WO2005075446A1 - Unsaturated carboxylic acid hemiacetal ester, polymer, and resin composition for photoresist - Google Patents

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

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

 The present invention relates to an unsaturated carboxylic acid useful as a monomer component of a resin for photoresist used when performing fine processing of a semiconductor, etc. The present invention relates to a polymer compound containing a repeating unit corresponding to a myacetal ester, a resin composition for a photoresist containing the polymer compound, and a method for producing a semiconductor. Background art

 Positive photoresists used in the semiconductor manufacturing process have properties such as the property that the irradiated area changes to alkali-soluble due to light irradiation, adhesion to silicon wafers, plasma etching resistance, and transparency to light used. Must be. The positive type photoresist is generally used as a solution containing a polymer as a main agent, a photoacid generator, and several additives for adjusting the above properties. In order to prepare a polymer, it is extremely important that the polymer as the main agent 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 As a monomer unit having a function of being soluble in a re-developing solution, a unit having a 2-methyladamantane_2-inole group ゃ 1-adamantinole 1-methylethyl group is known. (Japanese Patent Laid-Open No. 9-73173, etc.). 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 sufficient. Disclosure of the invention

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

 Another object of the present invention is to provide a polymer compound for photoresist having a good balance of substrate adhesion, etching resistance and acid desorption property, a resin composition for photoresist containing the polymer compound, and An object of the present invention is to provide 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 present inventors have conducted intensive studies to achieve the above object, and as a result, it has been found that an unsaturated carboxylic acid having a specific structure containing a polymer compound containing a repeating unit corresponding to a miacetal ester as a resin for photoresist is excellent. 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, RR ^{aa is a} hydrogen atom atom, a hahalogenogen atom atom, an aralkyquill group having a carbon number of 11 to 66 or 5 or a carbon number of 5 to 11 RR ^bb represents a hydrogenated hydrocarbon group having a hydrogen atom atom at the 11-position. In the above, RR indicates a hydrogen atom atom or a carbohydrocarbon group, and RR ^{dd includes a} cyclic bone skeleton. Shows organic organic base)))

 To provide the unsaturated unsaturated kacarrubovonic acid represented by the formula (1). .

The aforementioned cyclic skeleton of RR ^dd may be laratata tonton skeleton or non-aromatic aromatic polycyclic polycyclic 10 skeleton. The case remains good. .

The invention of the present invention is based on the following formula ((33))

1155 ((wherein, RR ^{aa is a} hydrogen atom atom, a hahalogenogen atom atom, an aralkylyl group or a carbon atom number of 11 to 66 carbon atoms) Shows 66 hahaloloaalkylalkyl groups))

The unsaturated unsaturated kacarbobonic acid represented by the formula is converted into the following formula ((44))

(In the formula, R represents a hydrogen atom or a hydrocarbon group, R ^d represents an organic group having a cyclic skeleton, and R ^B 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 \ R \ R d,} RR f have the same meanings as defined above)

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

R ^a

0, (I)

R ^b — C— R ^c

 0

 I,

R ^d

(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, and ^Rb 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.)

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

 The polymer compound further comprises at least one 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. And a repeating unit [excluding the repeating unit represented by the formula (I)] corresponding to the monomer of the formula (I). 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. You may go out.

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

The present invention further provides the resin composition for a photoresist as a substrate 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.

 It should be noted that the vinyl ether-based monomer and the vinyl ether compound in the present specification include a compound in which a hydrogen atom of a bullet 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 photoresists 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 methyl, ethynole, propynole, isopropynole, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl and the like. Of these, an alkyl group, particularly a methyl group, is preferred. Examples of the haloalkyl group having 1 to 6 carbon atoms include a chloroalkyl group such as a chloromethyl group; triphenylenomethylinole, 2,2,2-triphenylenoletinole, and pentafluoro. Examples include a fluoroanolealkyl group such as an ethyl group (preferably, a d- ₃ fluoroalkyl group).

Wherein is a hydrocarbon radical having 1-position a hydrogen atom in R ^b, for example, methyl, Echinore, propyl, i Sopuro Pinore, Puchinore, Lee Sopuchiru, alkyl groups such as s one-butyl group (e.g. C I ₆ Alkyl groups, especially —3 alkynole groups); cyclopropynole groups such as cyclopropynole, cyclopentynole, and cyclohexyl groups (for example, 3- to 6-membered cycloalkynole groups); cyclopentynolemethyl, cyclohexylmethyl groups Cycloalkyl groups such as mono- or di- (3- to 6-membered cycloalkyl) 1 C- ₃ alkyl groups; aralkyl groups such as benzinole, 1-methylbenzyl, 1-phenylpentyl, etc. For example, mono- or diphenyl-1-d-3 alkyl group). As R ^b , a C ^ ₃ alkyl group such as a methyl, ethyl, propyl, and isopropyl group is preferable, and a methyl group is particularly preferable.

Examples of the hydrocarbon group for R ^c include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and s-butyl groups (eg, C ぃ₆ alkyl groups, especially C _t - ₃ alkyl groups); Cycloalkynole groups (eg, 3- to 6-membered cycloalkyl groups) such as cyclopropyl, cyclopentynole, and cyclohexyl groups; and aryl groups such as phenyl groups. R. The by a hydrogen atom; methyl, Echiru, propyl, preferably C Bok ₃ alkyl groups such as isopropyl, especially, a hydrogen atom, a methyl group good or arbitrary.

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

The _lactone skeleton includes a _lactone ring (for example, a _lactone ring such as a _lipolactone ring, a δ-valerolactone ring, and an ε-force prolactone ring). Or aromatic carbocyclic or heterocyclic ring 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. Ring constituting the lactone skeleton, § alkyl group such as a methyl group (e.g., a d ₄ alkyl group), Haroanorekiru groups such as preparative Rifuruoromechiru group (e.g., C I ₄ haloalkyl group), a chlorine atom Ya off Tsu containing Halogen atom such as 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, protecting group May have a substituent such as a ropoxyl 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.

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

 (6b) (6c) (6d)

 (6e) (6f) (6g)

[In the formula,! ^{^ 1 ~! ^ 6, R} 9 ~R 3 6 are the same or different, a hydrogen atom, a halogen atom, Arukinore group, a haloalkyl group, an optionally protected human Dorokishiru group with a protecting group, is protected with a protecting group A hydroxyalkyl group which may be protected by a protecting group 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—. At least one of ν ′ to ν ³ is one COO—. In the formula (6f), at least two of R ^{27 to} R ³¹ may combine to form a ring together with a carbon atom or a carbon-carbon bond. In the formula (6g), at least two groups out of R ^{32 to} R ³⁶ may be bonded to form a ring together with a carbon atom or a carbon-carbon bond.

Equations (6a)-(6g) Medium! Examples of the halogen atom in ^ to ⁶ 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, isopropyl, butyl, isobutynole, s-butyl, t-butyl, hexyl, octyl, decyl, and dodecyl groups. And the like. Among them, carbon number :! Alkyl groups of 4 are preferred. Examples of the noroalkyl group include fluoroalkyl groups having 1 to 13 carbon atoms, such as trifluoromethyl and pentafluoroethyl groups. Examples of the hydroxyl group which may be protected with a protecting group include a hydroxyl group and a substituted oxy group (for example, a C alkoxy group such as methoxy, ethoxy, propoxy group, etc.). Examples of the hydroxyalkyl group which may be protected with a protecting group include a group in which a hydroxyl group which may be protected with the protecting group is bonded via an alkylene group having 1 to 6 carbon atoms. Is mentioned. Examples of the mercapto group that 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. The carboxyl group which may be protected by a protecting group, and the like one C_〇_〇_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, buty ^^, isobutyl, s-butyl, t-butyl, hexyl, etc. And branched or branched alkyl groups having 1 to 6 carbon atoms. The alkylene group for X includes a linear or branched alkylene group having about 1 to 3 carbon atoms (preferably 1 or 2) such as methylene, dimethylmethylene, ethylene, propylene, and trimethylene groups. And the like.

A ring formed by bonding at least two groups out of R ^{27 to} R ³¹ together with a carbon atom or a carbon-carbon bond; and bonding a carbon atom or carbon atom by bonding at least two groups out of R ^{32 to} R ^36. The ring formed together with the carbon bond includes an alicyclic carbocycle (including a bridged carbocycle) 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 lactone skeleton includes a monocyclic or polycyclic non-aromatic or aromatic ring. The monocyclic non-aromatic ring includes, 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, a cyclodecane ring; a tetrahydrofuran ring And a 3- to 15-membered non-aromatic heterocycle such as a pyrrolidine ring, a piperidine ring and a morpholine ring. Is a polycyclic nonaromatic ring, for example, Adamantan ring; norbornane ring, Bruno Ruborunen ring, bornane ring, isobornane ring, preparative Rishikuro [. 5.2.1 0 ^{2 '6]} decane ring, Te Torashikuro [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] A ring containing a norbornane ring or a norbornene ring such as a dodecane ring; a perhydro-indene ring, a decalin ring (a perhydrronaphthalene ring), and a perhydrorofluor Len ring (tricyclo [7.4.3 0.0 ^{3 '8]} tridecane ring), polycyclic aromatic condensed ring is hydrogenated ring such Pahi mud anthracene ring (rather preferably are fully hydrogenated添力D Tricyclo [4.2.2. 2. I ² ' ⁵ ] Bridged carbon ring such as bicyclic, tricyclic, or tetracyclic ring such as a pentadecane ring (for example, having about 6 to 20 carbon atoms) A bridged carbon ring). 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 preferably a polycyclic non-aromatic carbocyclic ring (bridged carbocyclic ring). 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.

Ring constituting the cyclic skeleton other than the lactone skeleton, Al kill group such as a methyl group (e.g., _alkyl group), triflate Ruo b Haroarukinore group such as a methyl group (e.g., 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 trimethylene groups; carbonyl groups; oxygen atoms (ether bonds; ___- 1); oxycarbonyl groups (ester bonds; —); An amino lponyl 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 alkylene group (particularly, a d- ₃ alkylene group) and the like. 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. The Uchiraku 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 compound having an organic group containing a lactone skeleton among the unsaturated carboxylic acid hemiacetal esters represented by the formula (1) [Lactone among the compounds containing the group represented by the formula (2)] The following compounds may be mentioned as examples of the compound having a skeleton. The present invention is not limited thereto.

[1-1] 1-1 [1 — (meta) atalyloyloxyethoxy] — 4-oxosatricyclo [4.3.1. I ³ ' ⁸ ] pentane-5-one [Z' = Formula (6a), A = single bond]

[1-2] 2- [1 one (meth) Atta Li Roiruokishe butoxy] - 4 Oki Satorishikuro [4.2.3 1.0 ^{3 '7]} nonane one 5- ON [Z] = formula (6b), A = Single bond]

[1-3] 2-[1- (meta) atari roiroxhetoxy] — 6-meth Lou 4 Okisatori cyclo [4.2.3 1.0 ^{3 '7]} nonane one 5- ON [Z' = formula (6b), A = single bond]

[1-4] 2- [1 one (meth) § click Re Roiruokishe butoxy] - 6 _ tri Furuoromechiru 4 Okisato Li cyclo [4.2.3 1.0 ^{3 '7]} nonane one 5- ON [Z ¹ ^ formula (6b), A = single bond]

[1-5] 2- [1 one (meth) § click Li Roy Ruo ethoxy] one 9-methylation one 4- Okisatorishikuro [4.2.3 1.0 ^{3 '7]} nonane one 5- ON [Z ¹ = Equation (6b), A = Single bond]

[1-6] 6-Fluoro-2 — [1- (meth) acryloyloxetoxy] 1-4-Oxatolycyclo [4.2.2.1.0 ³ ' ⁷ ] Nonan-5_one [Z formula ( 6b), A = single bond]

[1-7] 9 one carboxy one 2- [1 - (meth) § click Re Roiruokishieto carboxymethyl] one 4- Okisatori cyclo [4.2.3 1.0 ^{3 '7]} nonane one 5- ON

[Ze = Equation (6b), A = Single bond]

[1-8] 2— [1- (meta) acryloyllo: shetoxy] 1-9-methoxycarboninole 4-oxatricyclo [4 2.1.0 ³ ' ⁷ ] Nonane' 5 _ ON formula (6b), A = single bond]

[1-9] 9-1 E Toki Shikano repo Nino rate 2- [1 - (meth) Ata Li Roiruo Kishietokishi] one 4-O hexa tricyclo [4 2. 1.0 ^{3 '7]} nonane 5-on (6b ), A = single bond]

[1-10] 9 1 t-butoxycarbonyl 2 -— [1 (meta) attaliloyloxyethoxy] 1-4—oxatricyclo [4 2.1.0 ³ ' ⁷ ] nonan-5-one formula (6b ), A = single bond]

[1-11] 2 one [1 one (meth) § click Li Roy Ruo ethoxy] - 4, 8-di-O hexa tricyclo [. 4 2. 1.0 ^{3 '7]} nonane one 5- one [ Z ^! = Expression

(6b), A = single bond] [1-12] 4-[1- (meta) acryloyloxyethoxy]-6-oxo sabicyclo [3.2.1.1] 7-one [Z ¹ = formula (6b), A = single Join]

[1-13] 8 one [1- (meth) § click Re Roiruokishe butoxy] one 4-O key Satorishikuro [5.2.2 1.0 ^{2 '6]} decane one 5--on (6c), A = single Join]

[1-14] 9- [1- (meth) § click Li Roy Ruo ethoxy] - 4-O key Satorishikuro [5.2.2 1.0 ^{2 '6]} decane one 5- ON [Z ¹ = formula ( 6c), A = single bond]

 [1-15] a-[1- (Meth) acryloyloxyethoxy] 1'-dimethyl-γ-butyrolactone formula (6g), A = single bond

[1-16] 3-[(1- (meta) atali royloxyethoxy] 12-oxo- 1-oxaspiro [4.5] Decane [Z ¹ ^ formula (6g), A = single bond]

[1-17] a- [1- (meta) atali royloxyethoxy]-y-buta-mouth rataton [Z ¹ ^ formula (6g), A = single bond]

[1-18] a-[1- (meta) acryloyloxyethoxy]-, y, y— trimethyl-1 τ; 1-butyrolatatone [Z ¹ ^ formula (6g), A = single bond] [1-19] ] a — [11- (Meth) acryloyloxyethoxy] — β, β- _dimethyl- butyrolactone [Ζ '= Formula (6g), A = single bond]

[1-20] Compound represented by the following formula (7) [Z ¹ -Formula (6g), A = single bond

]

(7)

[1-21] 3- [1- (meta) acryloyloxyethoxy] 1-2-oxo 1-oxaspiro [4.4.] Nonane formula (6g), A = single bond]

 A typical example of a compound having an organic group containing a cyclic skeleton other than the ratatone skeleton among the unsaturated phenolic hemiacetal esters represented by the formula (1) [The group represented by the formula (2) Compounds having an organic group containing a cyclic skeleton other than the ratatone skeleton among the compounds contained therein include the following compounds, but are not limited thereto.

 [1-22] 1- (Adamantane 1-yloxy) ethyl (meta)

 [1-23] 1-(Adamantane 1 _ilmethoxy) ethyl (meta) acrylate

 [1-24] 1 1 [2— (Adamantane 1 1-inole) Ethoxy] ethyl (meta) acrylate

 [1-25] 1-[1-(Adamantane 11-yl) 1-1-methylethoxy] ethyl (meth) acrylate

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

 [1-27] 1-(3-Hydroxydamantane 1-yloxy) ethyl (meth) acrylate

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

 [1-29] 1- (3-carboxy adamantane 1-yloxy) ethyl (meth) acrylate

[1-30] 1- (3,5-dicanolepox-adamantane-1-yloxy) ethyl (meta) atalilate [1-31]! 1 1 (Norbonorenan 1-2-yloxy) ethyl (meta) acrylate

 1

 1

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

 (2-Methylnorbornane-1-yloxy) ethyl (meta)

 [1-34] 1 1 [1-(Norbornane 1-2-yl) 1 1 1 Methylethoxy

] Ethyl (meta) atari rate

 (3 — Hydroxynorbonorenane 21-inoleoxy)

(Meta) factory

 [1-36] 1-(3 —Hydroxymethinorenolenolevonolenane 2—Ilmethoxy

) Ethyl (meta) Atari rate

 (5, 6-dihydroxy-noroxy-bononorenane 2-irmethoxy

) Ethyl (meta) atari rate

 [1-38] 1 (3 -methylnorbornane 1-2-methoxy) ethyl (meta) acrylate

 [1-39] 1- (decalin-1-yloxy) ethyl (meta) acrylate

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

 [1-41] 1 — (5—Hydroxydecalin 1—Iroxy) ethyl (meta) atalilate

[1-42] 8 _ arsenide Dorokishimechiru 4 one [1 - (meth) Ata Li Roiruoki Shetokishimechiru] tricyclo [5.2.1 & 0 ^6] decane

[1-43] 4-Hydroxymethyl-8- [1— (meta) aryloyloxyethoxymethyl] tricyclo “5.2.1.0 ² ' ⁶ ] decane [1-44] 1- (Bornyloxy) ethy / le (meta) acrylate

 [1-45] 1- (Isopolnyroxy) ethyl (meth) acrylate

[1-46] 3-carboxy-1 8— [1- (meta) aryloyloxyethoxy] tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] dodecane

[1-47] 3-Carboxy-9-1 [1- (Meth) aryloyloxyethoxy] tetracyclo [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. and R ^d are the same as above. R ^e and R ^f each represent a hydrogen atom or a hydrocarbon group, and one CHR SR ^f corresponds to 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 any of an inorganic acid and 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; and polyacids such as phosphomolybdic acid, chemolybdic acid, phosphorus tungstic acid, and silicotungstic acid; Body catalyst and the like. Examples of the organic acid include carboxylic acids such as formic acid, acetic acid, and trifluoroacetic acid; and sulfonic acids such as methanesnolefonic acid, trifluoromethanesulfonic acid, benzenesnolefonic acid, p-tonolenesnolefonic acid, and naphthalenesulfonic acid. Can be 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; Alicyclic hydrocarbons such as mouth hexane; halogenated hydrocarbons such as methylene chloride; ethers such as tetrahydrofuran and ethylene glycol—non-resin-methinoleate; non-acetones such as N, N-dimethylformamide Examples include protonic 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 100 mol per 1 mol of the butyl ether compound represented by the formula (4). It is about 10 mol. The amount of the acid catalyst to be used is, for example, about 0.001 :! to about 1 mol, preferably about 0.001 to 0.3 mol, per 1 mol of the vinyl ether compound represented by the formula (4). It is.

 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 0.0001 to 0.05 mol, preferably 0.00001 to 1 mol of the vinyl ether compound represented by the formula (4). O.0.1 is about 1 mole.

 The reaction temperature varies depending on the type of the reaction raw material, the type of the catalyst used, and the like, but is usually about 10 to 100 ° C, preferably about 0 to 60 ° C.

After completion of the reaction, the reaction product can be separated and purified by a separation means such as liquid 1 production control, extraction, concentration, distillation, crystallization, recrystallization, and column chromatography. In addition, in addition to the unsaturated carboxylic acid hemiacetal ester represented by the formula (1), R ^b and R in the formula (1). Are all hydrogen atoms, and are also useful as monomers of polymer compounds for photoresist. 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 compounds corresponding to the examples of the unsaturated carboxylic acid hemiacetal ester represented by the above formula (1) (compounds in which R ^b = R. = H) and the like.

R ^b and R in the formula (1). Is a hydrogen atom [compound represented by the formula (:)], 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 Y include a chlorine, bromine, and iodine atom. 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 and pyridine, or an inorganic base such as sodium hydroxide, sodium carbonate and sodium hydrogen carbonate 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, per mol of the halomethyl ether compound represented by the formula (A). About 2 moles. The amount of the base used is, for example, about 1 to 5 mol per mol of the unsaturated carboxylic acid represented by the formula (3). Yes. 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 −10 ° C. to 100 ° C., preferably about 0 to 60 ° C. After the completion of the reaction, the reaction product can be separated and purified by a separation means such as liquid property adjustment, extraction, concentration, distillation, crystallization, recrystallization, column chromatography and the like.

 The halomethyl ether conjugate represented by the formula (A) is, for example, as shown in the following reaction formula, a hydroxy compound represented by the formula (C) added to formaldehyde or its equivalent (para). Formaldehyde, 1,3,5-trioxane, etc.) and a halogen hydride represented by the formula (D).

Rd-OH ^ Oki: Y-C¾-0-R ^d

( ^C )? 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 mol, preferably 1 to 1 mol, per mol of the hydroxy compound represented by the formula (C), in terms of formaldehyde. It is about 5 moles. The amount of the hydrogen halide represented by the formula (D) is, for example, about 1 to 5 mol per mol of the hydroxy compound represented by the formula (C), and a large excess may be used. The reaction temperature is usually about −10 ° C. to 100 ° C., preferably 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. [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 high molecular compound can be obtained by subjecting the above unsaturated carboxylic acid to a miacetal 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, which makes the ester 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 the wettability with respect to an alkaline developer are improved. Further, when the repeating unit represented by the formula (I) has a lactone 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. Substrate adhesion can be significantly increased while maintaining the number of leaving groups, so that high substrate adhesion can be achieved, and the number of acid-labile groups and the number of substrate adhesion groups are maintained In addition, by introducing a repeating unit having another function such as hydrophilicity, it is excellent in that both acid elimination property, substrate adhesion and other functions can be 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 a polymerizable unsaturated monomer corresponding to the repeating unit with the unsaturated rubonic acid and a miacetal ester. As the other repeating unit, for example, a repeating unit having a substrate adhesion and a Z or hydrophilic function, a repeating unit improving an acid desorption property, a repeating unit improving an etching resistance function, and improving transparency And repeating units. 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. A repeating unit having substrate adhesion and Z or 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) a lactone ring-containing group, a carbonyl group, an acid anhydride group, and an imido group; and (2) a hydroxyl group optionally having a protective group. A mercapto group which may have a protecting group, a carboxyl group which may have a protecting group, a diamino group which may have a protecting group and a sulfonic acid group which may have a protecting group And the like. Examples of the polymerizable unsaturated monomer having a polar group include: (a) a monomer containing a ratatone skeleton, a monomer containing a cyclic ketone skeleton, a monomer containing an acid anhydride group, and a monomer containing an imido group. A monomer such as a monomer, (b) a monomer containing a hydroxy group (including a compound in which a hydroxy group is protected), a monomer containing a mercapto group (a compound in which a mercapto group is protected) ), A carboxy group-containing monomer (including a compound having a protected carboxyl group), an amino group-containing monomer (including a compound having a protected amino group), and sulfonate Group-containing monomers (including conjugates in which the sulfonic acid group is protected) 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 the monomer belonging to the above (a) and the monomer belonging to the above (b), it is possible to develop a balanced resist property S.

The repeating unit that enhances the acid elimination function includes, for example, (c) a hydrocarbon group having a tertiary carbon, a 2-tetrahydrofuranyl group, or a 2-tetrahydro group at a position adjacent to the oxygen atom constituting the ester. (Meta) acrylic acid ester derivatives having a drobilanyl group, etc., and (d) hydrocarbon groups (alicyclic hydrocarbon groups, aliphatic hydrocarbon groups, etc.) bonded adjacent to the oxygen atoms constituting the ester And the hydrocarbon group is a COOR ^x group (R ^x represents a tertiary hydrocarbon group, 2-tetrahydrofuranyl group or 2-tetrahydrovinylyl group). A (meth) acrylate ester derivative or the like bonded directly or via a linking group can be introduced into a polymer by using as a comonomer. As such a (meth) atalinoleic acid ester 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, an unsaturated carboxylic acid used to impart various functions as a resist to the polymer compound of the present invention is represented by the following formula (8a) To (8g). These correspond to the lactone skeleton-containing monomer and the cyclic ketone skeleton-containing monomer.

(In the formula, R represents a hydrogen atom or a methyl group. 1 ^ to ¹⁶ , R ^{9 to} R ³⁶ , X, to V ³ are the same as described above.)

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

[2-1] 1 one (meth) § click Li Roiruokishi _ 4-O Kiso § Dammann Tan (R = H or _{^{CH 3, R x = R 2}} = R 3 = H N V = - C_〇 one, V ² = V ³ =-CH _2- )

[2-2] 1- (Meth) acryloyloxy-4-oxatricyclo [4 • 3. 1. I ³ ' ⁸ ] pentane-5-one (R = H or CH ₃ , R ^ R ² = R ³ = H, V ² =-CO-0- (left side is the side of the carbon atom to which R ² is bonded), V ^x = V ³ =-CH _2- )

[2-3] 1- (meta) acryloyloxy 4,7-dioxatrisic Mouth [. 4.4.1 1 ^3.9] dodecane one 5, 8- dione (1 = ^ 1 or Rei_1 _{"1 3, R ^ R ^} R ^ H, V ^ - C OO- ( left R ¹ binding to Les, Ru carbon atom ^{side), V 2 = - CO- 0-} ( left carbon atoms side bonded to ^{R 2), V 3 = -} CH 2 _)

[2-4] 1- (meta) acryloyloxy 4,8-dioxatrisic mouth [4.4.1. I ³ ' ⁹ ] Dodecane-1,5,7-dione (R = H or CH ₃ , R ^ R ^ R ^ H, V ^-O- CO- (left side is carbon atom side with R ¹ bonded), V ² = — CO— O— (left side is carbon atom with R ² bonded) Atomic side), V ³ =-CH _2- )

[2-5] 1- (Meth) acryloyloxy-5,7-dioxatricic mouth [4.4.1. I ³ ' ⁹ ] Dodecane-1,4,8-dione (R = H or CH ₃ , R ^ R ^ R ^ H, V ^-C O- O- (left side is carbon atom side bonded with R ¹ ), V ² = —〇— CO— (left side is R ² side Carbon atom), 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) acryloyloxy 4-oxatricyclo [4 • 2.1.0 ³ ' ⁷ ] Nonane-5-one (= 5— (Meth) acryloylo / reoxy one 2, 6 _ norbornanecarbolacton lactone) (R = H or ^{_{CH 3, R "= R 5}} = R 6 = H, X = methylene group)

[2-7] 2- (meth) § click Li Roiruokishi methyl one 4 one Okisa preparative Rishikuro [4.2.1 0 ^{3 '7.]} Nonane one 5 - one (R = H or CH _3, R ⁴ = CH ₃ , R ⁵ = R ⁶ = H, X = methylene group)

[2-8] 2- (meth) Ata Riroiruokishi one 6-methyl one 4 one Okisato Rishikuro [4.2.1 0 ^{3 '7.]} Nonane one 5 - one (R two H or Cti _3, R ⁵ = CH _{^{3, R 4 = R 6 =}} H, X = methylene group) [2-9] 2 - (meth) § click Li Roiruokishi 9-methyl-4-Okisa preparative Rishikuro [4.2.1 0 ^{3 '7.]} Nonan - 5- ON (R = H or CH _3, R ⁶ = CH _{^{3, R 4 = R 5 =}} H, X = methylene group)

[2-10] 2 - (meth) § click Li Roiruokishi one 9 - Karubokishi 4 one year old key Satori cyclo [. 4.2.1 0 ^{3 '7]} nonane one 5- ON (R = H or CH _3, R ⁴ = R ⁵ = H, R ⁶ = CO OH, X = methylene group)

[2-11] 2 - (meth) § click Li Roiruokishi one 9- main butoxy carbonitrile Nino laser 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 = Methoxycarbol group, X = Methylene group)

[2-12] · 21- (Meth) acryloyloxy 9 _ethoxycarboninole 4-oxatricyclo [4.2.1. 0 ³ ' ⁷ ] Nonan-5-one (R = H or CH ₃ , R ⁴ = R ⁵ = H, R ⁶ = ethoxycarbonyl group, X = methylene group)

[2-13] 2- (Meth) acryloyloxy _ 9 1 t-butoxycarbonyl 2- 4-oxatricyclo [4.2.1.0 ³ ' ⁷ ] Nonane 5-one (R = 11 or 11 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 the following compounds, but are not limited thereto.

[2 - 14] 8 one (meth) § click Li Roiruokishi one 4 Okisato Rishikuro [.. 5 2.1 0 ^{2 '6]} decane one 5- ON (R = H or CH ₃₎

[2-15] 9 - (meth) § click Li Roiruokishi one 4 one Okisato Li consequent opening [.. 5 2.1 0 ^{2 '6]} decane one 5- ON (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) § click Li Roiruokishi one 6- Okisabishikuro [3.2.1] octan one 7 _ On (R = H or _{^{CH 3, R 9 = R 10}} = R 1 R 12 = R ⁽¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = H)

[2-17] 4- (Meth) acryloyloxy 4- 4-methyl-6-oxabicyclo [3.2.1] octane-7-one (R = H or CH ₃ , RI ⁰ = R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = HR ⁹ = CH ₃ )

[2 - 18] 4- (meth) Atari Roiruokishi 5- methyl-6- Okisabi cyclo [3.2.1] octan one 7- ON (R = H or _{^{CH 3, R 9 = R 11}} = R 12 = R 13 = R ¹⁴ = R ¹⁵ = R ^l6 = R ¹⁷ = H, R ¹⁰ = CH ₃ )

[2-19] 4 one (meth) § click Li Roiruokishi one 4, 5- dimethyl one 6-O Kisabishikuro [3.2.1] octan one 7- ON (R = H or CH _3, R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = HR ⁹ = R ¹⁰ = CH ₃ ) Typical examples of the compound represented by the formula (8e) include the following compounds. It is not limited.

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

²¹ = R ²² = R ²³ = R ²⁴ : = R ²⁵ = R ²⁶ = H)

[2-21] 6 - (meth) Akuri Roiruokishi 6-methyl one 2- Okisabi cyclo [2.2.2] octan one 3-one (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) Akuri Roiruokishi 1-methyl _ 2- Okisabi cyclo [2.2.2] octan one 3-one (R = H or ^{_{CH 3, R '9 = R}} 20 = R 21 = (R ²² = R ²³ = R ²⁴ = R ²⁵ = R ²⁶ = H, R ¹⁸ = CH ₃ )

[2 - 23] 6- (meth) Akuri Roiruokishi one 1, 6-dimethyl-2- O Kisabishikuro [2.2.2] octan one 3 _ ON (R = H or _{^{CH 3, R 20 = R 21}} = R 22 = R ²³ = R ²⁴ = R ²⁵ = R ²⁶ = H, R ¹⁸ = R ¹⁹ = CH ₃ ) Representative examples of the compound represented by the formula (8f) include the following compounds, but are not limited thereto.

[2-24] β - (meth) Ata Li Roiruokishi gamma - Puchiroraku tons (R = is _{R 27 = R 28 = R 2} 9 = R 30 = R 3 1 = H)

 H or C H 3,

[2 - 25] β i (meth) Ata Li Roiruokishi one, C - dimethyl one "Y- Bed Chirorata tons (R = H or _{^{CH 3, R 27 = R 28}} = CH 3, R 29 = R 30 = R

³¹ = Η)

[2-26] β- (meta) atalyloyloxy-, γ-dimethinolate γ -—- futylolactone (R = H or CH ₃ , R ³⁰ = R ^ CH ₃ R ²⁷ = R ²⁸ = R

²⁹ = Η)

[2-27] β- (meth) acryloyloxy α, hi | 3-trimethyl-butyrolactone (R = Η or C Η ₃ , R ²⁷ = R ² = R ²⁹ = CH _a , R

[2-28] beta one (meth) Ata Li Roiruokishi one] 3, y-trimethyl one y - butyrolactone tons (R = H or _{^{CH 3, R 29 = R 3}} ^ CH- R 27 = R 28 = H)

[2-29] β — (meth) atalyloyloxy α, a, β, γ, γ-pentamethyl-γ — butyrolactone (R = Η or C Η ₃ , R ²⁷ = R ²⁸ = R ²⁹ =

_R 30 _{= R 31 = CH 3} ) Representative examples of the compound represented by the formula (8g) include the following compounds, but are not limited thereto.

[2-30] a- (meth) acryloyloxy-butyrolataton (R =-H or CH ₃ , R ³² = R ³³ = R ³⁴ = R ³⁵ = R ³⁶ = H)

[2-31] a- (meth) acryloyloxy-methyl-γ-butyrolatatone (R = H or CH ₃ , R ³² = CH ₃ , R ³³ = R ³⁴ = R ³⁵ = R ³⁶ = H

) [2-32] HI-(meth) atalyloyloxy β, jS — dimethyl γ — butyrolataton (R = H or CH ₃ , R ³³ = R ³⁴ = CH ₃ , R ³² = R ³⁵ = R ³⁶ = H)

[2-33] a- (Meth) acryloyloxy, β,] 3_trimethyl-γ-butyrolatatone (R = H or CH ₃ , R ³² = R ³³ = R ³⁴ = CH ₃ , R

³⁵ = R ³⁶ = W,

[2-34] a - (meth) § click Li Roinoreokishi one gamma, dimethyl γ- Bed Chiroraku tons (R = H or _{^{CH 3, R 35 = R 36}} = CH 3, R 32 = R 33 = R 34 = H )

[2-35] a- (meth) acryloyloxy, y, γ-trimethyl- _γ -petit mouth (R = H or CH ₃ , R ³² = R ³⁵ = R ³⁶ = CH ₃ , R

3 3 ₌ R 34 ₌ H)

[2-36] a one (meth) § click Li Roiruokishi β, β, y, Ichite Torame chill _ .gamma. Puchiroraku tons (R = H or _{^{CH 3, R 33 = R 34}} = R 35 = R 3 6 = CH _3, R ³² = H)

[2-37] a-(Meth) acryloyloxy α, β, β, y, y —pentamethyl_γ —ptyrolactone (R = Η or C Η ₃ , R ³² = R ³³ = R ³ "= R ₃₅ = R _{36; =} CH ₃ )

Other 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, such as maleic anhydride, Maleimide. These correspond to the acid anhydride group-containing monomer and the imide group-containing monomer. The following are typical 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. 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. Typical 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 (1, Rishikuro [7.4.3 0.0 ^{3' 8]} tridecane ring), Pahi Doroantora Sen ring, tricyclo [5.2.2 1.0 ^{2 '6]} decane ring, tricyclo ^{[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 Alkyl group such (e.g., C, etc. _ ₄ alkyl group), preparative Rifuruoromechiru haloalkyl group such as group, a fluorine atom or a halogen atom, an optionally protected coercive Mamorumoto human Dorokishiru group such as a chlorine atom, a protecting group Or protected with 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 protecting group. It may have a substituent such as a good amino group or a sulfonate group which may be protected with a protecting group. ■

In the formula (9), as the ano group for R ³⁷ : a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group And linear or branched alkyl groups having about 1 to 20 carbon atoms. As a protected or unprotected amino group, the amino group, substituted amino group (e.g., methylcarbamoyl Ruamino, Echiruamino, etc. c E one ₄ alkylamino group such as a propylamino group). It is a protected or unprotected sulfonic group with a protective group, and the like _ S 0 ₃ R ^Z group. R ^z represents a hydrogen atom or an alkyl group, and the alkyl group is a linear or branched chain such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butynole, t-butynole, 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—Hydroxy 3— (Meth) acryloyloxy-adamantane (R = H or CH ₃ , R ³⁷ = OH, n = l, Z ² = adamantane ring) [3-2] 1, 3-dihydrazide Dorokishi one 5- (meth) Ata Li Roiruokishiada Kalimantan (R = H or ^{_{CH 3, R 37 = OH,}} n = 2, Z 2 = Adamantan ring)

[3-3] 1 _ carboxy one 3- (meth) § click Li Roy Ruo carboxymethyl § Da manta emissions (R = H or ^{_{CH 3, R 37 = COOH,}} n = l, Z 2 = Adamantan ring)

[3-4] 1, 3 one Jikarubokishi 5- (meth) Ata Li Roiruokishiada Kalimantan (R = H or ^{_{CH 3, R 37 = COOH,}} n = 2, Z 2 = Adaman monocyclic)

[3-5] 1 one carboxy one 3- arsenide Dorokishi 5- (meth) Akuri Royle O carboxymethyl § Dammann Tan (R = H or CH _3, R ³⁷ = OH, C_〇 ^{OH, n = 2, Z 2} = Adamantan ring)

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

[3-7] 1, 3-bis (t-butoxycarbonyl) - 5 - (meth) § click V Roy Ruo carboxymethyl § Dammann Tan [R = H or CH _3, R ³⁷ = t- Butokishika Lupo - 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 ^{_{C II 3, R 37 = OH}} , t - butoxycarbonyl group , N = 2, Z ² = adamantane ring)

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

[3-10] 1,3-bis (2-tetrahidrobilo-roxycarbol) - 5 - (meth) § click Li Roy Ruo carboxymethyl § Dammann Tan (R = H or CH _3, R 7 = 2 over Te Torahi mud Vila sulfonyl O alkoxycarbonyl group, n = ^2, Z 2 = § da Kalimantan ring)

[3-11] 1—Hydroxy-1 3— (2-Tetrahydrobilanyloxycarponyl) -1 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 the polymerizable unsaturated monomer used to enhance the acid-eliminating function of the polymer compound include, for example, 1-1 [(1-1) (meth) atalyloyloxy-1- 1-methylethyl] ridamantane, 2- (Meth) acryloyloxy 2-Methyladamantane, 2- (Meth) acryloyloxy

2-Ethyladamantane, 2- [1- (Meth) acryloyloxy 1-methylethyl] norpornan, 2- (Meth) acryloyloxy-1 2-Methylnorbornane, 1- [1- (Meth) α Cryloyloxy 1-methyl ethynole] Hexane hex, 1- (meth) acryloylonoxy 1-methylcyclohexyl hexane, 3- [1- (meth) 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- or 6- (meth) atalyloyloxynorbornane, and analogs thereof (ethyl group instead of methyl group) And other compounds to which an alkyl group or a haloalkyl group such as a trifluoromethyl group is bonded.

In addition, in each monomer represented by the above formulas (8a) to (8g) and (9), The corresponding vinyl ether compound in which a (meth) acryloyloxy group is replaced by a vinyl 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, but the proportion of the repeating unit represented by formula (I) is limited, and with respect to the total monomer units constituting the polymer, typically. 1 to: 1 0 ◦ mole _^0/0, preferably 1 0-9 0 mole _^0/0, more preferably 3 0-8 about 0 mol%. A repeating unit 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 ratio of [excluding the repeating unit represented by the formula (I)] is 0 to 95 mol%, preferably 0 to 60 mol%, and more preferably about 10 to 40 mol%. . 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 0 to 95 mol. %, 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 polymerization of the monomer mixture is performed by a conventional method used for producing an acrylic polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, and the like. In particular, solution polymerization can be performed. 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. As the polymerization solvent, known solvents can be used, and examples thereof include ethers (chain ethers such as glycol ethers such as methyl alcohol, propylene glycol monomethyl ether and the like, cyclic ethers such as tetrahydrofuran and dioxane), and esters (esters). Methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, and other glycolone ethers, etc.), ketones (acetone, methylinoethyl ketone, methyl isobutyl ketone, cyclohexane) Xanone), amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfoxides (dimethinolesulfoxide, etc.), anorecols (methanol, ethanol, propanol, etc.), hydrocarbons (benzol, etc.) Emissions, 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: hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene, toluene, Aromatic hydrocarbons such as xylene), halogenated hydrocarbons (aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride); hydrogenated aromatics such as benzene and dichlorobenzene Group hydrocarbons), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), Monoethers (chain ethers such as getyl ether, diisopropyl ether and dimethoxyethane; cyclic ethers such as tetrahydrofuran and dioxane), ketones (acetone, methylethyl ketone, diisobutyl ketone, etc.), esters (ethyl acetate, Butyl acetate, etc.), carbonates (dimethinole carbonate, dithiotin carbonate, ethylene carbonate, propylene carbonate, etc.), alcohols (methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), phenolic 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 / the latter (volume ratio; 25 ° C) = 10 0 90-99 / 1, preferably the former / latter (volume ratio; 25 ° C) = 30 / 70-98 / 2, more preferably the former / latter (volume ratio) 25 ° C) = about 50/50 to 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 conventional or known compounds which efficiently generate an acid upon exposure to light, such as diazonium salts, odonium salts (e.g., diphenyl hexafluorophosphate), and snorephonium salts (e.g., For example, triphenylenolesnorrefoname hexafluoroantimonate, trifenenoles / levonihexene hexanoleophthalate phosphate, triphenylenolesnorrefonium methanesulfonate, etc.), sulfonic acid ester [ For example, 1-feninole 1-(4-methinolefenole) snorehoninoleoxy 1 1 benzoylmethane, 1,2,3-trisinolephonyloxymethylbenzene, 1, 3-dinitro-1- (4-phenylenolesulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl) 1-1-hydroxy-1 1-benzoylmethane, etc. ], Oxathiazole derivatives, s-triazine derivatives, disulfone derivatives (such as diphenyldisulfone), imid 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. 0.ι ~

It can be selected from a range of about 30 parts by weight, preferably about 1 to 25 parts by weight, and more preferably about 2 to 20 parts by weight.

 The resin composition for photoresist 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), a coloring agent (for example, a dye), and an organic compound. Solvents (eg, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents of these, etc.) Etc. may be included.

 After coating the resin composition for photoresist on a base material or a substrate and drying, the coating film (resist film) is exposed to a light beam through a predetermined mask (or, after the exposure, the beta film is exposed). A fine pattern can be formed with high precision by forming a latent image pattern and then developing.

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

Various wavelengths of light, such as ultraviolet rays and X-rays, can be used for the exposure. For semiconductor resists, g-rays, i-rays, excimer lasers (eg, XeC1, KrF) are usually used. , K r C l, A r F, A r C 1, F 2, K r 2, K r A r, etc. A r ₂₎ and the like are used. The exposure energy is, for example, about 0.1 to 100 mj / cm ² .

 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- 4-oxatricyclo [4. 2. 1. 0 ³ ' ⁷ ] nonan-5-one represented by the following formula (10) ;), Methacrylic acid 50.8 g (0.59 m 01), phosphoric acid 120 mg (12 mmol), 4-methoxyphenolone 15 mg (0.12 mm o 1), a mixture of toluene (210 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 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 (12) is obtained. Ruokishietokishi) to give an 4-O hexa tricyclo [4.2.3 1.0 ^{3 '7]} non Hmm 5-one 2 5. 5 g (9 6 mm o 1, 8 1% yield). This substance was a mixture of two isomers, and the abundance was about 1: 1. Incidentally, the formula represented by (1 0) 2- Biniruokishi one 4- Okisa tricyclo [4.2.3 1.0 ^{3 '7]} nonane one 5-on, the following equation (1 1) represented by 2-arsenide Doroki sheet one 4- Okisato Li cyclo from 4.2.3 1.0 ^{3 '7]} nonane _ 5-one and flop port propionate vinyl, JP 2 0 0 3 7 3 3 2 1 No. described in Synthesized using the method and purified by distillation.

[2-(1-Metalloyloxetoxy) 1-4-1-7-mouth] [4. 2. 1. 0 ³ ' ⁷ ] Nonan 1-5 -on spectrum data]

_{^{1 H- NMR (CDC1 3) δ}} : 1.40-1.44 (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 mmol), sodium carbonate 31.8 g (300 mmo1), toluene 600 ml And heated to 100 ° C. with stirring under a nitrogen atmosphere. The reaction vessel _{I r 2 C 1 2 (C} 8 H 12) 2 [ di one _mu - black port bis (1, 5-cyclopropyl O Kuta Zhen) Nii Rijiumu (I)] 3. 3 6 g (5 mmo 1) Was added, and 100 g (1 m 0 1) of propionate butyl was added dropwise over 2 hours, and the mixture was heated and refluxed to conduct a reaction 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 a colorless transparent liquid of 3-vinyloxy-1-oxaspiro [4.5] decane-2-one represented by the following formula (14) 22.5 g (114 mm o 1 , 23%). In addition, 3-hydroxy-11-spiroxaspiro [4.5] decane-2-one represented by the formula (13) can be obtained from cyc hexanol and methyl acrylate by the literature [Chem. Commun. 7, 613-614 (2000)], and used after purification by silica gel ram chromatography.

[3-vinyloxy 1-oxaspiro [4.5] Decane 1-one spectrum data] ^X H-NMR (CDCI3) δ: 1.35-1.89 (in, 10H), 2.04 (dd, IH), 2.50 (dd, IH), 4.20 (dd, IH), 4.42 (dd, IH), 4.65 (t, IH), 6.48 (q, IH) The resulting 3-vinyloxy-1-oxaspiro [4.5] decane-2-one 17.1 g (87 mmo 1), methacrylic acid 37.4 g (4 A mixture of 35 mmo 1), 0.85 g of phosphoric acid (8.7 mm o 1), 17.1 mg of 4-methoxyphenol (0.14 mm o 1), and 170 ml of toluene Was placed in a reaction vessel, and stirred at 50 ° C. for 4.5 hours in a dry air atmosphere. After completion of the reaction, the reaction solution was washed successively 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 expressed by the following formula (15): 3-(1 -metharyloyloxhetoxy) 1-oxaspiro [4.5] decane 1-2 -one [= This gave 17.3 g (61 mmo1, yield Ί 0%) of a colorless liquid of 3- (1-metharyloyloxyethoxy) -12-oxo-1-oxoxaspiro [4.5] decane]. . This substance was a mixture of isomer Α and isomer 、, and the abundance was approximately A: B = 3: 1.

[3- (1-methacryloyloxyethoxy) 1-1-oxaspiro [4.5] Decane 1-2-on spectral data]

 Isomer A

^{! H-NMR (CDCI3) δ} : 1.34-1.84 (m, 13H), 1.92- 1.97 (m, 4H), 2 .40 (dd, 1Η), 4.76 (t, IH), 5.64 (m, IH), 6.16 (m, IH), 6.28 (q, IH) isomer B '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, vinyl propionate 48.1 g, sodium carbonate 15.3 g, toluene 1200 m 1, dichlorobis (1,5-six) Loctadiene) Nitridium (I) 1.62 g of the mixture 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- (adamantane-1-yl) ethylvinyl-ether represented by the following formula (16).

 [2— (Adamantane 1 1 1 Nore) Spectral data of Echinorebininoreethenore]

 JH-NMR (CDCI3) δ: 1.46 (t, 2H), 1.53 (d, 6Η), 1.62-1.72 (m, 6H), 1.95 (m, 3H), 3.73 (t, 2H), 3.96 (ra, 1H) ), 4.16 (m, 1H), 6.46 (m, 1

H)

 Production Example 4

2- (adamantan-1-yl) ethylvinylinoleate 32,8 g, methacrylic acid 6,8.4 g, phosphoric acid 0.16 g, 4-methoxyphenol 0.16 4 g, and a mixture of toluene (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 the [1- (adamantan-1-yl) ethoxy] ethyl (meta) acrylate represented by the following formula (17) is obtained.

[1-[2-(Adamantane 1-1) ethoxy]] Ethyl (meta) acrylate spectrum data]

_{^{X H-NMR (CDC1 3)}} δ: 1.37-1.41 (m, 2H), 1.43 (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

 18.0 g (0.1 m 01) of vol vinyl ether represented by the following formula (18), 43.0 g (0.5 m 01) of methacrylic acid, 98 mg of phosphoric acid ( A mixture of 1 mm o 1), 12 mg (0.1 mmol) of 4-methoxyphenol and 180 ml of toluene was placed in a four-necked flask, and placed in a nitrogen atmosphere at 20 ° C for 6 hours. Stirred. 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 22.8 g (85 mmo1, yield 85%) represented by the following formula (19). . Bornyl vinyl ether was synthesized from (-)-borneol and propionate bull using the method described in JP-A-2003-73332 and purified by distillation. .

[11 (bonoleninoleoxy) methyl methacrylate

]

 'H-NMR (CDClg) δ: 0.80-0.84 (m, 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

In a separable flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube, propylene glycol monomethyl ether acetate (PGM EA) and propylene glycol monomethyl ether (P GME) (16.5 g each) After introducing the mixture and raising the temperature to 85 ° C, 1-methacryloyloxy 4-oxatricyclo [4.3.1.I ³ ' ⁸ ] pentane-5-one 4.93 g, 1-hydroxyl 3-Methacryloylocydamantane 4. 6 6 g, 2-(1 -methacryloyloxyshetoxy) _ 4 -oxatricyclo [4.2.1. 0 ³ ' ⁷ ] nonane-5-one 5.41 g and dimethyl -2, 2'-azobis (2-methylpropionate) (Initiator: Wako Pure Chemical Industries, trade name "V_601") 0.60 g, 34.2 g each for PGME A and PGME , 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 7333 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 980, and the molecular weight distribution (M _W / M _n ) was 1.88 (GPC measurement value, converted to polystyrene) i. Example 2

 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 after heating to 85 ° C, 1-hydroxy-3-methacryloyloxydamantane 4.1 3 g, 2-(1-methacryloyloxetoxy) 1-4-oxatricyclo [4.2.1. 0 ³ ' ⁷ ] nonane-1-one 10. 8 7 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, and these were treated for 4 hours. The solution was 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 Nutsuchi. 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 110,000, 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

In a separable flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube, propylene glycol monomethinole ether acetate (PGM EA) and propylene glycol alcohol monomethyl ether (PGME) were added, respectively. After introducing 5 g and raising the temperature to 85 ° C, 1-hydroxy-13-methacryloyloxyadamantane 4.44 g, 2- (1-methacryloyloxyxetoxy) -14-oxatotricyclo [ 4. 2. 1. 0 ³ ' ⁷ ] Nonane-5-one 10-0.2 g, methacrylic acid 0.54 g, dimethyl-1,2,2-azobis (2-methylpropionate) (start Agent; Wako Pure Chemical Industries, trade 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 resulting reaction solution was added dropwise to a mixture of heptane ⁷ 3 3 g of acetic acid Echiru 8 1 g, and the precipitated polymer was collected by Buchner funnel. 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 (Mw / MJ was 1.90 (measured GPC value, converted to polystyrene)).

 Example 4

 Synthesis of resin with the following structure

 Propylene glycol monomethyl ether acetate (PGM) was placed in a separable glass equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube.

EA) and 16.5 g of propylene daricol monomethyl ether (PGME) were introduced, and the temperature was raised to 85 ° C. After that, 1-methacryloyloxy-1-4-oxatricyclo [4.3.1.1.I ^{3 '8]} Undekan one 5-on-4. 8 8 g, 1 - human Dorokishi 3 Metaku Li Roy Ruo carboxymethyl § Dammann Tan 4. 6 1 g, 3 - (1 - Metaku Li Roy Ruo key shell butoxy) - 1 [4.5] decane-2-one 5.51 g, dimethyl-2,2'-azobis (2_methylpropionate) (Initiator: Wako Pure Chemical Industries, trade name "V- 0.61)) 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. 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

 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 after heating to 85 ° C, 1-hydroxy-13-methacryloyloxyadamantane 3. 9 6 g, 3- (1-methacryloyloxyxetoxy) -1-1-oxaspiro [4.5] decane-2-one-1.04 g, dimethyl_2,2, -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 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 90, and the molecular weight distribution (M _W ZMJ was 1.89 (GPC measurement value,-′ in terms of styrene)).

 Example 6

 Synthesis of resin with the following structure

In a separable glass 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 added. After introducing 5 g and raising the temperature to 85 ° C, 1-hydroxy_ 3 -methacryloyloxyadamantane 4.27 g, 3-(1 -metali- tal inoleoxetoxy) 1-1-oxaspiro [4.5] Decane-2-one 10.2 g, methacrylic acid 0.52 g, dimethyl 2,2'-azobis (2-methylpropionate) (Initiator: Wako Pure Chemical Industries 0.66 g was prepared as a mixed solution of 34.2 g each of PGME A 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 obtained polymer had a weight average molecular weight (M _w ) of 110,000 and a molecular weight distribution (M _w / M _n ) of 1.88. (GPC measurement value, converted to polystyrene).

 Example 7

 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 raising the temperature to 85 ° C, 1-methacryloyloxy 4-oxatricyclo [4.3.1.I ³ ' ⁸ ] pentane-5-one 4.77 g, 1-hydroxyl 3-methacryloyl Oxyadamantane 4.50 g, 1- [2- (adamantane 1-yl) ethoxy] ethyl methacrylate 5.74 g and dimethyl-1,2,2'-azobis (2-methylpropionate) (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, and these were taken over 4 hours. It was 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 collected by Nutsche. 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 / MJ 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 monomethyl ether acetate (PGM

EA) and propylene glycol monomethyl ether (PGME) (16.5 g each) were introduced, and after heating to 85 ° C, 1-methacryloyloxy 4-oxatricyclo [4.3.1.I ^{3 '8]} Undekan one 5-on 4. 9 3 g, 1 over human Dorokishi 3- methacrylic port Ino les oxy § Dammann Tan 4. 6 6 g, 1 i (Boruninoreokishi) Echirume Tak Li rate 5. 4 1 g And dimethyl-2,2'-azobis (2-methylpropionate) (initiator: Wako Pure Chemical Industries, trade name "V-601") 0.60 g, PGMEA and PGME each 34 2 g of a mixed solution was 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 9400, and the molecular weight distribution (M _w / M _n ) was 1.90 (GPC measurement value, polystyrene conversion). Comparative Example 1

 Synthesis of resin with the following structure

In a separate flask equipped with a stirrer, thermometer, dropping funnel and nitrogen inlet tube, propylene glycol monomethyl ether enorea acetate (PGM EA) and propylene glycol monomethyl ether '(pGME) were each added. After introducing 5 g and raising the temperature to 85 ° C, 1—metharyloyloxy-4-oxatricyclo [4.3.1 1. I ³ ' ⁸ ] pentane-5-one 5.16 g, 1 —Hydroxy-3—methacryloyloxyadamantane 4.87 g, 2-methacryloyloxy-2-methyladamantane 4.97 g, and dimethyl 2,2, —azobis (2-methylprod Pionate) (Initiator: 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. 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 7333 g of heptane and 81 g of ethyl acetate, and the precipitated polymer was recovered with a nut. The obtained polymer was dried under reduced pressure to obtain 13.5 g of the desired product. The obtained polymer had a weight average molecular weight (M _w ) of 980 and a molecular weight distribution (M _w ZM _n ) of 1.88 (GPC measurement value, converted to polystyrene).

 Evaluation test

For each polymer obtained in the above Examples and Comparative Examples, 100% by weight of the polymer Of phenylglycol monomethyl ether (PGME) as a solvent, and 10 parts by weight of triphenyl ^^ sulfoniumhexafluoroantimonate in a resin composition for photoresists having a polymer concentration of 17% by weight. 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 μπα. After prebaking 1 50 seconds at 1 00 a hot plate, using the K r F excimer laser with a wavelength of 247 nm, through a mask, after exposure in dose 30m jZcm ^2, 60 seconds post at a temperature 100 ° C Beta. Then, the film was developed with a 0.3 M aqueous solution of 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 μηι 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 scope of the claims

1. The following equation (1)

(i)

(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.)

A methacetal ester to an unsaturated carboxylic acid 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) R ^a

 ^ OH (3)

 0

(In the formula, 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 ^B and R ^f each represent a hydrogen atom or a hydrocarbon 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. Manufacturing of a semiconductor comprising a step of forming a resist coating by applying the resin composition for photoresist according to claim 7 onto a substrate or a substrate, and forming a pattern through exposure and development. Method.