WO2005075446A9

WO2005075446A9 - Unsaturated carboxylic acid hemiacetal ester, polymer, and resin composition for photoresist

Info

Publication number: WO2005075446A9
Application number: PCT/JP2005/000794
Authority: WO
Inventors: Hiroshi Koyama; Keizo Inoue; Takahiro Iwahama; Mari Sumida
Original assignee: Daicel Chem; Hiroshi Koyama; Keizo Inoue; Takahiro Iwahama; Mari Sumida
Priority date: 2004-02-04
Filing date: 2005-01-17
Publication date: 2005-10-06
Also published as: KR101115224B1; KR20060124738A; WO2005075446A1

Abstract

A polymer comprising repeating units corresponding to an unsaturated carboxylic acid hemiacetal ester represented by the following formula (1): (1) (wherein Ra represents hydrogen, halogeno, C1-6 alkyl, or C1-6 haloalkyl; Rb represents a hydrocarbon group having a hydrogen atom in the 1-position; Rc represents hydrogen or a hydrocarbon group; and Rd represents an organic group containing a cyclic skeleton). The polymer may further contain repeating units corresponding to at least one monomer selected among monomers having a lactone skeleton, monomers having a cyclic ketone skeleton, monomers having an acid anhydride group, and monomers having an imide group [excluding the repeating units corresponding to the unsaturated carboxylic acid hemiacetal ester] and/or repeating units corresponding to at least one monomer selected among monomers having a hydroxy group, etc. When used in a photoresist, this polymer has the excellent property to release an acid.

Description

Description Myacetal ester of unsaturated carboxylic acid, polymer compound, and resin composition for photoresist

The present invention provides an unsaturated carboxylic acid hemiacetal ester useful as a monomer component of a resin for photoresist used in performing microfabrication of a semiconductor and a method for producing the same. The present invention relates to a polymer compound containing a repeating unit corresponding to the following, a resin composition for a photoresist containing the polymer compound, and a method for producing a semiconductor. Background art

Positive photoresist used in the semiconductor manufacturing process has characteristics such as the property that the irradiated part changes to alkali-soluble by light irradiation, adhesion to silicon wafer, plasma etching resistance, and transparency to light used. Have to get it. The positive type photo resist is generally used as a solution containing a polymer as a main agent, a photoacid generator, and several additives for adjusting the above properties. For preparation, it is extremely important that the polymer as the main ingredient has the above-mentioned properties in a well-balanced manner.

The lithography exposure light source used in semiconductor manufacturing is becoming shorter and shorter each year, and is shifting from a 248 nm wavelength KrF excimer laser to a 193 nm wavelength ArF excimer laser. . The resist polymer used in these KrF or ArF excimer laser exposure machines is desorbed by the acid generated from the photoacid generator upon exposure to Al A monomer having a function of being soluble in a re-developing solution, such as a unit having 2-methinoreadamantane-1-inole group イ 1-adamantinole-1-methinoleethyl group, is known. Kaihei 9-1 7 3 1 7 3 gazette). However, conventional photoresist resins having these units have not always been satisfactory in terms of sensitivity and degree of development. In addition, the balance between substrate adhesion, etching resistance and acid desorption was not enough. Disclosure of the invention

An object of the present invention is to provide a polymer compound having excellent acid desorption property or excellent acid desorption property and excellent substrate adhesion when used for a photoresist, a monomer thereof, and a method for producing the monomer. An object of the present invention is to provide a resin composition for photoresist containing the polymer compound, and a method for producing a semiconductor using the resin composition.

Another object of the present invention is to provide a photoresist polymer compound having a good balance of substrate adhesion, etching resistance and acid desorption properties, a photoresist resin composition containing the polymer compound, And a method for manufacturing a semiconductor using the resin composition.

Still another object of the present invention is to provide a polymer compound for photoresist, a resin composition for photoresist, and a method for producing a semiconductor, which can form a fine pattern with high accuracy.

The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, it has been found that using a polymer compound containing a repeating unit corresponding to an carboxylic acid ester of an unsaturated carboxylic acid having a specific structure as a photoresist resin, The present inventors have found that acid desorption properties or excellent acid desorption properties and excellent substrate adhesion are exhibited, and fine patterns can be formed with high accuracy, and the present invention has been completed.

That is, the present invention provides the following formula (1)

(Wherein, R ^a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms, R ^b represents a hydrocarbon group having a hydrogen atom at the 1-position, R represents a hydrogen atom or a hydrocarbon group, and R ^d represents an organic group containing a cyclic skeleton.)

Providing a myacetal ester to an unsaturated carboxylic acid represented by the formula:

Examples of the cyclic skeleton in R ^d lactone skeleton or a non-aromatic polycyclic skeleton are preferable.

The present invention also provides the following formula (3)

(Where ^Ra is a hydrogen atom, a halogen atom, and a carbon number of 1

Represents a haloalkyl group having 1 to 6 carbon atoms)

The unsaturated carboxylic acid represented by the following formula (4)

(In the formula, R represents a hydrogen atom or a hydrocarbon group, R ^d represents an organic group having a cyclic skeleton, and R ^e and R ^f each represent a hydrogen atom or a hydrocarbon group.) By reacting with a butyl ether compound, the following formula (5)

(Wherein, R ^a , R \ R ^d , R ^e , and R ^f are the same as above)

A method for producing a myacetal ester to an unsaturated carboxylic acid, characterized by obtaining a myacetal ester to an unsaturated carboxylic acid represented by the formula: The present invention also provides the following formula (I):

R ^a

"C¾—C +

No C = 0

0, (I)

R ^b — C-R ^c

0

I,

A polymer compound comprising a repeating unit represented by the formula:

The polymer further comprises at least one monomer selected from a ratatone skeleton-containing monomer, a cyclic ketone skeleton-containing monomer, an acid anhydride group-containing monomer and an imido group-containing monomer. It may contain a repeating unit [excluding the repeating unit represented by the formula (I)] corresponding to the monomer. Further, the polymer compound further includes a repeating unit corresponding to at least one monomer selected from a hydroxyl group-containing monomer, a mercapto group-containing monomer and a carboxyl group-containing monomer. May be included.

The present invention further provides a resin composition for photoresist containing at least the polymer compound and a photoacid generator.

The present invention further provides the photoresist resin composition as a base material or Provided is a method for manufacturing a semiconductor, which comprises a step of forming a resist coating film by coating on a substrate and forming a pattern through exposure and development.

In this specification, the vinyl ether monomer and the vinyl ether compound include compounds in which a hydrogen atom of a vinyl group is substituted with a substituent. Further, as a protecting group such as a hydroxyl group, a commonly used protecting group in the field of organic synthesis can be used.

ADVANTAGE OF THE INVENTION According to this invention, the polymer compound and its monomer which show the outstanding acid desorption property or the excellent acid desorption property and substrate adhesiveness when used for photoresists are provided. Further, the resin composition for photoresist of the present invention is excellent in acid desorption properties, and exhibits well-balanced substrate adhesion, etching resistance and acid desorption properties. For this reason, a fine pattern can be accurately formed in the manufacture of a semiconductor. BEST MODE FOR CARRYING OUT THE INVENTION

[Measetal ester of unsaturated carboxylic acid]

The unsaturated carboxylic acid hemiacetal ester of the present invention is represented by the above formula (1). In the formula (1), Ra represents ^a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms, and R ^b represents a hydrocarbon group having a hydrogen atom at the 1-position. Indicates, R. Represents a hydrogen atom or a hydrocarbon group, and R ^d represents an organic group having a cyclic skeleton.

The halogen atom in ^Ra includes a fluorine atom, a chlorine atom, a bromine atom and the like. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl, ethynole, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl group and the like. Among these, a Ci- ₃ alkyl group, particularly a methyl group, is preferred. Examples of the haloalkynole group having 1 to 6 carbon atoms include a chloroalkynole group such as a chloromethinole group; trifrenoleolomethyl, 2,2,2-trifinoleolotineol, pentafluroe And a fluoroalkyl group such as a mouth ethyl group (preferably, a fluoroanolealkyl group).

Examples of the hydrocarbon group having a hydrogen atom at 1-position in the R ^b, for example, Mechinore, Echinore, Puropinore, isopropylidene Honoré, Puchinore, Isobuchinore, s - alkyl group (e.g. C ₆ alkyl group such as butyl group, especially d - Cycloalkynole groups such as cyclopropynole, cyclopentinole, and cyclohexynole groups (for example, 3- to 6-membered cycloanolequinolene groups); cyclopentyl methylenole, and cyclohexylmethyl groups Alkylalkyl group [for example, mono- or di- (3- to 6-membered cycloalkyl) 1 d- ₃ alkyl group]; aralkyl groups such as benzylino, 1-methylbenzyl, 1-phenylenobenzyl, etc. Or diphenyl-d- ₃ alkyl group). R ^b is preferably a C ₃ alkyl group such as a methyl, ethyl, propyl, or isopropyl group, and particularly preferably a methyl group.

Examples of the hydrocarbon group for R c include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and s-butyl groups (for example, C i-6 alkyl groups, particularly ₃ alkyl groups); cyclopropyl, cyclopropyl Examples thereof include cycloalkynole groups such as pentynole and cyclohexyl groups (for example, a 3- to 6-membered cycloanolealkyl group); and aryl groups such as a phenyl group. R. Is a hydrogen atom; methyl, Echiru, propyl, preferably C Bok ₃ alkyl groups such as isopropyl, especially, a hydrogen atom, a methyl group good preferable.

^Examples of the cyclic skeleton in the organic group including the cyclic skeleton of R ^d include a lactone skeleton and a cyclic skeleton other than the lactone skeleton.

The rataton skeleton includes a lactone ring (for example, γ-petit mouth rataton ring, δ-valerolactone ring, ε-force prolactone ring, etc.), and the lactone ring has a non-aromatic structure. Or aromatic carbocyclic or heterocyclic rings are fused Skeleton included. Of these, a skeleton composed of only a lactone ring, and a skeleton in which a non-aromatic carbon ring or a heterocyclic ring (particularly, a non-aromatic carbon ring) is fused to the lactone ring are preferable. The rings that make up the lactone skeleton include alkyl groups such as methyl groups (for example, d- ₄ alkyl groups), haloalkyl groups such as trifluoromethyl groups (for example, C-4, alkyl groups, etc.), and chlorine atoms.ハロゲン Halogen atom such as fluorine atom, hydroxy group optionally protected by a protecting group, hydroxyalkyl group optionally protected by a protecting group, mercapto group optionally protected by a protecting group May have a substituent such as a propyloxyl group which may be protected by a protecting group, an amino group which may be protected by a protecting group, and a sulfonic acid group which may be protected by a protecting group. . Examples of the protecting group include those commonly used in the field of organic synthesis.

Representative lactone skeletons include skeletons represented by the following formulas (6a), (6b), (6c), (6d), (6e), (6f), and (6g). .

(6b) (6c) (6d)

(6e) (6f) (6g)

[In the formula,! ^{^{^{^ ~ 6, R 9 ~R 3}}} 6 are the same or different, a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an optionally protected human Dorokishiru group with a protecting group, it may be protected by a protecting group Good hydroxyalkyl groups, protected with protecting groups X represents an alkylene group, an oxygen atom, a sulfur atom or no bond, and Vi V ³ represents the same or different, Indicates CH ₂ _, one CO— or one COO—. And伹, at least one of the ~ N ³ is an CQO-. In the formula (6f), at least two groups out of R ^{27 to} R ³¹ may combine to form a ring together with a carbon atom or a carbon-carbon bond. Further, in the equation (6 g), may form a ring together with the carbon atom or carbon one-carbon bond at least two groups are bonded to one of R ³² to R ^36]

In the formulas (6a) to (6g), examples of the halogen atom in 1 ^ to ¹⁶ and R ^{9 to} R ³⁶ include a fluorine atom and a chlorine atom. Examples of the alkyl group include straight- or branched-chain carbon atoms such as methyl, ethyl, propyl, isopropynole, butyl, isoptinole, s-butyl, t-butyl, hexyl, octyl, decyl, and dodecyl groups. And the like. Among these, an alkyl group having 1 to 4 carbon atoms is preferable. Examples of the haloalkyl group include fluoroalkyl groups having 1 to 13 carbon atoms such as trifluoromethyl and pentafluoroethyl groups. Is an optionally protected arsenide de port cyclohexyl group with a protecting group, for example, human Dorokishiru group, a substituted Okishi group (e.g., main butoxy, ethoxy, C ₄ alkoxy group such as a propoxy group), and the like . Examples of the hydroxyalkyl group which may be protected with a protecting group include a group in which the above-mentioned hydroxyyl group which may be protected with a protecting group is bonded via an alkylene group having 1 to 6 carbon atoms. Is mentioned. Examples of the mercapto group which may be protected with a protecting group include a mercapto group, a mercapto group protected with the same protecting group as the above-mentioned hydroxyl group, and the like. Examples of the carboxyl group that may be protected with a protecting group include a C—R ^y group. R ^y represents a hydrogen atom or an alkyl group, and the alkyl group is a straight-chain such as methyl, ethyl, propyl ^^, isopropyl, butyl, isobutyl, s-butyl, t_butyl, hexinole, etc. And branched or branched alkyl groups having 1 to 6 carbon atoms. Examples of the alkylene group for X include a linear or branched alkylene group having about 1 to 3 (preferably 1 or 2) carbon atoms such as methylene, dimethylmethylene, ethylene, propylene, and trimethylene. Is mentioned.

At least two rings of radicals form together with the bond to a carbon atom or a carbon one-carbon binding, carbon atom or carbon one-carbon at least two groups bonded to one of R ³² to R ³⁶ of R ²⁷ to R ³¹ Examples of the ring formed together with the bond include alicyclic carbocycles (including bridged carbocycles) such as a cyclopentane ring, a cyclohexane ring, and a norbornane ring. The rings constituting the skeleton represented by the formulas (6a) to (6g) may have the substituent as described above.

The “ring” constituting the cyclic skeleton other than the ratatone skeleton includes a monocyclic or polycyclic non-aromatic or aromatic ring. Examples of the monocyclic non-aromatic ring include, for example, an alicyclic ring such as a cycloalkane ring of about 3 to 15 members such as a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, and a cyclodecane ring; And a non-aromatic heterocyclic ring of about 3 to 15 members such as a ring, a pyrrolidine ring, a piperidine ring and a morpholine ring. The non-aromatic ring polycyclic, for example, Adamantan ring; norbornane ring, Bruno Ruborunen ring, bornane ring, isobornane ring, tricyclo [. 5.2.1 0 ² ^'6] decane ring, Te Torashikuro [4. ^{^{4. 0. I 2 '. 5 I}} 7' 10] dodecane cans ring, a norbornane ring or ring containing a norbornene ring; Pahi Doroi Nden ring, decalin ring (Pahi mud naphthalene ring), Pahi Dorofuruo Len ring (g Li cyclo [7.4.3 0.0 ³ ^'8] preparative Ridekan ring), Pahi mud anthracene polycyclic aromatic condensed ring is the added ring (rather preferably is added completely hydrogenated hydrocarbon ring such as a ring); Tricyclo [4.2.2.2 I ² ' ⁵ ] Bridged carbon rings such as bicyclic, tricyclic and tetracyclic rings such as pentadecane rings (for example, bridged carbon rings with about 6 to 20 carbon atoms) ) And the like. Monocyclic or polycyclic Examples of the aromatic ring include an aromatic carbon ring such as a benzene ring, a naphthalene ring, a pyridine ring and a quinoline ring, and an aromatic heterocyclic ring. Among these, a non-aromatic ring is preferable, and a polycyclic non-aromatic ring is more preferable from the viewpoints of light transmittance and etching resistance when polymerized and used as a photoresist resin. And particularly preferred are polycyclic non-aromatic carbocycles (bridged carbocycles). Further, among the bridged carbon rings, a ring containing a norbornane ring or a norbornene ring, or a ring obtained by hydrogenating a polycyclic aromatic condensed ring (particularly, a completely hydrogenated ring) is particularly preferable. Therefore, as the cyclic skeleton other than the rataton skeleton, a non-aromatic cyclic skeleton is preferable, and a non-aromatic polycyclic skeleton, particularly, a polycyclic non-aromatic carbocyclic skeleton is preferable.

Rings constituting a cyclic skeleton other than the ratatone skeleton include: an alkyl group such as a methyl group (for example, a ₄ alkyl group); a haloalkyl group such as a trifluoromethyl group (for example, a C ₄ haloalkyl group); A halogen atom such as a chlorine atom or a fluorine atom, a hydroxyl group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, or a mercapto which may be protected by a protecting group May have a substituent such as a group, a carboxyl group which may be protected with a protecting group, an amino group which may be protected with a protecting group, and a sulfonic acid group which may be protected with a protecting group. . Examples of the protecting group include those commonly used in the field of organic synthesis.

The organic group containing a cyclic skeleton in R ^d includes the following formula (2)

(Wherein, A represents a linking group, and Z ¹ represents a ring constituting a cyclic skeleton).

Examples of the linking group in A include a single bond; methylene, Linear or branched alkylene groups such as methylene, dimethylmethylene, ethylene, propylene, and trinotylene groups; carbonyl groups; oxygen atoms (ether bonds; 1 o—); oxycarbonyl groups (ester bonds; —CO

O—); an aminocarbonyl group (amide bond; one CONH—); and a group in which a plurality of these groups are bonded. Preferred linking groups include a single bond

, A linear or branched C i-6 alkylene group (especially a ₃ alkylene group

) Etc. are included. The linking group includes, for example, a halogen atom such as a chlorine atom or a fluorine atom, a hydroxyl group optionally protected by a protecting group, a hydroxyalkyl group optionally protected by a protecting group, or a protecting group. Substitution of an optionally protected mercapto group, a carboxyl group optionally protected by a protecting group, an amino group optionally protected by a protecting group, a sulfonate group optionally protected by a protecting group It may have a group. It is a Uchirata tons backbone cyclic skeleton in the Z ^1, skeleton represented by the formula (6a) ~ (6g) are exemplified up. Also, as the ring constituting the cyclic skeletal non Lata tons skeleton of the cyclic skeleton in Z ^1, include those exemplified above.

Representative examples of the unsaturated carboxylic acid hemiacetal ester represented by the formula (1) having an organic group containing a ratatone skeleton [lactone among the compounds containing the group represented by the formula (2)] Examples of the compound having a skeleton] include, but are not limited to, the following compounds.

[1-1] 1-[1-(meth) atalyloyloxyethoxy]-4-oxosatricyclo [4.3.1.1. I ³ ' ⁸ ] pentane-5-one Formula (6a), A = single bond

[1-2] 2- [1 one (meth) Atari Roiruokishie butoxy] one 4-O key Satorishikuro [4.2.3 1.0 ³ ^'7] nonane one 5- ON [Z ¹ = formula (6b), A = Single bond]

[1-3] 2— [1- (meta) atali royloxyethoxy] — 6-methyl Norre one 4- Okisatorishikuro [4.2.1 1.0 ³ ^'7] nonane one 5- ON [Z i = formula (6b), A two single bonds]

[1-4] 2- [1 one (meth) Atari Roy Ruo ethoxy] - 6 - tri Furuoromechiru 4 one Okisatorishiku port [. 4.2.1 0 ³ ^'7] nonane one 5--on (6b), A = single bond]

[1-5] 2-[1-(meta) acryloyloxyethoxy] 1-9 -methyl 4-oxatricyclo [4.2.1. 0 ³ ' ⁷ ] Nonane 5 -one [Z i = formula (6b), A = single bond]

[1-6] 6- Furuoro one 2- [1 - (meth) Ata Li Kuchii Noreokishe butoxy] - 4 Okisato Rishikuro [. 4.2.1 0 ³ ^'7] nonane one 5- ON [Z ¹ = Equation (6b), A = single bond]

[1-7] 9- Karubokishi 2 - [1 one (meth) Atari Roiruokishieto carboxymethyl] _ 4-O hexa tricyclo [. 4.2.1 0 ³ ^'7] nonane one 5--on (6b), A = Single bond]

[1-8] 2- [1 one (meth) Ata Li Roy Ruo key shell butoxy] _ 9-1 menu preparative Kishikarubo two Lou 4- Okisatorishikuro [4.2.1 1.0 ³ ^'7] nonane one 5--on (6b), A = single bond]

[1-9] 9 _ethoxycarbonyl 2 -— [1- (meta) aryloyloxyethoxy] -14-oxatricyclo [4 21.0 ′ '] nonane-5-one [Z ¹ ^ formula ( 6b), A = single bond]

[1-10] 9 one t Putokishikarupo two Lou 2- [1 (meth) Ata Li Roy Ruokishietokishi] one 4-O hexa tricyclo [4 2. 1.0 ³ ^'7] non Hmm 5--on (6b) , A = single bond]

[1-11] 2- [1 — (meth) atalyloyloxyethoxy] 1,4,8-dioxatricyclo [4.2.1.0 ³ ' ⁷ ] nonane-5-one [Z ¹ -Equation (6b), A = single bond] [1-12] 4 1 [1 (meta) atali leunolexoxy ethoxy] _ 6-oxabicyclo [3.2.1] octane 1 7-one [Z ¹ ^ formula (6b), A = Single bond]

[1-13] 8 — [1- (Meth) atalylo norexoxyethoxy] 1-4-oxosatricyclo [5.2.1. 0 ² ' ⁶ ] decane-5-one [Z ¹ -Formula (6c), A = Single bond]

[1-114] 91-1 [1-1 (meta) atari mouth inoleoxyethoxy]-4-oxosatricyclo [5.2.1.0 ² ' ⁶ ] decane-5-one formula (6c), A = single bond

[1-15] a 1 [1-(meth) atalyloyloxyethoxy] 1 y, γ-dimethyl- _γ -butyrolactone formula (6g), A = single bond]

[1-16] 3 one C 1 i (meth) § click Re Roiruokishie butoxy] one 2-O Kiso one 1 Okisasupiro [4.5] decane [Z ¹ ^ Equation (6 g), A = single bond]

[1-17] a ― [11- (meta) atali royloxyethoxy] 1-gamma-butyrolactone [Ζ = formula (6g), A = single bond]

[1-18] a- [1-(meth) atalyloyloxyethoxy] — α, 7, γ-trimethyl-γ-petit mouth lactone [Z i = Formula (6g), A = single bond] [1 - 19] a one [1 - (meth) § click re Roiruokishie butoxy] - beta, beta - Jimechinore one _gamma - Puchiroraku tons [Zeta ¹ ^ equation (6 g), A = single bond]

[1-20] A compound represented by the following formula (7): Formula (6g), where A is a single bond

]

(7)

[1-21] 3-[1- (meta) atali royloxyethoxy] — 2-oxo 1-oxaspiro [4.4.] Nonane [Z ¹ : Formula (6g), A = single bond]

Representative examples of the unsaturated carboxylic acid hemiacetal ester represented by the formula (1) having an organic group containing a cyclic skeleton other than the ratatone skeleton [including the group represented by the formula (2) Among the compounds, compounds having an organic group containing a cyclic skeleton other than the lactone skeleton] include the following compounds, but are not limited thereto.

[1-22] 1-(Adamantane_1-yloxy) ethyl (meta) acrylate

[1-23] 1- (Adamantane-11-ylmethoxy) ethyl (meth) acrylate

[1-24] 1 1 [2— (Adamantane 1 1 1 yl) Ethoxy] Ethyl (meta) Atarilate

[1-25] 1-[1-(adamantane _ 1 -yl) 1-1-methylethoxy] ethyl (meta) acrylate

[1-26] 1- (2-Methyladamantane-2-yloxy) ethyl (meta) acrylate

[1-27] 1- (3-Hydroxyadamantane-11-inoleoxy) ethyl (meth) atalylate

[1-28] 1- (3,5-dihydroxy-amantane-11-yloxy) ethyl (meta) acrylate

[1-29] 1— (3-Carboxyadamantane _1-inoleoxy) ethynole (meth) acrylate

[1-30] 1- (3,5-dicarboxy-adamantane-11-yloxy) ethyl (meth) acrylate [1-31] 1- (Norbornane-2-yloxy) ethyl (meta) acrylate

[1-32] 1- (Norbornane-2-ylmethoxy) ethyl (meth) acrylate

[1-33] 1- (2-Methylnorbornane-2-yloxy) ethyl (meta) acrylate

[1-34] 1- [1- (norbornane-2-yl)-1-methylethoxy] ethyl (meth) acrylate

[1-35] 1- (3-Hydroxynorponolenane 2- _inoleoxy) ethyl (meth) atalylate

[1-36] 1- (3-Hydroxymethylnorbornane-2-ylmethoxy) ethyl (meth) acrylate

[1-37] 1— (5,6-dihydroxynorpolnan-1-ylmethoxy) ethyl (meth) acrylate

[1-38] 1- (3-methylnorbornane-2-ylmethoxy) ethyl (meth) acrylate

[1-39] 1- (decalin_1-yloxy) ethyl (meth) acrylate

[1-40] 1- (decalin-2-yloxy) ethyl (meth) acrylate

[1-41] 1- (5-hydroxydecalin-1-yloxy) ethyl (meta) acrylate

[1-42] 8- arsenide Dorokishimechiru 4 one [1- (meth) Ata Li Roiruoki Shetokishimechiru] tricyclo [5.2.2 1.0 ² ^'6] decane

[1-43] 4-Hydroxymethyl- 8— [1- (Meth) atalyloyloxy shetoxymethyl] tricyclo [5.2.1.0 ² ' ⁶ ] decane [1-44] 1- (bornyloxy) ethyl (meta) acrylate

[1-45] 1— (Isobornyloxy) ethyl (meth) acrylate

[1-46] 3- Karubokishi 8- [1- (meth) Ata Li Roiruokishieto carboxymethyl] tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] dodecane

[1-47] 3- Karubokishi 9 one [1 - (meth) Ata Li Roiruokishieto carboxymethyl] te Torashikuro ^{[4. 4. 0. I 2 '.} 5 I 7' 10] dodecane

The unsaturated carboxylic acid hemiacetal ester represented by the formula (1) is, for example, as shown in the following reaction formula, the unsaturated carboxylic acid represented by the formula (3) and the unsaturated carboxylic acid represented by the formula (4). The reaction can be carried out in a solvent or under a non-solvent with the butyl ether compound to be produced. The product, the compound represented by the formula (5), corresponds to the compound represented by the formula (1).

(3) (4) (5)

(Wherein, R ^a, R., R ^d represents the same. Rs, respectively and R ^f a hydrogen atom or a hydrocarbon group in the one CHR.R ^f corresponds to the R ^b)

Although the above reaction proceeds without a catalyst, the reaction can be promoted by using an acid catalyst. The acid catalyst is not particularly limited, and either an inorganic acid or an organic acid can be used. Examples of the inorganic acid include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; heteropolyacids such as linmolybdic acid, chemolybdic acid, lintastanoic acid, and kytungstic acid; And solid catalysts such as Examples of the organic acid include carboxylic acids such as formic acid, acetic acid, and trifluoroacetic acid; and sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesnolephonic acid, p-toluenesulfonic acid, and naphthalenesulfonic acid. . As an acid catalyst An on-exchange resin may be used. Also, a Lewis acid can be used. Further, among the above-mentioned acids which can form a salt, it is also possible to use a pyridinium salt, an ammonium salt, an alkali metal salt, an alkaline earth metal salt, a transition metal salt, or the like. . Among these, phosphoric acid is particularly preferred in terms of the yield and selectivity of the target compound.

The solvent is not particularly limited as long as it is a solvent inert to the reaction. Examples thereof include aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; cyclohexane and methylcyclohexyl. Alicyclic hydrocarbons such as hexane; Halogenated hydrocarbons such as methylene chloride; Tetrahydrofuran, ethylene glycol, etc. Non-protonic substances such as N, N-dimethylformamide Examples include polar solvents.

The amount of the unsaturated carboxylic acid represented by the formula (3) is, for example, about 0.5 to 50 mol, preferably 0.9 to 1 mol per mol of the vinyl ether compound represented by the formula (4). It is about 0 mol. The amount of the acid catalyst to be used is, for example, about 0.000 :! to about 1 mol, and preferably about 0.001 to about 0.3 mol, per 1 mol of the vinyl ether compound represented by the formula (4). .

In order to suppress polymerization of the vinyl ether compound represented by the formula (4) and the reaction product, it is preferable to add a small amount of a polymerization inhibitor such as 4-methoxyphenol to the system. The amount of the polymerization inhibitor to be added is, for example, about 0.001 to 0.05 mol, preferably 0.000 to 1 mol, per 1 mol of the vinyl ether compound represented by the formula (4). 0.1 It is about 1 mole.

The reaction temperature varies depending on the type of the reaction raw materials, the type of the catalyst used, and the like, but is usually from 110 to 100 ° C, and preferably from about 0 to 60 ° C.

After completion of the reaction, the reaction product can be separated and purified by a separation means such as adjustment of liquid properties, extraction, concentration, distillation, crystallization, recrystallization, and column chromatography. Note that equation (1) In addition to Mi acetal ester to unsaturated carboxylic acids represented by, R ^B and R. In the formula (1) Are also useful as monomers of polymer compounds for photoresists. The repeating unit corresponding to this compound exerts an acid-eliminating function and a hydrophilic function in the polymer compound. Examples of such a compound include a compound corresponding to the example of the unsaturated carboxylic acid hemiacetal ester represented by the above formula (1) (a compound in which R ^B = R. = H) and the like.

R ^B及Pi R. In the formula (1) Is a hydrogen atom [compound represented by the formula (B)], for example, as shown in the following reaction formula, an unsaturated carboxylic acid represented by the formula (3) and a compound represented by the formula (A) It can be produced by reacting the represented halomethyl ether compound in the presence of a base.

(3) (B)

(In the formula, R ^A and R ^D are the same as above. Y represents a halogen atom.)

Examples of the halogen atom in Υ include chlorine, bromine, and iodine atoms. The reaction is performed in the presence or absence of a solvent. The solvent described above can be used as the solvent. As the base, for example, an organic base such as triethylamine or pyridine, or an inorganic base such as sodium hydroxide, sodium carbonate, or sodium hydrogencarbonate can be used. The amount of the unsaturated carboxylic acid represented by the formula (3) is, for example, about 0.5 to 10 mol, preferably 0.8 to 1 mol of the halomethyl ether compound represented by the formula (Α). About 2 moles. The amount of the base used is, for example, about 1 to 5 mol per 1 mol of the unsaturated carboxylic acid represented by the formula (3). Les ,. In order to suppress the polymerization of the halomethyl ether compound represented by the formula (A) and the reaction product, a small amount of a polymerization inhibitor such as 4-methoxyphenol may be added to the system. The reaction temperature is usually about 110 to 100 ° C, preferably about 0 to 60 ° C. After completion of the reaction, the reaction product can be separated and purified by separation means such as liquidity control, extraction, concentration, distillation, crystallization, recrystallization, and column chromatography.

The halomethyl ether compound represented by the formula (A) is, for example, as shown in the following reaction formula, a hydroxy compound represented by the formula (C) is added to formaldehyde or an equivalent thereof (paraformaldehyde, 1,3,5-trioxane) and the hydrogen halide represented by the formula (D).

(Where R ^d and Y are the same as above)

Examples of the hydrogen halide represented by the formula (D) include hydrogen chloride and hydrogen bromide. The reaction is performed in the presence or absence of a solvent. The solvents described above can be used as the solvent. The amount of formaldehyde or an equivalent thereof used is, for example, about 0.8 to 10 moles, preferably: !! to 1 mole of the hydroxy compound represented by the formula (C) in terms of formaldehyde. It is about 5 mol. The amount of the hydrogen halide represented by the formula (D) is, for example, about 1 to 5 mol with respect to 1 mol of the hydroxy compound represented by the formula (C), and a large excess may be used. The reaction temperature is usually from −10 ° C. to 100 ° C., preferably from about 0 ° to 60 ° C. After completion of the reaction, the reaction product can be separated and purified by separation means such as liquidity control, extraction, concentration, distillation, crystallization, recrystallization, and column chromatography. [Polymer compound]

The polymer compound of the present invention contains a repeating unit (monomer unit) corresponding to the above-mentioned unsaturated carboxylic acid mesacetal ester, that is, a unit represented by the formula (I). The repeating unit may be one kind or two or more kinds. Such a polymer compound can be obtained by subjecting the above unsaturated carboxylic acid hemiacetal ester to polymerization. Since the repeating unit represented by the formula (I) has a hemiacetal ester structure, it has an acid-eliminating function (alkali-soluble function). In other words, the acid generated from the photoacid generator upon exposure removes the alcohol portion (hemiacetal portion) of the ester to form a free carboxyl group, and thus becomes more soluble in the alkaline developer. In addition, since the hemiacetal ester structure contains three oxygen atoms, it has higher hydrophilicity than the conventional acid-eliminable unit having a simple ester structure (containing two oxygen atoms), and has a resist solvent. There is an advantage that the solubility and wettability with respect to an alkaline developer and an alkaline developer are improved. Further, when the repeating unit represented by the formula (I) has a ratatone skeleton, the adhesion to the substrate is excellent. Such a polymer compound having a repeating unit having both an acid-eliminating function and a substrate adhesion function has a higher acid-elimination property than a conventional polymer compound having a repeating unit having only an acid-eliminating function. Since the number of substrate-adhering groups can be significantly increased while maintaining the number of leaving groups, a high level of substrate-adhesion can be achieved, and the number of acid-labile groups and the number of substrate-adhering groups can be reduced. By introducing a repeating unit having another function such as hydrophilicity while maintaining the same, it is excellent in that both acid desorption property, substrate adhesion and other functions are sufficiently provided. When R ^d in the formula (I) is a group containing a polycyclic non-aromatic carbocyclic ring (bridged carbocyclic ring), it exhibits high light transmittance and dry etching resistance.

The polymer compound of the present invention can sufficiently perform various functions required as a resist. In order to provide a good balance, other repeating units may be provided in addition to the repeating unit represented by the above formula (I). Such another repeating unit can be formed by copolymerizing the polymerizable unsaturated monomer corresponding to the repeating unit with the above unsaturated carboxylic acid and a miacetal ester. As the other repeating unit, for example, a repeating unit having a substrate adhesion and / or hydrophilicity function, a repeating unit improving an acid desorption property, a repeating unit improving an etching resistance function, a repeating unit improving transparency, and the like Is mentioned. The hydrophilic function includes a function of increasing solubility in a resist solvent or an alkaline developer. In preparing the polymer compound of the present invention, a monomer used to promote copolymerization smoothly or to make the copolymer composition uniform may be used as a comonomer. The repeating unit having a substrate adhesion and / or a hydrophilic function can be introduced into a polymer by using a polymerizable unsaturated monomer having a polar group as a comonomer. Examples of the polar group include (1) groups such as a lactone ring-containing group, a carbonyl group, an acid anhydride group, and an imido group; (2) a hydroxyl group which may have a protecting group, and a protecting group. Groups such as a mercapto group, a carboxyl group, which may have a protecting group, an amino group, which may have a protecting group, and a sulfonic acid group, which may have a protecting group. No. Examples of the polymerizable unsaturated monomer having a polar group include (a) a lactone skeleton-containing monomer, a cyclic ketone skeleton-containing monomer, an acid anhydride group-containing monomer, and an imido group-containing monomer. (B) Hydroxyl group-containing monomer (including a compound having a protected hydroxy group), mercapto group-containing monomer (including a compound having a protected mercapto group) , A carboxy group-containing monomer (including a compound in which a carboxyl group is protected), an amino group-containing monomer (including a compound in which an amino group is protected), and a sulfonate group-containing monomer. Monomer (including compounds with protected sulfonic acid groups) And a compound known in the resist field can be used. These monomers can be used alone or in combination of two or more. For example, by combining a monomer belonging to the above (a) and a monomer belonging to the above (b), it is possible to exert a well-balanced resist characteristic.

The repeating unit that enhances the acid elimination function includes, for example, (c) a hydrocarbon group having a tertiary carbon, a 2-tetrahydrofuroyl group, or a 2-tetrane group adjacent to an oxygen atom constituting an ester. (Meta) acrylic acid ester derivatives to which a hydrhydryl group is bonded, and (d) a hydrocarbon group (alicyclic hydrocarbon group, aliphatic hydrocarbon group, etc.) adjacent to the oxygen atom constituting the ester. And the hydrocarbon group is a _COOR ^x group (R ^x is a tertiary hydrocarbon group, a 2-tetrahydrofuraell group or a 2-tetrahydrovinylal group) Can be introduced into the polymer by using as a comonomer a (meth) acrylic acid ester derivative or the like bonded directly or via a linking group. As such a (meth) acrylate derivative, a compound known in the field of resist can be used.

As a typical example of a polymerizable unsaturated monomer other than myacetal ester used for imparting various functions as a resist to the polymer compound of the present invention, the following formula (8a) To (8g). These correspond to the ratatone skeleton-containing monomer and the cyclic ketone skeleton-containing monomer.

: 8a) (8b) (8d)

(Wherein, R represents a hydrogen atom or a methyl ^{^{group.! ^ ~ 6, R 9}} ~R 36, X, ~ V 3 are the same)

Representative examples of the compound represented by the formula (8a) include the following compounds, but are not limited thereto.

[2-1] 1- (meta) atariloyloxy 4-oxodamantane (R = H or CH ₃ , R ^ R ^ R ^ H, V ¹ = — CO—, V ² = V ³ = -CH _2- )

[2-2] 1- (Meth) acryloyloxy-4-oxatricyclo [4-3.1.1 I ³ ' ⁸ ] pentane-5-one (R = H or CH ₃ , R ^X = R ² = R ³ = H, V ² = — CO— 0_ (left side is the carbon atom side to which R ² is bonded)

[2-3] 1- (meta) atariloyloxy 1, 4, 7-dioxatrisic Mouth [4.4.3 1.1 ^{^3.9]} dodecane one 5, 8-dione (R = H or _{^{^{CH 3, R 1 = R 2}}} = R 3 = H, V ^ -CO-O- ( left R ¹ bonded to that carbon atom ^{side), V 2 == - CO- O-} ( left carbon atoms side bonded to ^{^{R 2), V 3 = -}} CH 2 -)

[2-4] 1- (Meth) acryloxyloxy-1,4,8-dioxatolithic mouth [4. 4. 1. I ³ ' ⁹ ] Dodecane-1,5,7-dione (R = H or CH ₃ , R ^: = R ² = R ³ = H, V ^ -O-CO- (left side is the carbon atom side to which R ¹ is bonded), V ² = — CO—〇1 (left side is the R ² side Carbon atom side), V ³ = _CH ₂ —)

[2-5] 1- (Meth) acryloxyloxy 5,7-dioxatricic mouth [4. 4. 1. I ³ ' ⁹ ] Dodecane 1,4,8-dione (R = H or C'H ₃ , R ^ R ^ R ^ H, V ^ -CO-O- (left side is the carbon atom side to which R ¹ is bonded), V ² = — O— CO— (left side is the carbon atom side to which R ² is bonded) Side), V ³ = -CH _2- )

Representative examples of the compound represented by the formula (8b) include, but are not limited to, the following compounds.

[2-6] 2- (meth) § click Li Roiruokishi _ 4- Okisatorishikuro [4. 2. 1.0 ³ ^'7] nonane one 5- one (= 5- (meth) § click Li Roiruoki shea one 2, 6—Norbornane carboractone) (R = H or CH ₃ , R ⁴ = R ⁵ = R ⁶ = H, X = methylene group)

[2-7] 2- (meth) Ata Li Roiruokishi one 2-methyl-4 Okisato Rishikuro [4.2.3 1.0 ³ ^'7] nonane one 5- ON (R = H or CH _3, R ⁴ = CH ₃ , R ⁵ = R ⁶ = H, X = methylene group)

[2-8] 2- (meth) Ata Li Roiruokishi 6- methyl-4- Okisato Rishikuro [4.2.3 1.0 ³ ^'7] nonane one 5- ON (R = H or CH _{_3,} R ⁵ = CH ₃ , R ⁴ = R ⁶ = H, X = methylene group) [2-9] 2 - (meth) § click Li Roiruokishi 9-methyl-4 one Okisa preparative Rishikuro [4.2.3 1.0 ³ ^'7] nonane one 5- ON (R = H or CH _3, R ^e = CH _{^{^{3, R 4 = R 5 =}}} H, X = methylene group)

[2-10] 2 - (meth) § click Li Roiruokishi 9 Ichiriki Rupokishi 4 Oki Satorishikuro [4.2.3 1.0 ³ ^'7] nonane one 5 _ ON (R = H or CH _3, R ⁴ = R ⁵ = H, R ⁶ = CO〇H, X = methylene group)

[2 - 11] 2 - (meth) § click Li Roiruokishi 9-1 main Tokishikarubo two Lou 4-O hexa tricyclo [4.2.3 1.0 ³ ^'7] nonane one 5- ON (R = H or CH ₃ , R ⁴ = R ⁵ = H, R ⁶ = Methoxycarbonyl group, X = Methylene group)

[2-12] '2- (meth) § click Li Roiruokishi one 9 one ethoxycarbonyl two Lou 4- Okisatorishikuro [4.2.3 1.0 ^3' ^7] nonane one 5- ON (R = H or CH _3, R ⁴ = R ⁵ = H, R ⁶ = ethoxycarbonyl group, X = methylene group),

[2-13] 2 (meth) § click Li Roiruokishi 9 one t Putokishikarubo two Lou 4-O hexa tricyclo [4.2.3 1.0 ³ ^'7] nonane one 5- ON (R = H or CH ₃ , R ⁴ = R ⁵ = H, R ⁶ = t-butoxycarbonyl group, X = methylene group)

Representative examples of the compound represented by the formula (8c) include, but are not limited to, the following compounds.

[2-14] 8 one (meth) Ata Li Roiruokishi 4 Okisato Rishikuro [5. 2. 1.0 ^{^2'6]} decan one 5- ON (R two H or CH ₃₎

[2-15] 9 - (meth) Ata Li Roiruokishi 4 Okisato Rishikuro [. 5 2. 1.0 ^{^2'6]} Dekan 5--one (R = H or CH ₃₎

Representative examples of the compound represented by the formula (8d) include the following compounds, but are not limited thereto. [2-16] 4- (meth) acryloyloxy 6 —oxabicyclo [3.2.1] octane 7 _one (R = H or CH ₃ , R ⁹ = R ¹⁰ = R ¹¹ = R

1 2 _{= R} 1 3 _{= R l} 4 _{= R l 5 == R} 16 _{= R} 17 _{= H)}

[2-17] 4- (meth) acryloyloxy 4-methyl-6-oxabicyclo [3.2.1] octane-7-one (R = H or CH ₃ , R ¹⁰ = R ll = _R 1 2 _{= R l 3 = R l 4; = R l 5 = R l 6 = R l 7 = H} , _R 9 = CH ₃ )

[2-18] 4 one (meth) § click Li Roiruokishi 5- methyl-6- Okisabi cyclo [3.2.1] octan one 7- ON (R two H or _{^{^{CH 3, R 9 = R 11}}} = R i 2 = R ¹³ = R ^{l 4} = R ^{i 5} = R ^ie = R ¹ = HR ¹⁰ = CH ₃ )

[2-19] 4- (meth) acryloyloxy 4,5-dimethyl-6-oxabicyclo [3.2.1] octane-7-one (R = H or CH ₃ , R

_{1 1 = R 1 2 = R 1 3 = R 1 4 = R 15 = R 16 = R 17 = = H} , _R 9 _{= R} 10 _{= CH 3} ) of the compound represented by the formula (8e) Representative examples include the following compounds, but are not limited thereto.

[2 - 20] 6 - (meth) Ata Li Roiruokishi 2- Okisabishikuro [2.2.2] octan one 3-one (R = H or _{^{^{CH 3, R 18 = R 19}}} = R 20 = R

2 1 2 2 p 23 p 24 _ p 25 p 26 __ j ^ "^

[2-21] 6- (meth) § click Li Roiruokishi one 6- methyl-2 Okisabi cyclo [2.2.2] octan one 3 _ ON (R = H or _{^{^{CH 3, R 18 = R 20}}} = R 21 ^{^{= R 22 = R 23 = R}} 24 = R 25 = R 26 = H, R 19 = CH 3)

[2-22] 6 - (meth) § click Re Roiruokishi 1 - methyl-2 Okisabi cyclo [2.2.2] octan one 3-one (R = H or _{^{^{CH 3, R 19 = R 20}}} = R 21 = ^{^{^{R 22 = R 23 = R 24}}} = R 25 = R 26 = H, R 18 = CH 3)

[2-23] 6- (Meth) acryloyloxy 1,6-dimethyl-2-oxabicyclo [2.2.2] octane-3-one (R = H or CH ₃ , R 0 = R ²¹ = R ⁽²² = R ²³ = R ²⁴ = R ²⁵ = R ²⁶ = H _N R ¹⁸ = R ¹⁹ = CH ₃ ) Representative examples of the compound represented by (8f) include, but are not limited to, the following compounds.

[2-24] β-1 (meta) atalyroyloxy Ύ 1 -buty ratatone (R =

Η or C Η ₃ , _ ρ _ ρ H)

B

R

B

R

―

R

― _Γ -butyrolactone (R = H or CH ₃ , R ² : 1: R ³¹ = CH ₃ , R

[2-29] β- (meth) atalyloyloxy a, β, y, pentamethyl-γ-butyrolactone (R = H or CH ₃ , R ²⁷ = R ²⁸ = R ²⁹ =

R ³⁰ = R ³¹ = CH ₃ )

Representative examples of the compound represented by the formula (8g) include, but are not limited to, the following compounds.

[2-30] a-(meth) acryloyloxy γ _ petyrolactone (R =

H or CH ₃ , R 32

[2-31] a- (Meth) acryloyloxy α-methyl-γ-butyrolataton (R di or CH ₃ , R ³² = CH ₃ , R ³³ = R ³⁴ = R ³⁵ = R ³⁶ = H ) [2-32] a-(Meth) acryloyloxy β β -Dimethinoleate — tyrolactone (R = H or CH ₃ , R ³³ = R ³⁴ = CH ₃ , R ³² = R ³⁵ = R ³⁶ = H )

[2-33]-(Meth) acryloyloxy α β, iS—trimethyl-γ-butyrolactone (R = H or CH ₃ , R ³² = R ³³ = R ³⁴ = CH ₃ , R ³⁵ = R ³⁶ = H )

[2-34] a-(Meth) atalyloyloxy γ Ύ ― dimethyl-γ-butyrolactone (R di or CH ₃ , R ³⁵ = R ³⁶ = CH, R ³² = R ³³ = R ³⁴ = H)

[2-35] a-(meth) acryloyloxy _ α Ύ-trimethylbutyrolactone (R = H or CH ₃ , R ³² = R = R ⁶ = CH ₃ , R ³³ = R ³⁴ = H)

[2-36] a - (meth) § click Re Roiruokishi _ / 3 β Ύ, γ- Te Torame Chill one _gamma - butyrolactone tons (R = H or _{^{CH 3, R = R 4 =}} R 35 = R 3 6 = CH _3, R ³² = H)

[2-37] a-(Meth) acryloyloxy α, ββ, y, γ-hexamethyl-γ_butyrolactone (R = H or CH ₃ , R ³² = R

R ³⁵ = R ³⁶ = CH ₃ )

Other examples of polymerizable unsaturated monomers other than myacetal esters used for imparting various functions as a resist to the polymer compound of the present invention include maleic anhydride, Murray Mid. These correspond to the acid anhydride group-containing monomer and the imide group-containing monomer. Other typical examples of polymerizable unsaturated monomers other than myacetal esters include unsaturated carboxylic acids used to impart various functions as a resist to the polymer compound of the present invention. And a compound represented by the formula (9). These compounds are the same as those described above for the hydroxyl group-containing monomer, mercapto. It corresponds to a group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a sulfonic acid group-containing monomer, and a cyclic ketone skeleton-containing monomer.

(Wherein, ring Z ² represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms. R represents a hydrogen atom or a methyl group. R ³⁷ represents a substituent bonded to ring Z ² , Same or different, may be protected by an oxo group, an alkyl group, a hydroxyl group optionally protected by a protecting group, a hydroxyalkyl group optionally protected by a protecting group, or a protecting group A carboxyl group, an amino group which may be protected by a protecting group, or a sulfonic acid group which may be protected by a protecting group, provided that at least one of n R ^37s is an oxo group or a protecting group A hydroxyl group which may be protected with a group, a hydroxyalkyl group which may be protected with a protecting group, a carboxyl group which may be protected with a protecting group, an amino which may be protected with a protecting group Group or protected by a protecting group. Represents a sulfonic acid group, and n represents an integer of 1 to 3)

It is an alicyclic hydrocarbon ring monocyclic having 6 to 20 carbon atoms in the ring Z ^2, or may be a polycyclic ring, over fused ring and bridges. Representative alicyclic hydrocarbon rings include, for example, cyclohexane ring, cyclooctane ring, cyclodecane ring, adamantane ring, norbornane ring, norbornene ring, bornane ring, isobornane ring, perhydroindene ring, decalin ring, Pahi mud fluorene ring (tricyclo [7.4.3 0.0 ³ ^'8] tridecane ring), Pahi Doroantora Sen ring, preparative Rishikuro [5.2.2 1.0 ^2' ^6] decane ring, preparative Rishikuro [4 . 2. 2. I ² ^'5] Undekan ring, Te Torashikuro ^{^{[4. 4. 0. I 2' 5}} . 1 7 '10] dodecane ring. The alicyclic hydrocarbon ring has a methyl group (E.g., 4-alkyl group), haloalkyl group such as trifluoromethyl group, halogen atom such as fluorine atom and chlorine atom, hydroxyl group which may be protected by protecting group, and protecting group A hydroxyalkyl group, a mercapto group which may be protected with a protecting group, an oxo group, a carboxyl group which may be protected with a protecting group, or a group which may be protected with a protecting group. It may have a substituent such as a amino group or a sulfonate group which may be protected by a protecting group.

In the formula (9), it is a § kill group in R ^37, methyl, Echiru, flop port pills, isopropyl, butyl, Isopuchinore, s - Puchinore, t one-butyl, hexyl, Okuchiru, decyl, and dodecyl groups Examples thereof include a linear or branched alkyl group having about 1 to 20 carbon atoms. Examples of the amino group that may be protected with a protecting group include an amino group, a substituted amino group (for example, a C ぃ₄ alkylamino group such as a methylamino, ethylamino, propylamino group, and the like). It is a protected or unprotected sulfonic group with a protective group, and the like one S 0 ₃ R ^Z group. R ^z represents a hydrogen atom or an alkyl group; examples of the alkyl group include straight-chain or branched-chain groups such as methyl, ethyl, propyl, isopropyl, butynole, isobutyl, s-butyl, t-butyl, and hexyl. And an alkyl group having 1 to 6 carbon atoms. A hydroxy group which may be protected by a protecting group, a hydroxyalkyl group which may be protected by a protecting group, a mercapto group which may be protected by a protecting group, and a protecting group which are protected by R ³⁷ Possible carboxyl groups are the same as described above.

Representative examples of the compound represented by the formula (9) include, but are not limited to, the following compounds.

[3-1] -1-arsenide Dorokishi one 3- (meth) Ata Li Roy Ruo carboxymethyl § Da manta emissions (R = H or _{^{CH 3, R 37 = OH,}} n = l, Z 2 = Adamantan ring) [3-2] 1, 3- dihydric Dorokishi 5- (meth) Ata Li Roiruokishiada Kalimantan (R = H or _{^{CH 3, R 37 = OH,}} n = 2, Z 2 = Adamantan ring)

[3-3] 1-stroke / Repoxy 3— (Meth) acryloylonoxy-adamantane (R = H or CH ₃ , R ³⁷ = COOH, n = l, Z ² = adamantane ring)

[3-4] 1, 3 - dicarboxy - 5- (meth) § click Re Roiruokishiada Kalimantan (R = H or _{^{CH 3, R 37 = COOH,}} n = 2, Z 2 = Adaman monocyclic)

[3-5] 1 one Karubokishi 3- arsenide Dorokishi one 5- (meth) § click Li Roinore O carboxymethyl § Dammann Tan (R = H or CH _3, R ³⁷ = 〇_H, C_〇_〇_H, n = 2

, Z ² = adamantane ring)

[3-6] 1 _ t one butoxycarbonyl one 3- (meth) § click Re Roiruoki Shiadamantan (R = H or CH _3, R ³⁷ = t- butoxycarbonyl - le group, n = l, Z ² = Adamantan ring )

[3-7] 1, 3-bis (t-butoxycarbonyl - Le) Single 5- (meth) § click Li Roy Ruo carboxymethyl § Dammann Tan [R = H or CH _3, R ³⁷ = t- Butokishika carbonyl group, n = 2, Z ² = adamantane ring]

[3-8] 1-t-butoxycarbonyl one 3-arsenide Dorokishi one 5- (meth) § click Li Roy Ruo carboxymethyl § Dammann Tan (R = H or _{^{CH 3, R 37 = OH,}} t - butoxycarbonyl - Le Group, n = 2, Z ² = adamantane ring)

[3-9] 1 one (2-te Torahi mud Vila sulfonyl O propoxycarbonyl Interview le) one 3- (meth) § click Li Roy Ruo carboxymethyl § Dammann Tan (R = H or CH _3, R ³⁷ = 2 - Tetorahi Drobilanyloxycarbonyl group, n = 1, Z ² = adamantane ring)

[3-10] 1,3-bis (2-tetrahydrobiranyloxycarbonyl) - 5- (meth) § click Li Roy Ruo carboxymethyl § Dammann Tan (R = H or CH _3, R ³⁷ = 2- Te Torahi mud Vila sulfonyl O alkoxycarbonyl group, n = ^2, Z 2 = § da Kalimantan ring)

[3-11] 1-Hydroxy_3— (2-tetrahydropyranyloxyl carbonyl) 5- (Meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = OH , 2—tetrahydrobiranyloxycarbonyl group, n = 2, Z ² = adamantane ring)

Further, as the carboxyl group-containing monomer, for example, acrylic acid, methacrylic acid and the like can be used.

Representative examples of polymerizable unsaturated monomers used to enhance the acid-eliminating function of polymer compounds include, for example, 1-1 [1- (meth) atalyloyloxy_1-methylethyl] adamantane , 2 _ (meth) acryloyloxy 2- 2-methyladamantane, 2- (meta) acryloyloxy

2-Ethyladamantane, 2- [1- (meth) acryloyloxy 1-methylethyl] norbornane, 2- (meth) acryloyloxy-1-2-methylnorbornane, 1-1 [1- (meth) acryl Liloyloxy-1-methylethyl] cyclohexane, 11- (meth) acryloyloxy_1-methylcyclohexane, 3- [1- (meta) acryloyloxy 1-methylethyl] tetracyclo [4.4] . 0. I ² ' ^5. I ⁷ ' ¹⁰ ] dodecane, t-butyl (meth) acrylate, 1- (t-butoxycarbonyl)

3- (meth) acryloyloxyadamantane, 2- (t-butoxycarbonyl) -1-5- or 6- (meth) acryloyloxynorpornanane, and their analogs (of methyl group) Instead, other alkyl groups such as an ethyl group or a compound to which a haloalkyl group such as a trifluoromethyl group is bonded, etc.).

In addition, in each monomer represented by the above formulas (8a) to (8g), (9), Meta) A corresponding vinyl ether compound in which an attaryloyloxy group is replaced by a butyl group (including a vinyl group having a substituent such as a 1-methylvinyl group or a chloro group) is used as a monomer component of the polymer compound of the present invention. It can also be used.

In the polymer compound of the present invention, the proportion of the repeating unit represented by the formula (I) is not particularly limited, but is generally: ~ 1 0 0 mole ^_0/0, preferably 1 0-9 0 mole ^_0/0, more preferably 3 0-8 about 0 mol%. Repetition corresponding to at least one monomer selected from a lactone skeleton-containing monomer, a cyclic ketone skeleton-containing monomer, an acid anhydride group-containing monomer and an imido group-containing monomer The proportion of the unit [excluding the repeating unit represented by the formula (I)] is 0 to 95 mol%, preferably 0 to 60 mol ⁰ /. More preferably, 10 to 40 mol ⁰ /. Degree. The proportion of the repeating unit corresponding to at least one monomer selected from a monomer containing a hydroxyl group, a monomer containing a mercapto group and a monomer containing a carboxyl group is from 0 to 95 mole ^_0/0, preferably 5-9 0 mole ^_0/0, preferably in the al about 1 0-5 0 mol%.

In obtaining the polymer compound of the present invention, the monomer mixture is polymerized by a conventional method used for producing an acrylic polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. In particular, solution polymerization is preferable. Further, drop polymerization is preferable among solution polymerizations. In the drop polymerization, for example, (i) a monomer solution previously dissolved in an organic solvent and a polymerization initiator solution dissolved in an organic solvent are respectively prepared, and the organic solvent kept at a constant temperature is prepared. (Ii) a method in which the monomer solution and the polymerization initiator solution are respectively dropped into the organic solvent, and (ii) a mixed solution obtained by dissolving the monomer and the polymerization initiator in an organic solvent in an organic solvent maintained at a constant temperature. (Iii) a monomer solution previously dissolved in an organic solvent and a The polymerization initiator solution is prepared, and the polymerization initiator solution is dropped into the monomer solution maintained at a constant temperature. Known solvents can be used as the polymerization solvent. Examples of the polymerization solvent include ethers (eg, ethyl ether, propylene glycol, etc., chain ethers such as glyco- / re-ters, terehydrofuran, dioxane, etc.). Cyclic esters, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, ethynole lactate, propylene glycol cornolemono meth / leate enorea acetate, etc.), ketones (acetone, methino oleetene) Ketone, methyl isobutyl ketone, cyclohexanone), amide (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol) , Propanol, etc.), carbonization Arsenide (benzene, Torue emissions, aromatic hydrocarbons such as xylene, to the aliphatic hydrocarbons hexane and the like, and alicyclic hydrocarbons cyclohexane and the like consequent opening), and mixtures of these solvents like et be. Further, a known polymerization initiator can be used as the polymerization initiator. The polymerization temperature can be appropriately selected, for example, in the range of about 30 to 150 ° C.

The polymer obtained by polymerization can be purified by precipitation or reprecipitation. The precipitation or reprecipitation solvent may be either an organic solvent or water, or may be a mixed solvent. Examples of the organic solvent used as the precipitation or reprecipitation solvent include, for example, hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane); benzene; Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons (aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride); halogens such as benzene and dichlorobenzene Nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzo-tolyl, etc.) Chain ethers such as ethenoleatenore, diisopropinoleatenole and dimethoxyethane; cyclic ethers such as tetrahydrofuran and dioxane; ketones (acetone, methylethylketone, diisobutylketone, etc.) , Ester (ethyl acetate, butyl acetate, etc.), Carbonate (Dimethinolecarbonate, Jetinorecarbonate, Ethylenecarbonate, Propylenecarbonate, etc.) Butanol, carboxylic acid (such as acetic acid), and a mixed solvent containing these solvents. Among them, a solvent containing at least a hydrocarbon (particularly, an aliphatic hydrocarbon such as hexane) is preferable as the organic solvent used as the precipitation or reprecipitation solvent. In such solvents containing at least hydrocarbons, the ratio of hydrocarbons (for example, aliphatic hydrocarbons such as hexane) to other solvents is, for example, the former Z (the volume ratio; 25 ° C) = 10 0 90 ~ 991, preferably the former Z latter (volume ratio; 25 ° C) = 30/70 ~ 98/2, more preferably the former / latter (volume ratio; (25 ° C) = 50/50 ~ 97/3.

The resin composition for photoresist of the present invention contains the polymer compound of the present invention and a photoacid generator.

Examples of the photoacid generator include commonly used or known compounds that efficiently generate an acid upon exposure to light, such as diazonium salts, odonium salts (eg, diphenyl hexafluorophosphate), and sulfonium salts ( For example, triphenylsulfoniumhexafluoroantimonate, triphenyl-norethenophore-dimethylhexaphnoleophthalate phosphate, triphenylenolesnorenodium methanesulfonate, etc.), sulfonic acid ester [for example, 1 1-Feninole 1- (4-Methynolephenone) Snorehoninoleoxy-1-1-Benzylmethane, 1,2,3-Trisulfonyloxymethylbenzene, 1, 3-di-toro-2- (4-phenylphenylenolinoleoxymethyl) benzene, 1-phenyl-1- (4-methylphenylsolephoninoleoxymethyl) 1-hydroxy-1-benzoylmethane, etc.] , Oxathiazole derivatives, s-triazine derivatives, disulfone derivatives (such as diphenyldisulfone), imido compounds, oxime sulfonates, diazonaphthoquinone, and benzoin tosylate. These photoacid generators can be used alone or in combination of two or more.

The amount of the photoacid generator to be used can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each monomer unit (repeat unit) in the polymer compound, and the like. It can be selected from a range of about 0.1 to 30 parts by weight, preferably about 1 to 25 parts by weight, more preferably about 2 to 20 parts by weight based on parts by weight.

The resin composition for a photo resist includes an alkali-soluble component such as an alkali-soluble resin (for example, a novolak resin, a phenol resin, an imido resin, and a carboxyl group-containing resin), and a coloring agent (for example, a dye). Organic solvents (eg, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, etc.) Mixed solvent).

The resin composition for photoresist is applied on a substrate or a substrate, dried, and then exposed to a light beam (or a resist film) on a coating film (resist film) through a predetermined mask. A fine pattern can be formed with high precision by forming a latent image pattern and then developing.

Examples of the substrate or substrate include a silicon wafer, metal, plastic, glass, and ceramic. The application of the resin composition for photo resist is performed by a conventional coating method such as a spin coater, a dip coater, and a roller coater. This can be done using steps. The thickness of the coating film is, for example, about 0.01 to 20 m, preferably about 0.05 to 2 mm.

Various wavelengths of light, such as ultraviolet rays and X-rays, can be used for exposure. For semiconductor resists, g-rays, i-rays, excimer lasers (eg, XeCl, KrF, K r C l, A r F , A r C l, F 2, K r 2, K r A r, etc. A r ₂₎ and the like are used. The exposure energy is, for example, 0.1 to :! It is OOO mj Z cm ² about.

Upon irradiation with light, an acid is generated from the photoacid generator, and the acid generates a protective group (for example, a carboxyl group of a monomer unit having an acid-labile group of the polymer compound (alkaline soluble unit)). (Eliminable group) is rapidly eliminated, and a carboxyl group or the like contributing to solubilization is generated. Therefore, a predetermined pattern can be accurately formed by development with water or an alkaline developer.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Production Example 1

2-Buroxy-1-oxa represented by the following formula (10). Trisic mouth [4. 2. 1. 0 ³ ' ⁷ ] Nonan-5-one 2 1.3 g (0.11.8 mo 1) , Methacrylic acid 50.8 g (0.59 mo 1), phosphoric acid 120 mg (12 mmol), 4-methoxyphenolone 15 mg (0.12 mm o 1) A mixture of toluene and 210 m 1 was placed in a four-necked flask and stirred at 20 ° C. for 6 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was washed twice with 200 ml of a 10% by weight aqueous sodium carbonate solution and once with 200 ml of a 10% by weight saline solution, and the organic layer was concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography, and the 2- (1-methacryloyl) represented by the following formula (1 2) is obtained. Ruokishie butoxy) Single 4-O hexa tricyclo [4.2 1 0 ³ ^'7..] Non emissions - 5 -. On 2 5 5 g (9 6 mm o 1, to obtain a yield 81%). This substance was a mixture of two isomers, and the abundance was about 1: 1. Incidentally, the formula (1 0) represented by 2- Byuruokishi one 4-O hexa tricyclo Under 4.2.1 1.0 ³ ^'7] 2 nonan one 5-on, represented the following formula (1 1) - heat Doroki Sea 4 Okisa preparative Rishikuro from [. 4 2.1 0 ³ ^'7.] nonan one 5-one and flop port propionate vinyl, JP 2 0 0 3 - 7 3 3 2 1 No. described in The product was synthesized using the method and purified by distillation.

[2 — (1-Methacryloyloxyethoxy) 14-1-oxalic resin mouth [4.2.1. 0 ³ ' ⁷ ] Nonan-1 5-ON spectrum data]

^{_{X H-NMR (CDC1 3)}} δ 1.40-1. 4 (m, 3H), 1.56-1.63 (m, 2H), 1. 95 (s, 3H), 1.97-2.08 (m, 2H), 3.13-3 .16 (m, 1H), 3.59 (m, 0.5H), 3.67 (m, 0.5H), 4.49 (d, 0.5H), 4.57 (d, 0.5H), 5.62 (m, 1H), 6.05 (m , 1H), 6.14 (m, 1H)

Production Example 2

In a reaction vessel equipped with a Dean-Stark device and thermometer, the following formula (13) is used. 3-hydroxy 1-oxaspiro [4.5] decane-2-one 85 g (500 mm o 1), sodium carbonate 31.8 g (300 mm o 1), toluene 60 The mixture was heated to 100 ° C. while stirring under a nitrogen atmosphere. The reaction vessel _{_{I r 2 C 1 2 (C}} 8 H 12) 2 [ di eleven black port bis (1, 5-cyclopropyl O Kuta Zhen) diiridium (1)] 3. 3 6 g of (5 mmo 1) Then, 100 g (1 m 0 1) of propionate butyl was added dropwise over 2 hours, and the mixture was heated to reflux and reacted while azeotropically dehydrating. After completion of the dropwise addition, the reaction was continued for another 3 hours. After completion of the reaction, the reaction solution was allowed to cool, washed with 700 ml of water, and concentrated under reduced pressure. The concentrated residue is purified by distillation, and is a colorless transparent liquid of 3-vinyl xyl-1-oxaspiro [4.5] decane-2-one represented by the following formula (14) 22.5 g (114 mm o 1, 23%). The 3-hydroxy-1-oxaspiro [4.5] decane-2-one represented by the formula (13) can be obtained from cyclohexanol and methyl acrylate by the literature [Chem. Commun., 7, 613]. -614 (2000)] and purified by silica gel column chromatography.

[3-Vinyloxy-1-oxaspiro [4.5] Decane 2-on spectrum data] 'H-NMR (CDC) δ: 1.35-1.89 (m, 10H), 2.04 (dd, 1H), 2.50 (dd, 1H), 4.20 (dd, 1H), 4.42 (dd, 1H), 4.65 (t, 1H), 6.48 (q, 1H) 3-Vinyloxy 1-oxaspiro [4.5] decane-2-one 1 7.1 g (87 mm 01), methacrylic acid 37.4 g ( 43.5 mmo 1), 0.85 g of phosphoric acid (8.7 mmo 1), 4-methoxypheno 11.7 lmg (0.14 mm 0 1), tonoleen 170 ml The mixture was placed in a reaction vessel and stirred at 50 ° C. for 4.5 hours under a dry air atmosphere. After completion of the reaction, the reaction solution was washed sequentially with 170 ml of water, 170 ml (twice) of a 10% by weight aqueous sodium carbonate solution and 170 ml of water, and the organic layer was concentrated under reduced pressure. The concentrated residue is purified by silica gel column chromatography, and is represented by the following formula (15): 31- (1-metharyloyloxytoxy) -11-oxaspiro [4.5] decane-2-one [= 3- (1 Thus, 17.3 g (61 mmo1, yield 70%) of a colorless liquid of 1-oxo- 1-oxaspiro [4.5] decane] was obtained. This substance was a mixture of isomer A and isomer B, and its abundance was approximately A: B = 3: 1.

[3— (1-Metalloyloxyxetoxy) -1-oxoxaspiro [4.5] Decane 1-2-on spectral data]

Isomer A

'H-NMR (CDCI3) δ 1.34-1.84 (ra, 13H), 1.92-1.97 (m, 4H), 2.40 (dd, 1H), 4.76 (t, 1H), 5.64 (m, 1H), 6.16 (m, 1H), 6.28 (q, 1H) Isomer B ¹ H _ NMR (CDCI3) δ 1.35-1.86 (m, 13H), 1.94-1.99 (m, 4H), 2.53 (dd, 1H), 4.63 (t, 1H), 5.64 (m, 1H), 6.09 (q, 1H), 6.21 (m, 1H) Production example 3

Adamantane ethanol 43.2 g, butyl propionate 48.1 g, sodium carbonate 15.3 g, toluene 120 ml, di-μ-chlorobis (1,5-cyclooctadiene) ) A mixture of 1.62 g of iridium (I) was placed in a four-necked flask, and stirred for 4 hours while heating at 100 ° C under a nitrogen atmosphere. The precipitate in the reaction solution was separated by filtration, and the filtrate was concentrated under reduced pressure. The concentrate was purified by distillation under reduced pressure to obtain 34.8 g of 2- (adamantan-11-yl) ethylvilleether represented by the following formula (16).

[2— (adamantane 1-inole) ethyl vinyl ether spectral data]

— NMR (CDCI3) δ 1.46 (t, 2H), 1.53 (d, 6H), 1.62-1.72 (m,

6H), 1.95 (m, 3H), 3.73 (t, 2H), 3.96 (m, 1H), 4.16 (m, 1H), 6.46 (m, 1H)

Production Example 4

2- (adamantane-1-yl) ethylbutyl ether 32.8 g, methacrylic acid 68.4 g, phosphoric acid 0.16 g, 4-methoxyphenol 0.16 4 g, toluene The mixture of 290 ml was placed in a four-necked flask and stirred at 20 ° C for 6 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was washed twice with 500 ml of a 10% by weight aqueous sodium carbonate solution and once with 500 ml of a 10% by weight saline solution, and the organic layer was concentrated under reduced pressure. The concentrate is purified by silica gel column chromatography, and is obtained by the following formula (17): [2— (Adamantane-11-yl) ethoxy] ethyl (meth) acrylate 38

[1-[2-(Adamantane 1-yl) ethoxy] Etchyl (meta) Acct rate data

^{_{J H- NMR (CDC1 3) δ}} : 1.37-1.41 (m, 2H), 1. 3 (d, 3H), 1.50 (d, 6H), 1.60-1.71 (m, 6H), 1.93 (m, 3H) , 1.96 (m, 3H), 3.53 (m, 1H), 3.7 2 (m, 1H), 5.60 (m, 1H), 5.97 (m, 1H), 6.16 (m, 1H)

Production Example 5

Bornyl ether represented by the following formula (18): 18.0 g (0.1 m 01), methatrilic acid 43.0 g (0.5 m 01), phosphoric acid 9 mg, lmmol), 4-Methoxyphenolone 12 mg, 0.1 mmo1) and toluene 18 Om1 were placed in a four-necked flask and placed under a nitrogen atmosphere. The mixture was stirred at ° C for 6 hours. After completion of the reaction, the reaction solution was washed twice with 100 ml of a 10% by weight aqueous sodium carbonate solution and once with 200 ml of a 10% by weight saline solution, and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography to obtain 11- (bornyloxy) ethyl methacrylate represented by the following formula (19): 22.8 g (85 mmo1, yield: 85%) Was The bonoleninolebininoleatenole was synthesized from (i) -bonoreneo monole and propionate bull using the method described in JP-A-2003-73331, and purified by distillation. What was used was used.

(18)

[11- (Bornyloxy) ethyl methacrylate spectral data

]

_{^ -NMR (CDC1 3) δ:} . 0.80-0.84 (ra, 9H), 0.86 (d, 1H), 1.18-1 27 (m, 2H), 1.42-1.45 (d, 3H), 1.57-1.70 (m , 2H), 1.94 (s, 3H), 1.95-1.99 (m, 1H), 2.05-2.20 (m, 1H), 3.79-3.82 (m, 1H), 5.56 (m, 1H), 5.97- 6.00 (m, 1H), 6.12 (m, 1H)

Example 1

Synthesis of resin with the following structure

Propylene glycol monomethyl ether acetate (PGM) was added to a separable flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube.

EA) and propylene glycol monomethyl ether (PGME) (16.5 g each) were introduced, and the mixture was heated to 85 ° C and heated to 1-methacryloyloxy 4-oxatricyclo [4.3.1.1. I ³ ' ⁸ ]

9 3 g, 1-hydroxy-1-3-methacryloyloxydamantane 4. 6 6 g, 2-(1-methacryloyloxyethoxy) 14-oxatricyclo [4.2.1. 0 ³ ' ⁷ ] nonane-5-one 5. 41 g and dimethyl — 2, 2, 1-azobis (2-methylpropionate) (Initiator; Wako Pure Chemical Industries, trade name "V-601") 0.60 g of PGMEA and 34.2 g of PGME These were made into a mixed solution, and these were added dropwise over 4 hours. After dropping, the mixture was aged for 2 hours. The resulting reaction solution was added dropwise to a mixed solution of 733 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was collected with a nut. The obtained polymer was dried under reduced pressure to obtain 13.8 g of the desired product. The weight average molecular weight (M _w ) of the obtained polymer was 9800, and the molecular weight distribution (M / MJ was 1.88 (measured GPC value, in terms of polystyrene) i.

Synthesis of resin with the following structure

16.5 g of propylene glycol monomethyl ether acetate (PGM EA) and 16.5 g of propylene glycol monomethyl ether (PGME) were introduced into a separable flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube. After heating to 85 ° C, 1-hydroxy-13-methacryloyloxyadamantane 4.13 g, 2- (1-methacryloyloxyethoxyethoxy) 14-oxatricyclo [4.2 1. 0 ³ ' ⁷ ] Nonane-1-one 10.87 g and dimethyl-1,2,2-azobis (2-methyl Propionate) (Initiator: Wako Pure Chemical Industries, trade name “V-601”) 0.60 g was mixed with 34.2 g of PGME A and 34.2 g of PGME each. It was dropped over time. After dropping, the mixture was aged for 2 hours. The obtained reaction solution was added dropwise to a mixed solution of 733 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was collected with a nut. The obtained polymer was dried under reduced pressure to obtain 13.5 g of the desired product. The weight average molecular weight (M _w ) of the obtained polymer was 100 ° and the molecular weight distribution (M _w / M _n ) was 1.90 (GPC measurement value, converted to polystyrene).

Example 3

Synthesis of resin with the following structure

16.5 g of propylene glycol monomethyl ether acetate (PGM EA) and 16.5 g of propylene glycol monomethyl ether (PGME) were introduced into a separable flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube. After raising the temperature to 85 ° C, 1-hydroxy-13-methacryloyloxyadamantane 4.44 g, 2- (1-methacryloyloxyxetoxy) -14-oxatricyclo [4.2 . 1.0 ³ ^'7] nonane one 5- on-1 0. 0 2 g, and Metaku acrylic acid 0.5 4, dimethyl one 2, 2, Azobisu (2-methylpropionate) (initiator; Wako pure Pharmaceutical, product name "V_601") 0.60 g, PGMEA and PGME A mixed solution of 34.2 g was added dropwise over 4 hours. After dropping, the mixture was aged for 2 hours. The obtained reaction solution was added dropwise to a mixed solution of 7333 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was collected by Nutch. The obtained polymer was dried under reduced pressure to obtain 13.5 g of the desired product. The weight average molecular weight (M _w ) of the obtained polymer was 100,000, and the molecular weight distribution (M _W ZM J was 1.90 (measured GPC value, converted to polystyrene)).

Example 4

Synthesis of resin with the following structure

16.5 g of propylene glycol monomethyl ether acetate (PGM EA) and propylene glycol monomethyl ether (P GME) were placed in a separate flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube. After introducing the mixture and raising the temperature to 85 ° C, 1-methacryloyloxy 4-oxatricyclo [4.3.1. I ³ ' ⁸ ] pentane_ 5 -one 4.88 g, 1-hydroxyl 3- Methacryloyloxydamantane 4.6 1 g, 3- (1-methacryloyloxyxetoxy) -11-oxaspilot [4.5] decane-2-one 5.5 1 g, dimethyl-1,2,2'- Azobis (2-methylpropionate) (Initiator: Wako Pure Chemical Industries, trade name "V-601") 0.60 g, 34.2 g each of PGEA and PGME Solutions were added dropwise over 4 hours. 2 hours after dripping Matured. The obtained reaction solution was added dropwise to a mixture of 733 g of hexane and 81 g of ethyl acetate, and the precipitated polymer was collected by Nutsche. The obtained polymer was dried under reduced pressure to obtain 12.6 g of the desired product. The weight average molecular weight (M _w ) of the obtained polymer was 990, and the molecular weight distribution (M _w / M _n ) was 1.91 (measured GPC value, in terms of polystyrene).

Example 5

Synthesis of resin with the following structure

EA) and propylene glycol monomethyl ether (PGME) (16.5 g each) were introduced, and after heating to 85 ° C, 1-hydroxy-3-methacryloyloxydamantane 3.96 g, 3-(1-methacryloyloxyethoxy) 1 1 -oxaspiro [4.5] decane 1 -one 1 1.04 g and dimethyl 2,2 '-azobis (2-methylpropionate) (start Agent: Wako Pure Chemical Industries, trade name "V-601") 0.60 g was made into a mixed solution of 34.2 g each of PGME A and PGME, and these were added dropwise over 4 hours. . After dropping, the mixture was aged for 2 hours. The obtained reaction solution was dropped into a mixed solution of 733 g of hexane and 81 g of ethyl acetate, and the precipitated polymer was collected by Nutsche. The obtained polymer is dried under reduced pressure, 12.8 g were obtained. The weight average molecular weight (M _w ) of the obtained polymer was 980, and the molecular weight distribution (M _w / M _n ) was 1.89 (measured GPC value, in terms of polystyrene).

Example 6

Synthesis of resin with the following structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and 16.5 g of propylene glycol monomethyl ether (PGME) were introduced into a separable flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube. After heating to 85 ° C, 1-hydroxy-3-methacryloyloxyadamantane 4.27 g, 3- (1-methacryloyloxyxhetoxy) 1-1-oxaspiro [4.5] Decane-2-one 1 0.21 g, methacrylic acid 0.52 g, and dimethyl-1,2'-azobis (2-methylpropionate) (initiator; Wako Pure Chemical Industries, trade name " V—601 ”) 0.60 g was made into a mixed solution of 34.2 g each of PGMEA and PGME, and these were added dropwise over 4 hours. After dropping, it was aged for 2 hours. The obtained reaction solution was dropped into a mixed solution of 733 g of hexane and 81 g of ethyl acetate, and the precipitated polymer was collected by Nutsche. The obtained polymer was dried under reduced pressure to obtain 12.5 g of the desired product. The weight average molecular weight (M _w ) of the obtained polymer was 110,000, and the molecular weight distribution (M _W ZMJ was 1.88. (GPC measurement value, converted to polystyrene).

Example 7

Synthesis of resin with the following structure

Into a separable flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube, introduce propylene glycol monomethyl ether oleate acetate (PGMEA) and propylene glycol monomethyl ether (PGME) (16.5 g each). After raising the temperature to 85 ° C, 1-methacryloyloxy 4-oxatricyclo [4.3.1 1. I ³ ' ⁸ ] pentane-5-one 4.77 g, 1—hydroxy-3 —Methacryloyloxyadamantane 4.50 g, 1- [2- (adamantane-1 1-yl) ethoxy] ethyl metharylate 5.74 g and dimethyl-1,2,2'-azobis (2-methyl (Propionate) (Initiator: Wako Pure Chemical Industries, trade name “V-601”) 0.60 g was mixed with 34.2 g of PGME A and 34.2 g of PGME each. It was dropped over time. After dropping, the mixture was aged for 2 hours. The obtained reaction solution was added dropwise to a mixed solution of 733 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was collected by Nutch. The obtained polymer was dried under reduced pressure to obtain 13.5 g of the desired product. The weight average molecular weight (M _w ) of the obtained polymer was 930, and the molecular weight distribution (M _w ZM _n ) was 1.92 (GP C measurement value, converted to polystyrene).

Example 8

Synthesis of resin with the following structure

In a separable flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube, propylene glycol monomethinoleate enorea acetate (PGM

EA) and propylene glycol monomethyl ether (PGME) (16.5 g each) were introduced, and the mixture was heated to 85 ° C and heated to 1-methacryloyloxy 4-oxatricyclo [4.3.1.1.I ³ ^'8] Undekan one 5-on 4. 9 3 g, and 1-arsenide Dorokishi _ 3 Metaku Li Roy Honoré oxy § Dammann Tan 4. 6 6 g, 1 i (Boruniruokishi) Echirumetaku Li rate 5. 4 1 g Dimethyl-2,2'-azobis (2-methylpropionate) (Initiator: Wako Pure Chemical Industries, trade name "V-601") 0.60 g, 34.34 g each for PGMEA and PGME A mixed solution of 2 g was prepared and added dropwise over 4 hours. After dropping, the mixture was aged for 2 hours. The resulting reaction solution was added dropwise to a mixed solution of 733 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was collected by Nutsche. The obtained polymer was dried under reduced pressure to obtain 13.2 g of the desired product. The weight average molecular weight (M _w ) of the obtained polymer was 9,400, and the molecular weight distribution (M _w ZM _n ) was 1.90 (GPC measurement value, polystyrene conversion). Comparative Example 1

Synthesis of resin with the following structure

In a separable flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube, propylene glycol monomethyl enoate ethereal acetate (PGM EA) and propylene glycol monomethyl ether (PGME) were each added. After introducing 5 g and raising the temperature to 85 ° C, 1-methacryloyloxy 4-oxatricyclo [4.3.1.1. I ³ ' ⁸ ] pentane-5-one 5.16 g, 1-hydroxy _ 3-methacryloxydamantane 4.87 g, 2-methacryloyloxy 1-2-methyladamantane 4.97 g, and dimethyl-1,2'-azobis (2 _methylpropio (Initiator: Wako Pure Chemical Industries, trade name "V_601") 0.60 g was made into a mixed solution of 34.2 g of PGMEA and PGME, respectively, and these were taken for 4 hours. And dropped. After dropping, the mixture was aged for 2 hours. The obtained reaction solution was added dropwise to a mixed solution of 733 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was recovered with a nylon. The obtained polymer was dried under reduced pressure to obtain 13.5 g of the desired product. The weight average molecular weight (M _w ) of the obtained polymer was 980, and the molecular weight distribution (M _W / M J was 1.88 (measured GPC value, converted to polystyrene)).

Evaluation test

For each polymer obtained in the above Examples and Comparative Examples, 100% by weight of the polymer And propylene glycol monomethyl ether (PGME), which is a solvent, was mixed with 10 parts by weight of triphenylsulfo-dimethylhexafluoroantimonate and propylene glycol monomethyl ether (PGME) to obtain a polymer concentration of 17 parts by weight. / ₀ of the photoresist resin composition was prepared. This composition was applied on a silicon wafer by spin coating to form a light-sensitive layer having a thickness of 1.0 μπι. After pre-beta 1 for 50 seconds at a temperature of 100 ° C by a hot plate, using the K r F excimer laser with a wavelength of 247 nm, through a mask, after exposure in dose 3 Om J cm ^2, at a temperature of 100 ° C Bost peter for 60 seconds. Then, the film was developed with an aqueous solution of 0.3 M tetramethylammonium hydroxide for 60 seconds, and rinsed with pure water. As a result, in each case where the polymer of the example was used, a line 'and' space pattern of 0.20 μιη was clearly and accurately obtained, but when the polymer of the comparative example was used, the pattern of the pattern was obtained. Accuracy was poor and lacked clarity.

Claims

The following formula (1)

( ¹⁾

Unsaturated rubonic acid hemiacetal ester represented by

2. The unsaturated carboxylic acid hemiacetal ester according to claim 1, wherein the cyclic skeleton in R ^d is a lactone skeleton or a non-aromatic polycyclic skeleton. 3. The following formula (3)

(3)

(Wherein, ^Ra represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms)

The unsaturated carboxylic acid represented by the following formula (4)

(In the formula, R represents a hydrogen atom or a hydrocarbon group, R ^d represents an organic group having a cyclic skeleton, and R ^e and R ^f each represent a hydrogen atom or a hydrocarbon group.) Reacting with a vinyl ether compound represented by the following formula (5)

(Wherein, R ^a , R \ R ^d and R \ R ^f are the same as above)

A method for producing a myacetal ester of an unsaturated carboxylic acid, comprising obtaining a myacetal ester to an unsaturated carboxylic acid represented by the formula:

4. The following formula (I)

R ^a

I,

~ ("CH ₂ — C +

c = o

(i)

R ^b — C-R ^c

0

R ^d

A polymer compound containing a repeating unit represented by the formula:

5. In addition, at least one monomer selected from a ratatone skeleton-containing monomer, a cyclic ketone skeleton-containing monomer, an acid anhydride group-containing monomer, and a imide group-containing monomer 5. The polymer compound according to claim 4, comprising a repeating unit [excluding a repeating unit represented by the formula (I)] corresponding to a body.

6. In addition, at least one monomer selected from a monomer containing a hydroxyl group, a monomer containing a mercapto group, and a monomer containing a carboxyl group. 6. The polymer compound according to claim 4, which comprises a corresponding repeating unit.

7. A photoresist resin composition comprising at least the polymer compound according to any one of claims 4 to 6 and a photoacid generator.

8. A semiconductor comprising a step of applying a resin composition for photo resist according to claim 7 onto a substrate or a substrate to form a resist coating film, and forming a pattern through exposure and development. Manufacturing method.