;
Ethers such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, for example, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, etc. Organic solvents such as alcohols, for example, ketones such as methyl ethyl ketone and methyl isobutyl ketone. 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, another monomer are prepared in a suitable organic solvent in the presence of a catalytic amount of an organometallic catalyst, optionally under an inert gas atmosphere. The polymerization reaction is carried out at 〜0 ° C. for 0.5 to 20 hours according to a conventional method. After the reaction, post-treatment is carried out in accordance with a conventional method for obtaining a polymer, whereby a target polymer comprising a monomer unit represented by the general formula [1a] as a constituent unit can be obtained.

As the organometallic catalyst, for example, n-butyllithium, sec-butyllithium, tert-butyllithium,
Organic alkali metal compounds such as naphthalene sodium, naphthalene potassium, cumyl potassium and the like can be mentioned.

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 and acetone, esters such as ethyl acetate and n-butyl acetate, and hydrocarbons such as benzene, toluene and xylene 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 of the present invention and the other monomers during the polymerization reaction is usually 5 to 95% by weight, preferably 10 to 10% by weight, based on the solvent in both methods 1 and 2. ~ 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 constitutional unit is not particularly limited, but is usually 1,000 to 300,000, preferably 3,000 to 50,000 as a weight average molecular weight. More preferably, 5,000 to 30,000 are mentioned. The degree of polymerization is not particularly limited, but is usually 3 to 1500, preferably 6 to 250.

In the polymer of the present invention obtained by subjecting the monomer of the present invention to a polymerization reaction with another monomer, the constitutional ratio of the monomer unit represented by the general formula [1a] of the present invention to the other monomer units Is not particularly limited, but when the obtained polymer is used as a resist material, a binary copolymer composed of one monomer unit represented by each of the general formulas [1a] and [1b] is generally used. The proportion of the monomer unit represented by the formula [1a] is 10 to 95 mol%, preferably 20 to 80 mol%, and at least one monomer unit represented by the general formulas [1a], [1b] and [6a] In the ternary or quaternary copolymer consisting of: the total of the monomer units represented by the general formula [1a] and the monomer units represented by the general formula [6a] is 10 to 95 mol , Preferably from 20 to 70 mol%, and the general formula [6a] 1 to 25 mol% of the total proportion of the monomer unit represented by, preferably from 2 to 20 mol%.

The polymer of the present invention thus obtained is characterized by having a protected hydroxyalkyl group represented by, for example, the general formula [2] or [3] in the molecule.

That is, when the polymer of the present invention is used as a resist material, the protected hydroxyalkyl group-protecting group represented by the general formula [2] or [3] in the polymer is generated by exposure. by being deprotected by the acid, a group represented by a soluble group conventionally used novolac resins and phenolic resins a phenolic hydroxyl group equivalent pK _a (12~13). Therefore, by using the polymer of the present invention having a protected hydroxyalkyl group represented by the general formula [2] or [3], 2.38% of the existing alkali developing solution in the post-exposure development processing can be obtained. A TMAH aqueous solution can be used, and it is possible to provide a resist material which can easily control the dissolution rate during alkali development and has excellent dissolution characteristics.

A resist composition comprising the polymer of the present invention, a photosensitive compound capable of generating an acid upon exposure, and a solvent capable of dissolving them, is a resist for ArF excimer laser, which is a promising next-generation exposure technique. It is extremely effective as a material.

When the polymer of the present invention is used as a resist composition, a photosensitive compound which generates an acid upon exposure to light (hereinafter abbreviated as an acid generator) used in combination with the resist composition has an adverse effect on resist pattern formation. As long as it does not affect, it can maintain the high transparency of the resist composition with good light transmittance around 193 nm,
Alternatively, an acid generator capable of increasing light transmittance around 193 nm by exposure and maintaining high transparency of the resist composition is more preferable.

Particularly preferred acid generators in the present invention include, for example, commercially available 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 .1] Sulfonimide 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-butylsulfonyl) diazomethane, tert-butylsulfonylmethylsulfonyldiazomethane , Cyclohe Diazodisulfone compounds such sill sulfonyl ethylsulfonyl diazomethane.

The solvent used when the polymer of the present invention is used as a resist composition may be any solvent that can dissolve the polymer of the present invention and an acid generator. Those which are good and do not have absorption around 190 to 400 nm are more preferable. Specifically, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, 2-ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, and 3-methoxypropionic acid Methyl, 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, etc. No.

The resist composition containing the polymer of the present invention usually comprises the above three components (the polymer of the present invention, an acid generator and a solvent) as main components, and if necessary, an ultraviolet absorber may be added. May be. Specific examples of the ultraviolet absorber, 9-diazofluorene and its derivatives, 1-diazo-2-tetralone, 2-diazo-1-tetralone, 9-diazo-1
0-phenanthrone, benzophenone, 9- (2-methoxyethoxy) methylanthracene, 9- (2-ethoxyethoxy)
Methylanthracene, 9- (4-methoxybutoxy) methylanthracene, 9-anthracenemethyl acetate and the like can be mentioned.

Further, a sensitivity adjuster, a plasticizer, an organic acid, a surfactant and the like usually used in this field may be added to a resist composition containing at least one polymer of the present invention, if necessary. Good. Examples of the sensitivity adjuster include polyvinylpyridine, poly (vinylpyridine / 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.

Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dipropyl phthalate and the like. Organic acids include, for example, salicylic acid, lactic acid, 2-
Examples thereof include hydroxynaphthalene-3-carboxylic acid, 2-nitrobenzoic acid, phthalic acid, succinic acid, and malonic acid.

Examples of the surfactant include commercially available various nonionic surfactants, cationic surfactants, anionic surfactants, and various fluorine surfactants. For example, Florard (trade name of Sumitomo 3M Co., Ltd.) ), F-Top (trade name of Tochem Products Co., Ltd.), Surflon (trade name of Asahi Glass Co., Ltd.), Fentgent (trade name of Neos Co., Ltd.), Megafac (trade name of Dai Nippon Ink Co., Ltd.), Unidyne (Daikin Industries, Ltd.). ｝
And the like.

The pattern formation using the resist composition containing the polymer of the present invention is performed, for example, as follows.
That is, a resist composition containing the polymer of the present invention is applied on a semiconductor substrate such as a silicon wafer, for example, with a thickness of
It is applied so as to have a thickness of about 0.3 to 2.0 μm (about 0.1 to 0.5 μm when it is used as an upper layer of three layers), and this is placed in an oven at 70 to 130 ° C. for 10 to 30 minutes, or on a hot plate for 60 to Prebake at 150 ° C, preferably 60-110 ° C for 60-180 seconds.

Next, a mask for forming a target pattern is held over the resist film obtained as described above, and a deep ultraviolet ray of, for example, 220 nm or less is irradiated so as to have an exposure amount of about 1 to 100 mJ / cm ^2. And then 60-150 on hot plate
Bake at 60 ° C, preferably 60-110 ° C for 60-180 seconds. Further, using a developing solution such as a 0.1-5% aqueous solution of tetramethylammonium hydroxide (TMAH), for about 0.5-3 minutes, dipping method, puddle method, spraying
Develop by a conventional method such as a method. Through this series of operations, a target pattern can be formed on the substrate.

The mixing ratio of the polymer of the present invention to the acid generator in the resist composition is 1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the polymer. . Further, the amount of the solvent in the resist composition according to 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 of the present invention and the acid generator onto a substrate. The amount is usually 1 to 20 weight, preferably 1.5 to 10 weight per 1 weight of the polymer.

As the developing solution used in the pattern forming method using various developing solutions as described above, an appropriate developing solution which can increase the difference in solubility between exposed and unexposed portions according to the solubility of the resist material. An alkaline aqueous solution having a suitable concentration is mentioned, and the concentration is usually 0.01 to 20%. Examples of the alkaline aqueous solution include organic amines such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline, triethanolamine, morpholine, and 1-methylmorpholine. For example, an aqueous solution containing an inorganic alkali compound such as sodium hydroxide, potassium hydroxide or the like can be used.

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).

As described above, in the resist composition containing the polymer of the present invention, the protected hydroxyalkyl group-protecting group represented by the general formula [2] or [3] in the polymer is generated by exposure. Is converted to a β-ketoester group by deprotection with the acid, and the tautomerism causes the same p-type as a phenolic hydroxyl group which is a soluble group of a novolak resin or a phenol resin conventionally used.
Since an enol hydroxyl group having K _a (12 to 13) is generated, an existing alkaline developer 2.38% TMAH aqueous solution can be used in the development processing after exposure, and the dissolution rate during alkaline development can be reduced. Control became possible. That is, by using the resist composition containing the polymer of the present invention, a good resist pattern can be obtained, and thus it becomes possible to manufacture a semiconductor device such as a semiconductor integrated circuit having a higher degree of integration.

Further, it has been confirmed that the resist composition containing the polymer of the present invention generates an acid even by irradiation with deep ultraviolet light, KrF excimer laser light, and electron beam or soft X-ray, and has a chemical amplification effect. I have. Therefore, the resist composition of the present invention uses low-exposure deep ultraviolet light, Kr
It is a resist material that can be patterned by F excimer laser light and electron beam or soft X-ray irradiation.

The resist material containing the polymer of the present invention will be described in a concrete example. A deep ultraviolet light having a wavelength of 220 nm or less, for example, an ArF excimer laser light (λ = 193n)
An acid is generated at the site exposed by m) or the like according to a photoreaction represented by the following [Formula 1], [Formula 2], or [Formula 3].

[0153]

(Equation 1)

[0154]

(Equation 2)

[0155]

(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 following formulas [Equation 4] and [Equation 5], becomes alkali-soluble and develops upon development. It elutes in the developer.

[0157]

(Equation 4)

[0158]

(Equation 5)

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

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

[0161]

【Example】

Example 1. Synthesis of 2- (methacryloyloxy) ethyl 3-methoxy-2-butanoate 2- (methacryloyloxy)
32.1 g (150 mmol) of ethyl acetoacetate and 49 ml (450 mmol) of methyl orthoformate were mixed, and 1.74 g (7.5 mmol) of camphorsulfonic acid was added thereto. The mixture was stirred and reacted at room temperature for 5 hours. After the reaction is completed, the reaction solution is
After dilution with 100 ml, saturated aqueous sodium hydrogen carbonate solution 5
The mixture was washed twice with 0 ml, 50 ml of water and 50 ml of saturated saline in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was subjected to column chromatography [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent:
n-hexane / ethyl acetate = 4/1] to give 2- (methacryloyloxy) ethyl
3-methoxy-2-butanoate

[0162]

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13.7 g (40.0% yield) was obtained. ¹ H-NMR δ ppm (CDCl ₃ , 270 MHz): 1.96 (s, 3H),
2.29 (s, 3H), 3.64 (s, 3H), 4.33-4.39 (m, 4H), 5.0
4 (s, 1H), 5.59 (s, 1H), 6.14 (s, 1H).

Example 2. Synthesis of 2- (methacryloyloxy) ethyl 3,3-ethylenedioxybutanoate 2- (methacryloyloxy) ethyl acetoacetate 2
1.4 g (100 mmol) and ethylene glycol 18.62 g (30
0 mmol) was dissolved in 100 ml of toluene, and 0.19 g (1 mmol) of p-toluenesulfonic acid monohydrate was added thereto, and the mixture was refluxed for 2 hours while removing water produced as a by-product with a water separator. . After the completion of the reaction, the reaction solution was diluted with 50 ml of a saturated aqueous solution of sodium bicarbonate and 50 ml of water.
2. Washed successively with 50 ml of saturated saline and dried over anhydrous magnesium sulfate. After evaporating the solvent, the obtained crude product is purified by column chromatography [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent: n-hexane / ethyl acetate = 3/2] To produce the desired slightly yellow oily 2-
(Methacryloyloxy) ethyl 3,3-ethylenedioxybutanoate

[0165]

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19.44 g (75.3% yield) was obtained. ¹ H-NMR δ ppm (CDCl ₃ , 270 MHz): 1.51 (s, 3H),
1.95 (s, 3H), 2.71 (s, 2H), 3.98 (s, 4H), 4.36 (s,
4H), 5.59 (s, 1H), 6.14 (s, 1H).

Example 3. Synthesis of 2- (methacryloyloxy) ethyl 3,3- (2 ', 2'-dimethylpropylenedioxy) butanoate 2- (methacryloyloxy) ethyl acetoacetate 2
1.4 g (100 mmol) and 3,1.25 g (300 mmol) of 2,2-dimethylpropylene glycol were dissolved in 100 ml of toluene, and 0.19 g (1 mmol) of p-toluenesulfonic acid monohydrate and 0.5 g of phenothiazine were added thereto. A reflux reaction was performed for 2 hours while removing water produced as a by-product with a water separator. After completion of the reaction, the reaction solution was washed sequentially with 50 ml of a saturated aqueous solution of sodium bicarbonate, 50 ml of water × 2 and 50 ml of a saturated saline solution, and dried over anhydrous magnesium sulfate. After distilling off the solvent, the obtained crude product was distilled under reduced pressure to obtain the desired light yellow oil, 2- (methacryloyloxy) ethyl 3,3- (2 ′, 2′-dimethylpropylenedioxy) butanoate.

[0168]

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20.69 g (68.9% yield) were obtained. Boiling point: 151-156 ° C / 4mmHg. ¹ H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.94, 0.98
(S, 3H x 2), 1.54 (s, 3H), 1.95 (s, 3H), 2.82 (s, 2
H), 3.98 (s, 4H), 4.36 (s, 4H), 5.59 (s, 1H), 6.1
3 (s, 1H).

Example 4. Synthesis of 4- (3-methoxy-2-butenoyloxymethyl) -8- (methacryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane (1) Tricyclo [5.2.1.0 ^2,6 ] decane-4,8-dimethanol 98.15 g (0.50 mol) and pyridine 41.53 g (525
mmol) in 600 ml of anhydrous tetrahydrofuran.
Cool to the following, 52.27 g of methacrylic acid chloride (0.50mo
l) is added dropwise over 1 hour. After stirring at the same temperature for another hour, the mixture is stirred at room temperature for 6 hours. The resulting pyridinium salt is removed by filtration, and the mother liquor is concentrated under reduced pressure. The obtained residue was dissolved in 1 liter of methylene chloride, and 2% hydrochloric acid and saturated saline were added, each of which was 500 ml.
Wash sequentially. It was 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 = 3/2] As a result, 52.73 g (yield: 39.9%) of 8- (methacryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane-4-methanol as a desired slightly yellow oil was obtained. ¹ H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.83-1.04 (m, 1
H), 1.20-1.88 (m, 7H), 1.95 (s, 3H), 2.01-2.22
(M, 4H), 2.32-2.58 (m, 2H), 3.36-3.52 (m, 2H), 3.
89-4.02 (m, 2H), 5.55 (s, 1H), 6.10 (s, 1H).

[0171] (2) obtained in (1) 8- (methacryloyloxymethyl) tricyclo [5.2.1.0 ^{2, 6]} decan-4-methanol 50.23G (0.19 mol) and triethylamine 0.
05 g was dissolved in 100 ml of toluene, and 16.3 g of diketene (193.
8 mmol) was added dropwise at 30 ° C. over 1 hour, and the mixture was stirred and reacted at the same temperature for 4 hours. After standing overnight, the reaction mixture was washed with 1N-H ₂ SO ₄ 1
The mixture was washed four times with 00 ml and 100 ml of water four times with 100 ml of saturated saline, and dried over anhydrous magnesium sulfate. Evaporate the solvent,
4-acetoacetoxymethyl-8-
(Methacryloyloxymethyl) tricyclo [5.2.1.
0 ^2,6 ] decane

[0172]

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66.0 g (yield 100%) was obtained. ¹ H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.87-1.05 (m, 1
H), 1.21-1.88 (m, 7H), 1.94 (s, 3H), 1.99-2.24
(M, 4H), 2.27 (s, 3H), 2.30-2.56 (m, 2H), 3.45
(S, 2H), 3.86-4.05 (m, 4H), 5.55 (s, 1H), 6.10
(S, 1H). (3) 4-acetoacetoxymethyl-8- obtained in (2)
(Methacryloyloxymethyl) tricyclo [5.2.1.
0 ^2,6 ] decane 34.84 g (100 mmol) was added to methyl orthoformate 33
Dissolve in 300 ml (300 mmol) and add camphorsulfonic acid 1.
After charging 16 g (5 mmol), the mixture was stirred and reacted at room temperature for 8 hours. After standing overnight, the reaction mixture was diluted with 120 ml of toluene, washed successively with 50 ml of saturated aqueous sodium bicarbonate, 50 ml of water and 50 ml of saturated saline, and dried over anhydrous magnesium sulfate. After evaporating the solvent,
The obtained crude product is subjected to column chromatography [filler:
Purified by Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd .; eluent: n-hexane / ethyl acetate = 4/1) to obtain 4- (3-methoxy-2) as a target light yellow oil -Butenoyloxymethyl) -8- (methacryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane

[0174]

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There were obtained 10.79 g (yield 29.8%). ¹ H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.92-1.08 (m, 1
H), 1.21-1.90 (m, 7H), 1.94 (s, 3H), 2.01-2.24
(M, 4H), 2.29 (s, 3H), 2.30-2.58 (m, 2H), 3.64
(S, 3H), 3.84-4.03 (m, 4H), 5.02 (s, 1H), 5.55
(S, 1H), 6.10 (s, 1H).

Example 5. Synthesis of 3- (methacryloyloxy) menthan-8-yl 3-methoxy-2-butenoate (1) Menthane-3,8-diol 50.0 g (290 mmol) and pyridine 24.11 g (305 mmol) Is dissolved in 350 ml of anhydrous tetrahydrofuran, cooled to 5 ° C. or lower, and 30.34 g (290 mmol) of methacrylic chloride is added dropwise over 1 hour. After stirring at the same temperature for another hour, the mixture is stirred at room temperature for 6 hours. The resulting pyridinium salt is removed by filtration, and the mother liquor is concentrated under reduced pressure. The obtained residue was dissolved in methylene chloride (600 ml),
The mixture was washed sequentially with 2% hydrochloric acid and saturated saline and 300 ml each, and dried over anhydrous magnesium sulfate. The solvent is distilled off, and the desired slightly yellow oily 3- (methacryloyloxy) menthane-8
69.0 g (99% yield) of all were obtained. ¹ H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.88 (d, 3H, J =
6.59Hz), 1.15 (s, 3H), 1.20 (s, 3H), 0.92-1.13
(M, 2H), 1.41-1.48 (m, 1H), 1.61-1.88 (m, 4H), 1.
96 (s, 3H), 1.94-2.09 (m, 1H), 5.30 (s, 1H), 5.59
(S, 1H), 6.12 (s, 1H).

(2) 67.01 g (280 mmol) of 3- (methacryloyloxy) menthan-8-ol obtained in (1) and 0.57 g of triethylamine were dissolved in 140 ml of toluene.
After 24.7 g (294 mmol) of diketene was added dropwise at 30 ° C. over 30 minutes, the mixture was reacted at the same temperature for 4 hours with stirring. After standing overnight, the reaction solution was washed with 150 ml of 1N-H ₂ SO _4, 150 ml of water four times and then with 150 ml of saturated saline, and dried over anhydrous magnesium sulfate. After distilling off the solvent, the obtained crude product is subjected to column chromatography [filler: Wakogel C-200 (Wako Pure Chemical Industries, Ltd.)
Eluent: n-hexane / ethyl acetate = 3/2]
3- (methacryloyloxy) menthan-8-yl acetoacetate

[0178]

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66.5 g (73.4% yield) was obtained. ¹ H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.87 (d, 3H, J =
6.6Hz), 0.98-1.19 (m, 2H), 1.46 (s, 6H), 1.43-1.5
1 (m, 1H), 1.60-1.68 (m, 3H), 1.71-1.90 (m, 1H),
1.95 (s, 3H), 2.11-2.17 (m, 1H), 2.24 (s, 3H), 3.3
7 (s, 2H), 5.36 (s, 1H), 5.58 (s, 1H), 6.11 (s, 1
H). (3) 32.34 g (100 mmol) of 3- (methacryloyloxy) menthan-8-yl acetoacetate obtained in (2) was dissolved in 66 ml (600 mmol) of methyl orthoformate, and 1.16 g (5 mmol) of camphorsulfonic acid was added thereto. And then at room temperature
The reaction was stirred for a period of time. After standing overnight, the reaction solution is
The mixture was diluted with 20 ml, washed successively with 50 ml of saturated aqueous sodium bicarbonate, 50 ml of water and 50 ml of saturated saline, and dried over anhydrous magnesium sulfate. After distilling off the solvent, the obtained crude product is subjected to column chromatography [filler: Wakogel C-200 (Wako Pure Chemical Industries, Ltd.)
Eluent: n-hexane / ethyl acetate = 3/2]
Purified by purification, the desired pale yellow oily 3- (methacryloyloxy) menthan-8-yl 3-methoxy-2-butenoate

[0180]

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6.75 g (yield 20.0%) was obtained. ¹ H-NMR δ ppm (CDCl ₃ , 270 MHz): 0.87 (d, 3H, J =
6.23Hz), 1.06-1.19 (m, 2H), 1.45 (s, 6H), 1.43-1.
51 (m, 3H), 1.64-1.74 (m, 1H), 1.92-1.99 (m, 1H),
2.17 (s, 3H), 2.18-2.30 (m, 1H), 2.23 (s, 3H), 3.6
0 (s, 3H), 4.93 (s, 1H), 5.36 (s, 1H), 5.56 (s, 1
H), 6.12 (s, 1H).

Example 6. Synthesis of polymer 4.0 g (40 mmol) of methyl methacrylate, 2- (methacryloyloxy) ethyl 3-methoxy-2- obtained in Example 1
A mixture of 11.4 g (50 mmol) of butenoate, 2.14 g (10 mmol) of 2- (methacryloyloxy) ethyl acetoacetate and 60 ml of dry tetrahydrofuran (THF) was heated to 65 ° C., and then azobisisobutyronitrile 1.9 was heated.
7 g (12 mmol) was added and a polymerization reaction was carried out at the same temperature for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution is
The polymer was precipitated by pouring into 50 ml. This is filtered,
Drying yielded 14.6 g (83% yield) of the desired product. The composition ratio of methyl methacrylate unit, 2- (methacryloyloxy) ethyl 3-methoxy-2-butenoate unit and 2- (methacryloyloxy) ethyl acetoacetate unit in the obtained polymer was about 0.47: 0.47 by ¹ H-NMR measurement. 0.06
Met. GPC (gel permeation chromatography, solvent: tetrahydrofuran) measurement using polystyrene as a standard showed a weight average molecular weight (Mw) of 12,700,
The dispersity was 2.11.

Example 7. Synthesis of polymer 4-acetoacetoxymethyl obtained in Example 4 (2)
-8- (methacryloyloxymethyl) tricyclo [5.2.1.0
^2,6 ] decane 7.67 g (22 mmol), 2-
4.11 g (18 mmol) of (methacryloyloxy) ethyl 3-methoxy-2-butenoate and 25 ml of dry tetrahydrofuran (THF) were mixed and heated to 65 ° C.
0.79 g (4.8 mmol) of azobisisobutyronitrile was added, and a polymerization reaction was carried out at the same temperature for 5 hours in a nitrogen stream. After completion of the reaction, the reaction solution was poured into 300 ml of n-hexane to precipitate a polymer. This is collected by filtration, dried and the desired product is 9.04 g.
(76% yield). The composition ratio of 4-acetoacetoxymethyl-8- (methacryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane unit and 2- (methacryloyloxy) ethyl 3-methoxy-2-butenoate unit in the obtained polymer is ¹ It was about 0.46: 0.54 by H-NMR measurement. Also, from GPC (solvent: tetrahydrofuran) measurement using polystyrene as a standard, the weight average molecular weight (Mw) was 42200,
The degree of dispersion was 2.96.

Example 8. Synthesis of polymer 3- (methacryloyloxy) obtained in Example 5 (2)
Mentan-8-yl acetoacetate 9.06g (28mmo
l), 4.05 g of 3- (methacryloyloxy) menthan-8-yl 3-methoxy-2-butenoate obtained in Example 5 (12
mmol) and 27 ml of dry tetrahydrofuran (THF), and the mixture was heated to 65 ° C., and 0.79 g (4.8 mmol) of azobisisobutyronitrile was added.
The polymerization reaction was carried out at the same temperature for 5 hours. After the reaction is completed,
The polymer was precipitated by pouring into 300 ml of n-hexane. This was collected by filtration and dried to obtain 6.03 g of the desired product (yield 46%). The composition ratio of 3- (methacryloyloxy) menthan-8-yl acetoacetate unit and 3- (methacryloyloxy) menthan-8-yl 3-methoxy-2-butenoate unit of the obtained polymer was about ¹ H-NMR measurement. 0.62: 0.38. In addition, GPC (solvent: tetrahydrofuran) measurement using polystyrene as a standard indicates a weight average molecular weight (M
w) was 12,700 and the degree of dispersion was 2.11.

Application Example 1 A resist composition having the following composition was prepared. (A) 4.0 g of the polymer obtained in Example 6 (b) 80 mg of an acid generator (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
After filtration with a Teflon (trade name) filter, and spin-coating the obtained filtrate on a silicon wafer, 60 ° C at 90 ° C
Baking on a hot plate for 2 seconds, the film thickness is 0.5
A μm resist film was obtained. Next, the wafer having the film formed thereon is allowed to stand in a contact type exposure test machine sufficiently purged with nitrogen, and a mask on which a pattern is drawn is brought into close contact with the resist film. (Λ = 1
93 nm; NA 0.55) 16 mJ / cm ² was exposed. 60 at 60 ° C after exposure
Heat on a hot plate for 2 seconds, and use developer [2.38% TMA]
H aqueous solution. Liquid temperature 23 ° C. ], Using a paddle method for 60 seconds, followed by rinsing with ultrapure water for 60 seconds, 0.25 μm
A line and space pattern (exposure amount: about 14 mJ / cm ² ) was obtained.

Application Example 2 Applying the resist composition prepared in (a), (b) and (c) of Application Example 1 to 0.1 μm Teflon
The solution was filtered through a (trade name) filter, and the obtained filtrate was spin-coated on a silicon wafer, and baked on a hot plate at 90 ° C. for 60 seconds to obtain a resist film having a thickness of 0.5 μm. Next, the wafer having the film formed thereon is allowed to stand in a contact type exposure test machine sufficiently purged with nitrogen, and a mask on which a pattern is drawn is brought into close contact with the resist film. (Λ = 193 nm; NA 0.5
5) 16 mJ / cm ² was exposed. After exposure, the film was heated on a hot plate at 60 ° 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 0.18 μm (exposure amount: about 17 mJ / c
m ² ) was obtained.

Application Example 3 A resist composition having the following composition was prepared. (A) 1.0 g of the polymer obtained in Example 7 (b) 20 mg of an acid generator (triphenylsulfonium trifluoromethanesulfonate) (c) 4.0 g of ethylene glycol dimethyl ether

The resist composition having the above composition was used in an amount of 0.1 μm
After filtration with a Teflon (trade name) filter, and spin-coating the obtained filtrate on a silicon wafer, 60 ° C at 90 ° C
Baking on a hot plate for 2 seconds, the film thickness is 0.5
A μm resist film was obtained. Next, the wafer having the film formed thereon is allowed to stand in a contact type exposure test machine sufficiently purged with nitrogen, and a mask on which a pattern is drawn is brought into close contact with the resist film. (Λ = 1
93 nm; NA 0.55) 16 mJ / cm ² was exposed. 60 at 90 ° C after exposure
Heat on a hot plate for 2 seconds, and use developer [2.38% TMA]
H aqueous solution. Liquid temperature 23 ° C. ], Using a paddle method for 60 seconds, followed by rinsing with ultrapure water for 60 seconds, 0.25 μm
A line and space pattern (exposure amount: about 14 mJ / cm ² ) was obtained.

Application Example 4 A resist composition having the following composition was prepared. (A) 1.0 g of the polymer obtained in Example 8 (b) 20 mg of an acid generator (triphenylsulfonium trifluoromethanesulfonate) (c) 4.0 g of ethylene glycol dimethyl ether

The resist composition having the above composition was used in an amount of 0.1 μm
After filtration with a Teflon (trade name) filter, and spin-coating the obtained filtrate on a silicon wafer, 60 ° C at 90 ° C
Baking on a hot plate for 2 seconds, the film thickness is 0.5
A μm resist film was obtained. Next, the wafer having the film formed thereon is allowed to stand in a contact type exposure test machine sufficiently purged with nitrogen, and a mask on which a pattern is drawn is brought into close contact with the resist film. (Λ = 1
93 nm; NA 0.55) 16 mJ / cm ² was exposed. 6 at 110 ° C after exposure
Heat on a hot plate for 0 seconds, and use a developer [2.38% TM
AH aqueous solution. Liquid temperature 23 ° C. ], Using a paddle method for 60 seconds, followed by rinsing with ultrapure water for 60 seconds, 0.25 μm
A line and space pattern (exposure amount: about 25 mJ / cm ² ) was obtained.

[0192]

As described above, the present invention provides a novel polymer useful for a resist composition used in the production of semiconductor devices and the like, and a novel monomer which can be a raw material of the polymer. The resist composition using the polymer 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. In addition, since the polymer of the present invention has a chelating ability, it can be used as a functional resin for analysis and separation in analytical chemistry, separation and purification of metals, and the like.

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────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 319/06 C07D 319/06 319/08 319/08 G03F 7/033 G03F 7/033 7/039 501 7/039 501

Claims (14)

[Claims] 1. A compound of the general formula [1] (Wherein, R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a cyano group, an alkyloxycarbonyl group or a carbamoyl group, Z represents a spacer or a bond, and R represents a terminal hydroxyl group. Represents a protected hydroxyalkyl group.) 2. A compound represented by R in the general formula [1],
A hydroxyalkyl group in which a terminal hydroxyl group is protected is represented by the general formula [2]: (Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group which may have a substituent or an alicyclic hydrocarbon group, and R ¹ and R ² represent an aliphatic ring And R ³ represents an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkyloxycarbonyl group or an alkylsilyl group.) Or a general formula [3] (In the formula, R ⁴ represents an alkyl group, R ¹ , R ² and R ³ are the same as above, and R ³ and R ⁴ may form an aliphatic ring.) The monomer of claim 1, wherein 3. The spacer represented by the general formula [4]: (Where 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 represents 0 or 1, and p represents , Q and r each independently represent 0 or 1. However, when m is 1, q is 1
Represents The monomer according to claim 1, which is a group represented by: 4. A compound represented by R in the general formula [1],
A hydroxyalkyl group in which a terminal hydroxyl group is protected is represented by the general formula [2]: (Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group which may have a substituent or an alicyclic hydrocarbon group, and R ¹ and R ² represent an aliphatic ring Wherein R ³ represents an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkyloxycarbonyl group or an alkylsilyl group.) Or a general formula [3] (In the formula, R ⁴ represents an alkyl group, R ¹ , R ² and R ³ are the same as above, and R ³ and R ⁴ may form an aliphatic ring.) Wherein A ₂ represents a divalent hydrocarbon group which may have an oxygen atom, and A ₁ and A ₃ each independently represent a lower group; Represents an alkylene group, m represents 0 or 1, and p, q and r each independently represent 0 or 1. However, when m is 1, q represents 1.) The monomer of claim 1. 5. A compound of the general formula [1a] (Wherein, R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a cyano group, an alkyloxycarbonyl group or a carbamoyl group, Z represents a spacer or a bond, and R represents a terminal hydroxyl group. Represents a protected hydroxyalkyl group.) As a constituent unit. 6. In the general formula [1a], the terminal-protected hydroxyalkyl group represented by R is represented by the general formula [2]: (Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group which may have a substituent or an alicyclic hydrocarbon group, and R ¹ and R ² represent an aliphatic ring Wherein R ³ represents an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkyloxycarbonyl group or an alkylsilyl group.) Or a general formula [3] (In the formula, R ⁴ represents an alkyl group, R ¹ , R ² and R ³ are the same as above, and R ³ and R ⁴ may form an aliphatic ring.) The polymer of claim 5, which is 7. The spacer represented by the general formula [4]: (Where 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 represents 0 or 1, and p represents , Q and r each independently represent 0 or 1. However, when m is 1, q is 1
Represents The polymer according to claim 5, which is a group represented by the formula: 8. In the general formula [1a], a hydroxyalkyl group represented by R and whose terminal hydroxyl group is protected is represented by the general formula [2]: (Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group which may have a substituent or an alicyclic hydrocarbon group, and R ¹ and R ² represent an aliphatic ring Wherein R ³ represents an alkyl group, an alkenyl group, a hydroxyalkyl group, an alkyloxycarbonyl group or an alkylsilyl group.) Or the general formula [3] (In the formula, R ⁴ represents an alkyl group, R ¹ , R ² and R ³ are the same as above, and R ³ and R ⁴ may form an aliphatic ring.) Wherein the spacer is represented by the general formula [4]: (Where 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 represents 0 or 1, and p represents , Q and r each independently represent 0 or 1. However, when m is 1, q is 1
Represents The polymer according to claim 5, which is a group represented by the formula: 9. The polymer according to claim 5, wherein the polymer is a homopolymer having a monomer unit represented by the general formula [1a] as a constituent unit. 10. The polymer according to claim 5, wherein the polymer is a copolymer having two or more monomer units represented by the general formula [1a] as constituent units. 11. A polymer comprising one or more monomer units represented by the general formula [1a] and a polymer represented by the general formula [1b]: (Wherein R ^{5 ′} , R ^{6 ′} and R ^{7 ′} are each independently a hydrogen atom,
Represents an alkyl group, a cyano group, an alkyloxycarbonyl group or a carbamoyl group, Z ′ represents a spacer or a bond, and R ′ represents a hydroxyalkyl group. 6. The polymer according to claim 5, which is a copolymer comprising, as a constitutional unit, at least one monomer represented by the formula (1). 12. A polymer comprising one or more monomer units represented by the general formula [1a] and a polymer represented by the general formula [6a]: (Wherein, 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, and R ¹¹ represents 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, and R ¹³ represents a hydrogen atom, an alkyl group, a haloalkyl group. , Aryl group, aliphatic heterocyclic group, aromatic heterocyclic group, halogen atom, alkyloxycarbonyl group, aralkyloxycarbonyl group, hydroxyalkyloxycarbonyl group, aryloxycarbonyl group, acyloxy group, cyano group, carboxyl group, formyl Group, amino group, sulfonic group, carbamoyl group or hydroxy Represents Le group. Incidentally, R ¹⁰ and R ¹³ are bonded to -CO-O-CO- or -CO-NH-CO- may form.) In monomer unit one or more indicated and 6. The polymer according to claim 5, which comprises a structural unit. 13. A monomer represented by the general formula [1]:
General formula [1] -1 (Wherein Q represents a divalent hydrocarbon group optionally having an oxygen atom, E represents a lower alkyl group, E ₁ and E ₂ represent hydrogen, or E ₁ and E ₂ represent May form an aliphatic ring) or the general formula [1] -2 (Wherein Q represents a divalent hydrocarbon group optionally having an oxygen atom, G represents a lower alkylene group, E ₁ and E ₂ represent hydrogen, or E ₁ and E ₂ represent May form an aliphatic ring.) The monomer according to claim 1, which is a monomer represented by the formula: 14. A monomer represented by the general formula [1]:
General formula [1] -3 (In the formula, X represents an alkyl group, E represents a lower alkyl group, E ₁ and E ₂ each represent hydrogen, or E ₁ and E ₂ may form an aliphatic ring.) Or the general formula [1] -4: (In the formula, X represents an alkyl group, G represents a lower alkylene group, E ₁ and E ₂ each represent hydrogen, or E ₁ and E ₂ may form an aliphatic ring.) The monomer according to claim 1, which is a monomer represented by the formula: