KR101115224B1 - Unsaturated carboxylic acid hemiacetal ester, polymer, and resin composition for photoresist - Google Patents

Abstract

A high molecular compound comprising a repeating unit corresponding to the unsaturated carboxylic acid hemiacetal ester represented by the following formula (1).

<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 1 position, and R ^c represents a hydrogen atom or Hydrocarbon group, R ^d represents an organic group containing a cyclic skeleton). This high molecular compound further contains 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 imide group-containing monomer [corresponding to the above unsaturated carboxylic acid hemiacetal ester Exclusion of repeating units], and / or hydroxyl group-containing monomers, and the like. This polymer compound exhibits excellent acid leaving property when used as a photoresist.

Unsaturated carboxylic acid hemiacetal esters, high molecular compounds, photoresists, photoacid generators

Description

Unsaturated carboxylic acid hemiacetal ester, resin composition for high molecular compound and photoresist {UNSATURATED CARBOXYLIC ACID HEMIACETAL ESTER, POLYMER, AND RESIN COMPOSITION FOR PHOTORESIST}

The present invention relates to a unsaturated carboxylic acid hemiacetal ester useful as a monomer component of a resin for photoresists used for fine processing of semiconductors, a method for producing the same, and a high molecular compound comprising repeating units corresponding to the unsaturated carboxylic acid hemiacetal ester. The present invention relates to a resin composition for photoresists containing the polymer compound, and a method for producing a semiconductor.

The positive type photoresist used in the semiconductor manufacturing process should have characteristics such as the property that the irradiated portion is changed to alkali solubility by light irradiation, adhesion to a silicon wafer, plasma etching resistance, transparency to light used, and the like. The positive photoresist is generally used as a solution containing a main polymer, a photoacid generator, and a variety of additives for adjusting the above properties. It is very important to equilibrate each of the above characteristics.

The lithography exposure light source used for the manufacture of a semiconductor is shortening year by year, and has shifted from the KrF excimer laser of wavelength 248 nm to the ArF excimer laser of wavelength 193 nm. In the polymers for resists used in these KrF or ArF excimer laser exposure machines, 2-methyladamantane is a monomer unit that gives a function of being soluble in an alkaline developer by being separated by an acid generated from a photoacid generator by exposure. The unit etc. which have a 2-yl group and a 1-adamantyl-1-methylethyl group are known (Unexamined-Japanese-Patent No. 9-73173, etc.). However, conventional photoresist resins having these units were not necessarily satisfactory in terms of sensitivity and development. In addition, the balance between substrate adhesiveness, etching resistance and acid leaving property was not sufficient.

An object of the present invention is a polymer compound exhibiting excellent acid leaving property or excellent acid leaving property and substrate adhesion when used as a photoresist, a monomer thereof, a method for preparing the monomer, a resin composition for photoresist comprising the polymer compound, and It is providing the manufacturing method of the semiconductor using a resin composition.

Another object of the present invention is to prepare a photoresist polymer compound having a balanced substrate adhesion, etch resistance and acid leaving property, a photoresist resin composition containing the polymer compound, and a semiconductor using the resin composition. To provide a way.

It is still another object of the present invention to provide a polymer compound for photoresists, a resin composition for photoresists, and a semiconductor manufacturing method capable of forming fine patterns with high precision.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, when the high molecular compound containing the repeating unit corresponding to the unsaturated carboxylic acid hemiacetal ester which has a specific structure is used as resin for photoresists, it is excellent in acid leaving property or excellent. The present invention has been completed by discovering that acid leaving property and substrate adhesiveness can be expressed and fine patterns can be formed with high accuracy.

That is, the present invention provides an unsaturated carboxylic hemiacetal ester represented by 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 1 position, and R ^c represents a hydrogen atom or Hydrocarbon group, R ^d represents an organic group containing a cyclic skeleton)

As said cyclic skeleton in R <^d> , a lactone skeleton or a non-aromatic polycyclic skeleton is preferable.

The present invention also provides a unsaturated carboxylic acid hemiacetal ester represented by the following formula (5) by reacting an unsaturated carboxylic acid represented by the following formula (3) with a vinyl ether compound represented by the following formula (4): Provided are methods for preparing the acid hemiacetal ester.

(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)

(Wherein R ^c represents a hydrogen atom or a hydrocarbon group, R ^d represents an organic group containing a cyclic skeleton, and R ^e , R ^f each represent a hydrogen atom or a hydrocarbon group)

Wherein R ^a , R ^c , R ^d , R ^e , and R ^f are the same as above.

The present invention also provides a polymer compound comprising a repeating unit represented by the following formula (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 1 position, and R ^c represents a hydrogen atom or Hydrocarbon group, R ^d represents an organic group containing a cyclic skeleton)

The polymer compound further includes 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 imide group-containing monomer [excluding the repeating unit represented by the formula (I). ] May be included. In addition, the polymer compound may further include 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.

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

This invention also provides the manufacturing method of the semiconductor which includes the process of apply | coating the said resin composition for photoresists on a base material or a board | substrate, forming a resist coating film, and forming a pattern through exposure and image development.

In addition, the vinyl ether monomer and vinyl ether compound in this specification shall also contain the compound by which the hydrogen atom of the vinyl group was substituted by the substituent. As a protecting group such as a hydroxyl group, a protecting group commonly used in the field of organic synthesis can be used.

According to the present invention, when used as a photoresist, there is provided a polymer compound and its monomer which exhibit excellent acid leaving property or excellent acid leaving property and substrate adhesiveness. Moreover, the resin composition for photoresists of this invention is excellent in acid detachability, and exhibits the board | substrate adhesiveness, etching resistance, and acid leaving property in balance. For this reason, in a semiconductor manufacture, a fine pattern can be formed with high precision.

Best Mode for Carrying Out the Invention

Unsaturated Carboxylic Acid Hemiacetal Ester

Unsaturated carboxylic acid hemiacetal ester of the present invention is represented by the formula (1). In formula (1), 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 1 position, and R ^c represents a hydrogen atom or Hydrocarbon group is shown and R <^d> represents the organic group containing a cyclic skeleton.

The halogen atom in R ^a 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, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl group, and the like. Among these, C _1-3 alkyl groups, especially methyl groups are preferable. As a C1-C6 haloalkyl group, For example, Chloroalkyl groups, such as a chloromethyl group; Fluoroalkyl groups (preferably C _1-3 fluoroalkyl groups) such as trifluoromethyl, 2,2,2-trifluoroethyl and pentafluoroethyl groups.

As a hydrocarbon group which has a hydrogen atom in 1 position in said R <^b> , For example, Alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl group (for example, _C1-6 alkyl group, Especially a C _1-3 alkyl group); Cycloalkyl groups such as cyclopropyl, cyclopentyl and cyclohexyl groups (for example, 3- to 6-membered cycloalkyl groups); Cycloalkylalkyl groups such as cyclopentylmethyl and cyclohexylmethyl groups [eg, mono or di- (3- to 6-membered cycloalkyl) -C _1-3 alkyl groups]; And aralkyl groups such as benzyl, 1-methylbenzyl, and 1-phenylbenzyl groups (for example, mono or diphenyl-C _1-3 alkyl groups). As R <^b> , C _1-3 alkyl groups, such as methyl, ethyl, a propyl, and an isopropyl group, are preferable, and a methyl group is especially preferable.

As a hydrocarbon group in R <^C> , For example, Alkyl groups, such as a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl group (for example, a C _1-6 alkyl group, especially a C _1-3 alkyl group); Cycloalkyl groups such as cyclopropyl, cyclopentyl and cyclohexyl groups (for example, 3- to 6-membered cycloalkyl groups); Aryl groups, such as a phenyl group, etc. are mentioned. As R ^{c, a} hydrogen atom; C _1-3 alkyl groups, such as methyl, ethyl, propyl, and isopropyl, are preferable, and a hydrogen atom and a methyl group are especially preferable.

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

The lactone skeleton has a non-aromatic or aromatic carbocyclic ring or a compound in addition to the skeleton consisting of only a lactone ring (e.g., γ-butyrolactone ring, δ-valerolactone ring, ε-caprolactone ring, etc.). Skeletons containing condensed summons are included. Especially, the skeleton which consists only of a lactone ring, and the skeleton which the non-aromatic carbocyclic ring or heterocycle (especially non-aromatic carbocyclic ring) condensed to the lactone ring are preferable. The ring constituting the lactone skeleton may be an alkyl group such as a methyl group (e.g., a C _1-4 alkyl group), a haloalkyl group such as a trifluoromethyl group (e.g., a C _1-4 haloalkyl group, etc.), a chlorine atom or a fluorine atom A halogen atom, a hydroxyl group protected by a protecting group, a hydroxyalkyl group protected by a protecting group, a mercapto group protected by a protecting group, a carboxyl group protected by a protecting group, an amino group protected by a protecting group, It may have a substituent such as a sulfonic acid group which can be protected with a protecting group. As a protecting group, the protecting group normally used in the field of organic synthesis is mentioned.

As typical lactone skeleton, the skeleton (group) represented by the following general formula (6a, 6b, 6c, 6d, 6e, 6f, 6g) is mentioned.

[Wherein, R ¹ to R ⁶ , R ⁹ to R ³⁶ are the same or different and a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a hydroxyl group which can be protected with a protecting group, a hydroxy that can be protected with a protecting group An alkyl group, a mercapto group which can be protected with a protecting group, or a carboxyl group that can be protected with a protecting group, X represents an alkylene group, an oxygen atom, a sulfur atom or no bond, and V ¹ to V ³ are the same or different,- CH _2- , -CO- or -COO-. Provided that at least one of V ¹ to V ³ is -COO-. In Formula 6f, two or more groups of R ²⁷ to R ³¹ may combine to form a ring together with a carbon atom or a carbon-carbon bond. In addition, in Formula 6g, two or more groups of R ³² to R ³⁶ may be bonded to form a ring together with a carbon atom or a carbon-carbon bond.]

In the formulas (6a) to (6g), examples of the halogen atom in R ¹ to R ⁶ and R ⁹ to R ³⁶ include fluorine and chlorine atoms. Examples of the alkyl group include linear or branched alkyl groups having 1 to 13 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl, and dodecyl groups. have. Among these, alkyl groups having 1 to 4 carbon atoms are preferable. As a haloalkyl group, C1-C13 fluoroalkyl groups, such as a trifluoromethyl and a pentafluoroethyl group, etc. are mentioned. As the hydroxyl group which may be protected by a protective group, for example, there may be mentioned a hydroxyl group, a substituted oxy group (e.g., methoxy, ethoxy, C _1-4 alkoxy groups such as a propoxy group), etc. . As a hydroxyalkyl group which can be protected by a protecting group, the group etc. which the hydroxyl group which can be protected by the said protecting group is couple | bonded through the alkylene group of C1-C6 are mentioned. As a mercapto group which can be protected by a protecting group, in addition to a mercapto group, the mercapto group etc. which were protected by the same protecting group as the said hydroxyl group are mentioned. As a carboxyl group which can be protected by a protecting group, -COOR ^y group etc. are mentioned. R <^y> represents a hydrogen atom or an alkyl group, and as an alkyl group, C1-C6 linear or branched carbons, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, a hexyl group, etc. Alkyl group etc. are mentioned. Examples of the alkylene group in X include linear or branched alkylene groups having 1 to 3 carbon atoms (preferably 1 or 2), such as methylene, dimethyl methylene, ethylene, propylene, and trimethylene groups.

Rings formed by bonding two or more groups of R ²⁷ to R ³¹ together with carbon atoms or carbon-carbon bonds, and rings formed by combining two or more groups of R ³² through R ³⁶ together with carbon atoms or carbon-carbon bonds include Alicyclic carbocyclic rings (including a crosslinked carbocyclic ring), such as a cyclopentane ring, a cyclohexane ring, and a norbornane ring, etc. are mentioned. The ring constituting the skeleton represented by the formulas (6a to 6g) may have a substituent as described above.

The "ring" constituting a cyclic skeleton other than the lactone skeleton includes monocyclic or polycyclic non-aromatic or aromatic rings. As a monocyclic non-aromatic ring, For example, alicyclic rings, 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; Non-aromatic heterocycles of about 3 to 15 members, such as a tetrahydrofuran ring, a pyrrolidine ring, a piperidine ring, and a morpholine ring, are mentioned. Examples of the polycyclic nonaromatic ring include adamantane rings; Norbornane rings such as norbornane ring, norbornene ring, bornan ring, isobornane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane ring Or a ring including a norbornene ring; Rings in which polycyclic aromatic condensed rings such as perhydroindene ring, decalin ring (perhydronaphthalene ring), perhydrofluorene ring (tricyclo [7.4.0.0 ^3,8 ] tridecane ring), and perhydroanthracene ring are hydrogenated (Preferably fully hydrogenated rings); And cross-linked carbocyclic rings such as tricyclic [4.2.2.1 ^2,5 ] undecane rings, such as bicyclic, tricyclic, and tetracyclic systems (for example, crosslinked carbocyclic rings having about 6 to 20 carbon atoms). As a monocyclic or polycyclic aromatic ring, aromatic carbocyclic rings and aromatic heterocycles, such as a benzene ring, a naphthalene ring, a pyridine ring, and quinoline ring, are mentioned. Among them, non-aromatic rings are preferable in terms of light transmittance and etch resistance when polymerized and used as a resin for photoresist, more preferably polycyclic non-aromatic rings, and particularly preferably polycyclic non-aromatic rings. It is a sex carbocyclic ring (crosslinked carbocyclic ring). Among the crosslinked carbon rings, the ring containing the norbornane ring or the norbornene ring or the ring in which the polycyclic aromatic condensed ring is hydrogenated (particularly a completely hydrogenated ring) is particularly preferable. Therefore, as a cyclic skeleton other than a lactone skeleton, a non-aromatic cyclic skeleton is preferable, and especially a non-aromatic polycyclic skeleton, especially a polycyclic non-aromatic carbocyclic skeleton is preferable.

Rings constituting a cyclic skeleton other than the lactone skeleton include an alkyl group such as a methyl group (for example, a C _1-4 alkyl group), a haloalkyl group such as a trifluoromethyl group (for example, a C _1-4 haloalkyl group, and the like), Halogen atoms such as chlorine or fluorine atoms, hydroxyl groups protected by protecting groups, hydroxyalkyl groups protected by protecting groups, mercapto groups protected by protecting groups, carboxyl groups protected by protecting groups, protected by protecting groups It may have a substituent such as an amino group which can be, a sulfonic acid group which can be protected with a protecting group. As a protecting group, the protecting group normally used in the field of organic synthesis is mentioned.

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

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

As a linking group in said A, For example, A single bond; Linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene and trimethylene groups; Carbonyl group; Oxygen atom (ether bond; -0-); Oxycarbonyl group (ester bond; -COO-); Aminocarbonyl group (amide bond; -CONH-); And groups in which a plurality of these are bonded to each other. Preferred linking groups include single bonds, straight or branched C _1-6 alkylene groups (particularly C _1-3 alkylene groups) and the like. The linking group may be, for example, a halogen atom such as a chlorine atom or a fluorine atom, a hydroxyl group protected by a protecting group, a hydroxyalkyl group protected by a protecting group, a mercapto group protected by a protecting group, or a protecting group. It may have a substituent such as a carboxyl group, an amino group that can be protected with a protecting group, a sulfonic acid group that can be protected with a protecting group. Examples of the lactone skeleton in the cyclic skeleton in Z ¹ include a skeleton represented by the above formulas 6a to 6g. Moreover, what was illustrated above is mentioned as a ring which comprises cyclic skeletons other than a lactone skeleton among the cyclic skeleton in Z <^1> .

The following compounds are mentioned as a typical example of the compound which has an organic group containing a lactone skeleton among the unsaturated carboxylic acid hemiacetal ester represented by General formula (1) [The compound which has a lactone skeleton among the compounds containing the group represented by Formula 2]. Can be, but is not limited thereto.

[1-1] 1- [1- (meth) acryloyloxyethoxy] -4- ^oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one [Z ¹ = Formula 6a, A = Single Combination]

[1-2] 2- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [Z ¹ = Formula 6b, A = Single bond ]

[1-3] 2- [1- (meth) acryloyloxyethoxy] -6-methyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [Z ¹ = Formula 6b, A = single bond]

[1-4] 2- [1- (meth) acryloyloxyethoxy] -6-trifluoromethyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [Z ¹ = Formula 6b, A = single bond]

[1-5] 2- [1- (meth) acryloyloxyethoxy] -9-methyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [Z ¹ = Formula 6b, A = single bond]

[1-6] 6-fluoro-2- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [Z ¹ = Formula 6b , A = single bond]

[1-7] 9-carboxy-2- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [Z ¹ = Formula 6b, A = single bond]

[1-8] 2- [1- (meth) acryloyloxyethoxy] -9-methoxycarbonyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [Z ¹ = Formula 6b, A = single bond]

[1-9] 9-ethoxycarbonyl-2- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [Z ¹ = Formula 6b, A = single bond]

[1-10] 9-t-butoxycarbonyl-2- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [ Z ¹ = Formula 6b, A = single bond]

[1-11] 2- [1- (meth) acryloyloxyethoxy] -4,8-dioxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one [Z ¹ = Formula 6b, A = Single combination]

[1-12] 4- [1- (meth) acryloyloxyethoxy] -6-oxabicyclo [3.2.1] octane-7-one [Z ¹ = Formula 6b, A = Single bond]

[1-13] 8- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [5.2.1.0 ^2,6 ] decane-5-one [Z ¹ = Formula 6c, A = Single bond ]

[1-14] 9- [1- (meth) acryloyloxyethoxy] -4-oxatricyclo [5.2.1.0 ^2,6 ] decane-5-one [Z ¹ = Formula 6c, A = Single bond ]

[1-15] α- [1- (meth) acryloyloxyethoxy] -γ, γ-dimethyl-γ-butyrolactone [Z ¹ = Formula 6g, A = Single bond]

[1-16] 3- [1- (meth) acryloyloxyethoxy] -2-oxo-1-oxaspiro [4.5] decane [Z ¹ = Formula 6g, A = Single bond]

[1-17] α- [1- (meth) acryloyloxyethoxy] -γ-butyrolactone [Z ¹ = Formula 6g, A = Single bond]

[1-18] α- [1- (meth) acryloyloxyethoxy] -α, γ, γ-trimethyl-γ-butyrolactone [Z ¹ = Formula 6g, A = single bond]

[1-19] α- [1- (meth) acryloyloxyethoxy] -β, β-dimethyl-γ-butyrolactone [Z ¹ = Formula 6g, A = Single bond]

[1-20] A compound represented by the following Formula 7 [Z ¹ = Formula 6g, A = Single bond]

[1-21] 3- [1- (meth) acryloyloxyethoxy] -2-oxo-1-oxaspiro [4.4] nonane [Z ¹ = Formula 6g, A = single bond]

Representative examples of the compound having an organic group containing a cyclic skeleton other than the lactone skeleton in the unsaturated carboxylic acid hemiacetal ester represented by the formula (1) [In the compound containing a group represented by the formula (2), including a cyclic skeleton other than the lactone skeleton Although the following compounds are mentioned as a compound which has an organic group to make], It is not limited to this.

[1-22] 1- (adamantane-1-yloxy) ethyl (meth) acrylate

[1-23] 1- (adamantane-1-ylmethoxy) ethyl (meth) acrylate

[1-24] 1- [2- (adamantan-1-yl) ethoxy] ethyl (meth) acrylate

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

[1-26] 1- (2-methyladamantan-2-yloxy) ethyl (meth) acrylate

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

[1-28] 1- (3,5-dihydroxyadamantan-1-yloxy) ethyl (meth) acrylate

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

[1-30] 1- (3,5-dicarboxylamantan-1-yloxy) ethyl (meth) acrylate

[1-31] 1- (norbornane-2-yloxy) ethyl (meth) acrylate

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

[1-33] 1- (2-methylnorbornane-2-yloxy) ethyl (meth) acrylate

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

[1-35] 1- (3-hydroxynorbornan-2-yloxy) ethyl (meth) acrylate

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

[1-37] 1- (5,6-dihydroxynorbornan-2-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 (meth) acrylate

[1-42] 8-hydroxymethyl-4- [1- (meth) acryloyloxyethoxymethyl] tricyclo [5.2.1.0 ^2,6 ] decane

[1-43] 4-hydroxymethyl-8- [1- (meth) acryloyloxyethoxymethyl] tricyclo [5.2.1.0 ^2,6 ] decane

[1-44] 1- (Bornyloxy) ethyl (meth) acrylate

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

[1-46] 3-carboxy-8- [1- (meth) acryloyloxyethoxy] tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane

[1-47] 3-carboxy-9- [1- (meth) acryloyloxyethoxy] tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane

The unsaturated carboxylic acid hemiacetal ester represented by the formula (1) is, for example, by reacting the unsaturated carboxylic acid represented by the formula (3) with the vinyl ether compound represented by the formula (4) in a solvent or in a solvent-free manner, as shown in the following scheme. It can manufacture. The compound represented by the formula (5) as a product corresponds to the compound represented by the formula (1).

(Wherein, R ^a , R ^c , R ^d are the same as above. R ^e , R ^f each represent a hydrogen atom or a hydrocarbon group, and -CHR ^e R ^f corresponds to R ^b above).

Although the reaction proceeds even without a catalyst, the reaction can be promoted by using an acid catalyst. The acid catalyst is not particularly limited, and both inorganic and organic acids can be used. As an inorganic acid, For example, mineral acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, a boric acid; Heteropolyacids such as phosphorus molybdate, silicon molybdate, phosphorus tungstic acid and silicon tungstic acid; Solid catalysts, such as a zeolite, etc. are mentioned. As an organic acid, For example, carboxylic acids, such as formic acid, acetic acid, and trifluoroacetic acid; And sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and naphthalenesulfonic acid. Cation exchange resin can also be used as an acid catalyst. Lewis acids may also be used. It is also possible to use pyridinium salts, ammonium salts, alkali metal salts, alkaline earth metal salts, transition metal salts, and the like, among which the salts can be formed. Among them, phosphoric acid is particularly preferable in terms of yield and selectivity of the target compound.

The solvent is not particularly limited as long as it is a solvent inert to the reaction, and examples thereof include aliphatic hydrocarbons such as hexane and octane; Aromatic hydrocarbons such as benzene, toluene and xylene; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Halogenated hydrocarbons such as methylene chloride; Ethers such as tetrahydrofuran and ethylene glycol dimethyl ether; Aprotic polar solvents, such as N, N- dimethylformamide, etc. are mentioned.

The amount of the unsaturated carboxylic acid represented by the general formula (3) is, for example, about 0.5 to 50 moles, preferably about 0.9 to 10 moles, per 1 mole of the vinyl ether compound represented by the general formula (4). The amount of the acid catalyst used is, for example, about 0.0001 to 1 mol, preferably about 0.01 to 0.3 mol, based on 1 mol of the vinyl ether compound represented by the formula (4).

In order to suppress the polymerization of the vinyl ether compound and the reaction product represented by the formula (4), it is preferable to add a small amount of a polymerization inhibitor such as 4-methoxyphenol in the system. The addition amount of the polymerization inhibitor is, for example, about 0.00001 to 0.05 mole, preferably about 0.0001 to 0.01 mole with respect to 1 mole of the vinyl ether compound represented by the formula (4).

Although reaction temperature changes also with the kind of reaction raw material, the kind of catalyst used, etc., it is usually -10 degreeC-100 degreeC, Preferably it is about 0-60 degreeC.

After completion of the reaction, the reaction product can be separated and purified by separation means such as liquid control, extraction, concentration, distillation, crystallization, recrystallization, column chromatography, and the like.

On the other hand, in addition to the unsaturated carboxylic acid hemiacetal ester represented by the general formula (1), compounds in which R ^b and R ^c are both hydrogen atoms in the general formula (1) are also useful as monomers of the polymer compound for photoresist. The repeating unit corresponding to this compound exhibits an acid leaving function or a hydrophilic function in a high molecular compound. As such a compound, there may be mentioned a compound (R ^b = R ^c = H in the compound) or the like corresponding to the examples of the unsaturated carboxylic acid hemiacetal ester of the formula (1).

In Formula 1, a compound in which R ^b and R ^c are both hydrogen atoms [compound represented by Formula B] is, for example, an unsaturated carboxylic acid represented by Formula 3 and a halo represented by Formula A, as shown in the following scheme. It can be prepared by reacting a methyl ether compound in the presence of a base.

(Wherein R ^a and R ^d are the same as described above, Y represents a halogen atom)

Examples of the halogen atom in Y include chlorine, bromine and iodine atoms. The reaction is carried out in the presence or absence of a solvent. The solvent can be used as the solvent. As a base, organic bases, such as triethylamine and pyridine, or inorganic bases, such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, can be used, for example. The amount of the unsaturated carboxylic acid represented by the formula (3) is, for example, about 0.5 to 10 mol, preferably about 0.8 to 2 mol, relative to 1 mol of the halomethyl ether compound represented by the formula (A). The use amount of base is about 1-5 mol with respect to 1 mol of unsaturated carboxylic acids represented by General formula (3), and can also be used in large excess. In order to suppress the polymerization of the halomethyl ether compound and the reaction product represented by the formula (A), a small amount of a polymerization inhibitor such as 4-methoxyphenol may be added to the system. The reaction temperature is usually from -10 deg. C to 100 deg. C, preferably from 0 to 60 deg. After completion of the reaction, the reaction product can be separated and purified by separation means such as liquid control, extraction, concentration, distillation, crystallization, recrystallization, column chromatography, and the like.

The halomethyl ether compound represented by Chemical Formula A is, for example, formaldehyde or an equivalent thereof (paraformaldehyde, 1,3,5-trioxane, etc.) to the hydroxy compound represented by Chemical Formula C, as shown in the following scheme. It can manufacture by reacting with the hydrogen halide represented by general formula (D).

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

As hydrogen halide represented by general formula (D), hydrogen chloride, hydrogen bromide, etc. are mentioned, for example. The reaction is carried out in the presence or absence of a solvent. The solvent can be used as the solvent. The amount of formaldehyde or its equivalent used is, for example, about 0.8 to 10 moles, preferably about 1 to 1.5 moles, relative to 1 mole of the hydroxy compound represented by the formula (C). The amount of the hydrogen halide represented by the formula (D) is, for example, about 1 to 5 moles with respect to 1 mole of the hydroxy compound represented by the formula (C), and may be used in an excessive amount. The reaction temperature is usually from -10 deg. C to 100 deg. C, preferably from 0 to 60 deg. After completion of the reaction, the reaction product can be separated and purified by separation means such as liquid control, extraction, concentration, distillation, crystallization, recrystallization, column chromatography, and the like.

[Polymer compound]

The high molecular compound of this invention contains the repeating unit (monomer unit) corresponding to the said unsaturated carboxylic acid hemiacetal ester, ie, the unit represented by General formula (I). The repeating unit may be one kind or two or more kinds. Such a high molecular compound can be obtained by polymerizing the unsaturated carboxylic acid hemiacetal ester.

Since the repeating unit represented by the formula (I) has a hemiacetal ester structure, it has an acid leaving function (alkali soluble function). That is, since the alcohol part (hemiacetal part) of ester leaves | separates by the acid which generate | occur | produces from a photo-acid generator by exposure, and a free carboxyl group is produced, it becomes soluble by alkaline developing solution. In addition, since the hemiacetal ester structure contains three oxygen atoms, the hydrophilicity is higher than that of a conventional acid ester dissociable unit having a simple ester structure (including two oxygen atoms), and solubility and wettability in a resist solvent or an alkaline developer. This has the advantage of being improved. In addition, when the repeating unit represented by the formula (I) has a lactone skeleton, the substrate adhesion is excellent. The polymer compound having a repeating unit having both an acid leaving function and a substrate adhesion function greatly increases the substrate adhesive group while maintaining the number of acid leaving groups compared with a polymer compound containing a repeating unit having only an acid leaving function. It is possible to achieve high substrate adhesiveness, and by introducing repeating units having other functions such as hydrophilicity while maintaining the number of acid leaving groups and the number of substrate adhesive groups, thereby providing acid leaving properties and substrate adhesion properties. It is excellent in that it can fully provide other functions together. In addition, when R ^d in the general formula (I) is a group containing a polycyclic non-aromatic carbocyclic ring (crosslinked carbocyclic ring), it exhibits high light transmittance and dry etching resistance.

Since the polymer compound of the present invention has a sufficient balance of various functions required as a resist, not only the repeating unit represented by the above formula (I) but may have other repeating units. Such another repeating unit can be formed by copolymerizing a polymerizable unsaturated monomer corresponding to the repeating unit with the unsaturated carboxylic acid hemiacetal ester. As said other repeating unit, the repeating unit which has a board | substrate adhesiveness and / or a hydrophilic function, the repeating unit which raises an acid leaving property, the repeating unit which raises a etch resistance function, the repeating unit which raises transparency, etc. are mentioned, for example. . The hydrophilic function includes a function of increasing solubility in a resist solvent or an alkaline developer. In the production of the polymer compound of the present invention, a monomer used to smoothly copolymerize or to uniformize the copolymer composition may be used as a comonomer.

Repeating units having a substrate adhesion and / or a hydrophilic function can be introduced into the polymer by using a polymerizable unsaturated monomer having a polar group as a comonomer. As said polar group, For example, (1) group, such as a lactone ring containing group, a carbonyl group, an acid anhydride group, an imide group, (2) the hydroxyl group which may have a protecting group, the mercapto group which may have a protecting group, and a protecting group Groups, such as the carboxyl group which may have, the amino group which may have a protecting group, and the sulfonic acid group which may have a protecting group are mentioned. Moreover, as a polymerizable unsaturated monomer which has a polar group, (a) lactone frame | skeleton containing monomer, cyclic ketone frame | skeleton containing monomer, monomers, such as an acid anhydride group containing monomer, an imide group containing monomer, (b) hydroxyl group containing monomer (hydroxyl group Mercurto group-containing monomers (including compounds protected by mercapto groups), carboxyl group-containing monomers (including compounds protected by carboxyl groups), amino group-containing monomers (compounds protected by amino groups) Monomers such as a sulfonic acid group-containing monomer (including a compound in which a sulfonic acid group is protected), and compounds known in the resist field can be used. These monomers can be used 1 type or in combination of 2 or more types. For example, a balanced resist characteristic can be expressed by combining the monomer which belongs to said (a), and the monomer which belongs to (b).

The repeating unit for enhancing the acid leaving function is, for example, (c) a hydrocarbon group having a tertiary carbon, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, or the like bonded to an oxygen atom constituting the ester. A (meth) acrylic acid ester derivative and a hydrocarbon group (alicyclic hydrocarbon group, aliphatic hydrocarbon group, a group to which they are bonded, etc.) adjacent to an oxygen atom constituting the (d) ester, and further -COOR ^x The polymer is obtained by using a (meth) acrylic acid ester derivative or the like, in which a group (R ^x represents a tertiary hydrocarbon group, 2-tetrahydrofuranyl group or 2-tetrahydropyranyl group) is bonded directly or through a linking group. Can be introduced in As such a (meth) acrylic acid ester derivative, a compound known in the resist field can be used.

Representative examples of the polymerizable unsaturated monomers other than the unsaturated carboxylic acid hemiacetal ester used to impart various functions as resists to the polymer compound of the present invention include compounds represented by the following formulas (8a) to (8g). These correspond to the said lactone skeleton containing monomer and cyclic ketone skeleton containing monomer.

(Wherein R represents a hydrogen atom or a methyl group. R ¹ to R ⁶ , R ⁹ to R ³⁶ , X, and V ¹ to V ³ are the same as above).

Although the following compound is mentioned as a typical example of a compound represented by General formula (8a), It is not limited to this.

[2-1] 1- (meth) acryloyloxy-4-oxoadamantane (R = H or CH ₃ , R ¹ = R ² = R ³ = H, V ¹ = -CO-, V ² = V ³ = -CH _2- )

[2-2] 1- (meth) acryloyloxy-4- ^oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one (R = H or CH ₃ , R ¹ = R ² = R ³ = H, V ² = -CO-O- (left side is the carbon atom side where R ² is bonded), V ¹ = V ³ = -CH _2- )

[2-3] 1- (meth) acryloyloxy-4,7- ^{dioxatricyclo} [4.4.1.1 ^3,9 ] dodecane-5,8-dione (R = H or CH ₃ , R ¹ = R ² = R ³ = H, V ¹ = -CO-O- (left side is the carbon atom side to which R ¹ is bonded), V ² = -CO-O- (the left side is the carbon atom side to which R ² is bonded), V ³ = -CH _2- )

[2-4] 1- (meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-5,7-dione (R = H or CH ₃ , R ¹ = R ² = R ³ = H, V ¹ = -O-CO- (left side is the carbon atom side where R ¹ is bonded), V ² = -CO-O- (left side is the carbon atom side where R ² is bonded), V ³ = -CH _2- )

[2-5] 1- (meth) acryloyloxy-5,7- ^{dioxatricyclo} [4.4.1.1 ^3,9 ] dodecane-4,8-dione (R = H or CH ₃ , R ¹ = R ² = R ³ = H, V ¹ = -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) , V ³ = -CH _2- )

Although the following compound is mentioned as a typical example of a compound represented by General formula (8b), It is not limited to this.

[2-6] 2- (meth) acryloyloxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one (= 5- (meth) acryloyloxy-2,6-nor Borancarbolactone) (R = H or CH ₃ , R ⁴ = R ⁵ = R ⁶ = H, X = methylene group)

[2-7] 2- (meth) acryloyloxy-2-methyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one (R = H or CH ₃ , R ⁴ = CH ₃ , R ⁵ = R ⁶ = H, X = methylene group)

[2-8] 2- (meth) acryloyloxy-6-methyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one (R = H or CH ₃ , R ⁵ = CH ₃ , R ⁴ = R ⁶ = H, X = methylene group)

[2-9] 2- (meth) acryloyloxy-9-methyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one (R = H or CH ₃ , R ⁶ = CH ₃ , R ⁴ = R ⁵ = H, X = methylene group)

[2-10] 2- (meth) acryloyloxy-9-carboxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one (R = H or CH ₃ , R ⁴ = R ⁵ = H, R ⁶ = COOH, X = methylene group)

[2-11] 2- (meth) acryloyloxy-9-methoxycarbonyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one (R = H or CH ₃ , R ⁴ = R ⁵ = H, R ⁶ = methoxycarbonyl group, X = methylene group)

[2-12] 2- (meth) acryloyloxy-9-ethoxycarbonyl-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-t-butoxycarbonyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one (R = H or CH ₃ , R ⁴ = R ⁵ = H, R ⁶ = t-butoxycarbonyl group, X = methylene group)

Although the following compound is mentioned as a typical example of a compound represented by General formula (8c), It is not limited to this.

[2-14] 8- (meth) acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-5-one (R = H or CH ₃ )

[2-15] 9- (meth) acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-5-one (R = H or CH ₃ )

Although the following compound is mentioned as a typical example of a compound represented by General formula (8d), It is not limited to this.

[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 ¹² = R ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = H)

[2-17] 4- (meth) acryloyloxy-4-methyl-6-oxabicyclo [3.2.1] octan-7-one (R = H or CH ₃ , R ¹⁰ = R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = H, R ⁹ = CH ₃ )

[2-18] 4- (meth) acryloyloxy-5-methyl-6-oxabicyclo [3.2.1] octan-7-one (R = H or CH ₃ , R ⁹ = R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = H, R 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 ¹¹ = R ¹² = R ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = H, R ⁹ = R ¹⁰ = CH ₃ )

Although the following compound is mentioned as a typical example of the compound represented by General formula (8e), It is not limited to this.

[2-20] 6- (meth) acryloyloxy-2-oxabicyclo [2.2.2] octan-3-one (R = H or CH ₃ , R ¹⁸ = R ¹⁹ = R ²⁰ = R ²¹ = R ²² = R ²³ = R ²⁴ = R ²⁵ = R ²⁶ = H)

[2-21] 6- (meth) acryloyloxy-6-methyl-2-oxabicyclo [2.2.2] octan-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) acryloyloxy-1-methyl-2-oxabicyclo [2.2.2] octan-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] octan-3-one (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 )

Although the following compound is mentioned as a typical example of a compound represented by General formula (8f), It is not limited to this.

[2-24] β- (meth) acryloyloxy-γ-butyrolactone (R = H or CH ₃ , R ²⁷ = R ²⁸ = R ²⁹ = R ³⁰ = R ³¹ = H)

[2-25] β- (meth) acryloyloxy-α, α-dimethyl-γ-butyrolactone (R = H or CH ₃ , R ²⁷ = R ²⁸ = CH ₃ , R ²⁹ = R ³⁰ = R ³¹ = H)

[2-26] β- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone (R = H or CH ₃ , R ³⁰ = R ³¹ = CH ₃ , R ²⁷ = R ²⁸ = R ²⁹ = H)

[2-27] β- (meth) acryloyloxy-α, α, β-trimethyl-γ-butyrolactone (R = H or CH ₃ , R ²⁷ = R ²⁸ = R ²⁹ = CH ₃ , R ³⁰ = R ³¹ = H)

[2-28] β- (meth) acryloyloxy-β, γ, γ-trimethyl-γ-butyrolactone (R = H or CH ₃ , R ²⁹ = R ³⁰ = R ³¹ = CH ₃ , R ²⁷ = R ²⁸ = H)

[2-29] β- (meth) acryloyloxy-α, α, β, γ, γ-pentamethyl-γ-butyrolactone (R = H or CH ₃ , R ²⁷ = R ²⁸ = R ²⁹ = R ³⁰ = R ³¹ = CH ₃ )

Although the following compound is mentioned as a typical example of a compound represented by General formula (8g), It is not limited to this.

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

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

[2-32] α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone (R = H or CH ₃ , R ³³ = R ³⁴ = CH ₃ , R ³² = R ³⁵ = R ³⁶ = H)

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

[2-34] α- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone (R = H or CH ₃ , R ³⁵ = R ³⁶ = CH ₃ , R ³² = R ³³ = R ³⁴ = H)

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

[2-36] α- (meth) acryloyloxy-β, β, γ, γ-tetramethyl-γ-butyrolactone (R = H or CH ₃ , R ³³ = R ³⁴ = R ³⁵ = R ³⁶ = CH ₃ , R ³² = H)

[2-37] α- (meth) acryloyloxy-α, β, β, γ, γ-pentamethyl-γ-butyrolactone (R = H or CH ₃ , R ³² = R ³³ = R ³⁴ = R ³⁵ = R ³⁶ = CH ₃ )

Maleic anhydride and maleimide are mentioned as another example of the polymerizable unsaturated monomers other than the unsaturated carboxylic acid hemiacetal ester used in order to provide the high molecular compound as a resist to the high molecular compound of this invention. These correspond to the said acid anhydride group containing monomer and imide group containing monomer.

As another representative example of a polymerizable unsaturated monomer other than the unsaturated carboxylic acid hemiacetal ester used to impart various functions as a resist to the polymer compound of the present invention, a compound represented by the following formula (9) may be mentioned. These compounds correspond to the said hydroxyl group containing monomer, a mercapto 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 is a substituent bonded to ring Z ² , the same or different, and an oxo group, An alkyl group, a hydroxyl group which can be protected by a protecting group, a hydroxyalkyl group which can be protected by a protecting group, a carboxyl group which can be protected by a protecting group, an amino group which can be protected by a protecting group, or a sulfonic acid group which can be protected by a protecting group. at least one of n R ³⁷ is an oxo group, a hydroxyl group which may be protected with a protecting 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 group which may be protected with a protecting group, or A sulfonic acid group which may be protected by a protecting group, n represents an integer of 1 to 3)

The alicyclic hydrocarbon ring having 6 to 20 carbon atoms in ring Z ² may be monocyclic or may be polycyclic such as condensed ring or temporary exchange. As typical alicyclic hydrocarbon rings, for example, cyclohexane ring, cyclooctane ring, cyclodecane ring, adamantane ring, norbornane ring, norbornene ring, bornan ring, isobornane ring, perhydroindene ring, decalin ring, Perhydrofluorene ring (tricyclo [7.4.0.0 ^3,8 ] tridecane ring), perhydroanthracene ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tricyclo [4.2.2.1 ^2,5 ] A kan ring, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane ring, etc. are mentioned. The alicyclic hydrocarbon ring includes an alkyl group such as a methyl group (for example, a C _1-4 alkyl group), a haloalkyl group such as a trifluoromethyl group, a halogen atom such as a fluorine atom or a chlorine atom, and a hydroxyl group that can be protected with a protecting group. Substituents such as hydroxyalkyl groups which may be protected with protecting groups, mercapto groups which may be protected with protecting groups, oxo groups, carboxyl groups which may be protected with protecting groups, amino groups which may be protected with protecting groups, and sulfonic acid groups which may be protected with protecting groups May have

In the formula (9), the alkyl group for R ³⁷ is a linear or branched carbon number such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl or dodecyl group. Alkyl groups of about 1-20 are mentioned. As the amino group which may be protected by a protective group may include an amino group, a substituted amino group (e.g., C _1-4 alkylamino group such as methylamino, ethylamino, propylamino group, etc.), and the like. The sulfonic acid group which can be protected with a protecting group includes -SO ₃ R ^z group and the like. R ^z represents a hydrogen atom or an alkyl group, and examples of the alkyl group include linear or branched carbon atoms having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and hexyl groups. Alkyl group etc. are mentioned. The hydroxyl group which can be protected by the protecting group for R ³⁷ , the hydroxyalkyl group which can be protected by the protecting group, the mercapto group which can be protected by the protecting group, and the carboxyl group which can be protected by the protecting group are the same as above.

Although the following compound is mentioned as a typical example of the compound represented by General formula (9), It is not limited to this.

[3-1] 1-hydroxy-3- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = OH, n = 1, Z ² = adamantane ring)

[3-2] 1,3-dihydroxy-5- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = OH, n = 2, Z ² = adamantane ring)

[3-3] 1-carboxy-3- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = COOH, n = 1, Z ² = adamantane ring)

[3-4] 1,3-dicarboxy-5- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = COOH, n = 2, Z ² = adamantane ring)

[3-5] 1-carboxy-3-hydroxy-5- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = OH, COOH, n = 2, Z ² = adamantane ring )

[3-6] 1-t-butoxycarbonyl-3- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = t-butoxycarbonyl group, n = 1, Z ² = A Just bullet)

[3-7] 1,3-bis (t-butoxycarbonyl) -5- (meth) acryloyloxyadamantane [R = H or CH ₃ , R ³⁷ = t-butoxycarbonyl group, n = 2 , Z ² = adamantane]

[3-8] 1-t-butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = OH, t-butoxycarbonyl group, n = 2, Z ² = adamantane ring)

[3-9] 1- (2-tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = 2-tetrahydropyranyloxycarbonyl group, n = 1, Z ² = adamantane ring)

[3-10] 1,3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = 2-tetrahydropyranyl Oxycarbonyl group, n = 2, Z ² = adamantane ring)

[3-11] 1-hydroxy-3- (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ³⁷ = OH, 2- tetrahydropyranyl oxy group, n = ^2, Z 2 = adamantyl bullet)

Moreover, acrylic acid, methacrylic acid, etc. can also be used as said carboxyl group-containing monomer.

Representative examples of the polymerizable unsaturated monomers used to enhance the acid leaving function of the polymer compound include, for example, 1- [1- (meth) acryloyloxy-1-methylethyl] adamantane, 2- (meth ) Acryloyloxy-2-methyladamantane, 2- (meth) acryloyloxy-2-ethyladamantane, 2- [1- (meth) acryloyloxy-1-methylethyl] norbor Egg, 2- (meth) acryloyloxy-2-methylnorbornane, 1- [1- (meth) acryloyloxy-1-methylethyl] cyclohexane, 1- (meth) acryloyloxy- 1-methylcyclohexane, 3- [1- (meth) acryloyloxy-1-methylethyl] tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, t-butyl (meth) acrylate, 1- (t-butoxycarbonyl) -3- (meth) acryloyloxyadamantane, 2- (t-butoxycarbonyl) -5 or 6- (meth) acryloyloxynorbornan, and These flexible bodies (instead of methyl groups, other alkyl groups such as ethyl groups or haloalkyl groups such as trifluoromethyl groups That may be mentioned compounds, etc.), and the like.

On the other hand, the corresponding (meth) acryloyloxy group in each monomer represented by the above formulas (8a) to (8g) and (9) is substituted with a vinyl group (including vinyl groups having substituents such as 1-methylvinyl group and crotyl group). A vinyl ether compound can also be used as a monomer component of the high molecular compound of this invention.

In the polymer compound of the present invention, the ratio of the repeating unit represented by the formula (I) is not particularly limited, but is generally 1 to 100 mol%, preferably 10 to 90 mol%, based on the total monomer units constituting the polymer, More preferably, it is about 30-80 mol%. The ratio of repeating units (except for repeating units represented by Formula I) corresponding to at least one monomer selected from lactone skeleton-containing monomers, cyclic ketone skeleton-containing monomers, acid anhydride group-containing monomers and imide group-containing monomers is 0 to 95. It is mol%, Preferably it is 0-60 mol%, More preferably, it is about 10-40 mol%. The proportion of the repeating unit corresponding to at least one monomer selected from the hydroxyl group-containing monomer, the mercapto group-containing monomer and the carboxyl group-containing monomer is 0 to 95 mol%, preferably 5 to 90 mol%, more preferably 10 to 50 It is about mol%.

In obtaining the polymer compound of the present invention, the polymerization of the monomer mixture can be carried out by conventional methods used for producing acrylic polymers, such as solution polymerization, bulk polymerization, suspension polymerization, block-suspension polymerization, emulsion polymerization, and the like. In particular, solution polymerization is preferred. Moreover, dripping polymerization is preferable also in solution polymerization. Specifically, the dropping polymerization is, for example, (i) preparing a monomer solution previously dissolved in an organic solvent and a polymerization initiator solution dissolved in an organic solvent, respectively, and the monomer solution and the polymerization initiator solution in an organic solvent maintained at a constant temperature. Method to drop each, (ii) Method to drop the mixed solution which melt | dissolved the monomer and the polymerization initiator in the organic solvent in the organic solvent hold | maintained at constant temperature, (iii) The monomer solution melt | dissolved in the organic solvent previously, and the polymerization melt | dissolved in the organic solvent. Each initiator solution is prepared and carried out by a method such as dropping a polymerization initiator solution into the monomer solution maintained at a constant temperature.

As a polymerization solvent, a well-known solvent can be used, For example, ether (chain ether, such as glycol ethers, such as diethyl ether, propylene glycol monomethyl ether, cyclic ether, such as tetrahydrofuran, dioxane, etc.), ester ( Glycol ether esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, and the like), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfoxide (dimethyl sulfoxide, etc.), alcohol (methanol, ethanol, propanol, etc.), hydrocarbons (aromatic hydrocarbons such as benzene, toluene, xylene, hexane, etc.) Alicyclic hydrocarbons such as aliphatic hydrocarbons and cyclohexane); and mixed solvents thereof. Moreover, a well-known polymerization initiator can be used as a polymerization initiator. Polymerization temperature can be suitably selected, for example in the range of about 30-150 degreeC.

The polymer obtained by polymerization can be purified by precipitation or reprecipitation. The precipitation or reprecipitation solvent can be either an organic solvent or water, and can also be a mixed solvent. As an organic solvent used as a precipitation or reprecipitation solvent, For example, hydrocarbon (aliphatic hydrocarbons, such as pentane, hexane, heptane, octane; alicyclic hydrocarbons, such as cyclohexane and methylcyclohexane; aromatic hydrocarbons, such as benzene, toluene, and xylene) ), Halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.), nitrile (acetonitrile, benzonitrile, etc.) , Ethers (chain ethers such as diethyl ether, diisopropyl ether, dimethoxyethane; cyclic ethers such as tetrahydrofuran and dioxane), ketones (acetone, methyl ethyl ketone, diisobutyl ketone, etc.), esters (acetic acid) Ethyl, butyl acetate, etc.), carbonate (dimethyl carbonate, diethyl carbonate, ethylene carbonate There may be mentioned propylene carbonate, and the like), alcohols (methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acids (acetic acid, etc.), mixed solvents containing these solvents.

Especially, as an organic solvent used as said precipitation or reprecipitation solvent, the solvent containing at least a hydrocarbon (especially aliphatic hydrocarbons, such as hexane), is preferable. In the solvent containing at least such a hydrocarbon, the ratio of the hydrocarbon (for example, aliphatic hydrocarbon such as hexane) and other solvent is, for example, the former / the latter (volume ratio; 25 ° C.) = 10/90 to 99/1, preferably Preferably, the former / the latter (volume ratio; 25 ° C.) = 30/70 to 98/2, and more preferably the former / the latter (volume ratio; 25 ° C.) = 50/50 to 97/3.

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

As the photoacid generator, conventional or known compounds which efficiently generate an acid by exposure, for example, diazonium salt, iodonium salt (for example, diphenyliodohexafluorophosphate, etc.), sulfonium salt (for example, For example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonic acid ester [for example, 1-phenyl-1- (4-methylphenyl) Sulfonyloxy-1-benzoylmethane, 1,2,3-trisulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4 -Methylphenylsulfonyloxymethyl) -1-hydroxy-1-benzoylmethane and the like], oxatizol derivatives, s-triazine derivatives, disulfone derivatives (such as diphenyldisulfone), imide compounds, oxime sulfonates, Diazonaptoquinone, benzoin tosylate, etc. can be used. These photo-acid generators can be used individually or in combination of 2 or more types.

The amount of the photoacid generator can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each monomer unit (repeated unit) in the polymer compound, and the like, for example, to 100 parts by weight of the polymer compound. 0.1-30 weight part, Preferably it is 1-25 weight part, More preferably, it can select from the range of about 2-20 weight part.

Resin compositions for photoresists include alkali-soluble components such as alkali-soluble resins (e.g., novolak resins, phenol resins, imide resins, carboxyl group-containing resins, etc.), colorants (e.g., dyes), organic solvents (e.g. For example, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, these mixed solvents, and the like) may be included.

The resin composition for photoresist is applied onto a substrate or a substrate, dried, and then exposed to light (or further post-exposure bake) on a coating film (resist film) through a predetermined mask to form a latent image pattern. By developing, a fine pattern can be formed with high precision.

Examples of the substrate or substrate include silicon wafers, metals, plastics, glass, ceramics, and the like. Application of the resin composition for photoresist can be performed using conventional coating means, such as a spin coater, a dip coater, and a roller coater. The thickness of a coating film is 0.01-20 micrometers, Preferably it is about 0.05-2 micrometers.

Light of various wavelengths, for example, ultraviolet rays, X-rays, and the like can be used for exposure, and g-rays, i-rays, and excimer lasers (for example, XeCl, KrF, KrCl, ArF, ArCl, F) are generally used for semiconductor resists. ₂ , Kr ₂ , KrAr, Ar _2, etc.) may be used. Exposure energy is about 0.1-1000 mJ / cm <2>, for example.

An acid is produced | generated from a photo-acid generator by light irradiation, and by this acid, protecting groups, such as a carboxyl group of the monomeric unit (alkali-soluble unit) which has an acid leaving group of the said high molecular compound, (e.g. The carboxyl group etc. which contribute to solubilization are produced | generated. Therefore, a predetermined pattern can be formed with high precision by image development by water or an alkaline developing solution.

The present invention will be described in more detail based on Examples below, but the present invention is not limited to these Examples.

Preparation Example 1

21.3 g (0.118 mol) of 2-vinyloxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one represented by the following formula (10), methacrylic acid 50.8 g (0.59 mol), phosphoric acid 120 mg ( 12 mmol), a mixture of 15 mg (0.12 mmol) of 4-methoxyphenol, and 210 ml of toluene were put into 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 10 wt% aqueous sodium carbonate solution and once with 200 ml of 10 wt% saline, and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography to give 2- (1-methacryloyloxyethoxy) -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one 25.5 represented by the following formula (12): g (96 mmol, yield 81%) was obtained. This material is a mixture of two isomers with an abundance ratio of about 1: 1. On the other hand, 2-vinyloxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one represented by the formula (10) is 2-hydroxy-4-oxatricyclo [4.2. 1.0 ^3,7 ] The nonan-5-one and vinyl propionate were synthesize | combined using the method of Unexamined-Japanese-Patent No. 2003-73321, and the distillation refine | purified was used.

[Spectral data of 2- (1-methacryloyloxyethoxy) -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one]

¹ H-NMR (CDCl 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, 1 H)

Production Example 2

85 g (500 mmol) of 3-hydroxy-1-oxaspiro [4.5] decan-2-one represented by the following Chemical Formula 13 in a reaction vessel equipped with a Dean-Stark apparatus and a thermometer, and 31.8 g of sodium carbonate ( 300 mmol) and 600 ml of toluene were added thereto, and the mixture was heated to 100 ° C. while stirring under a nitrogen atmosphere. 3.36 g (5 mmol) of Ir ₂ Cl ₂ (C ₈ H ₁₂ ) ₂ [di-μ-chlorobis (1,5-cyclooctadiene) 2iridium (I)] was added to the reaction vessel, followed by further addition of vinyl propionate 100 The reaction was carried out while azeotropic dehydration by heating and refluxing g (1 mol) dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours. After the reaction was completed, the reaction solution was allowed to cool, washed with 700 ml of water, and concentrated under reduced pressure. The concentrated residue was distilled and purified to obtain 22.5 g (114 mmol, 23%) of a colorless transparent liquid of 3-hydroxy-1-oxaspiro [4.5] decane-2-one represented by the following formula (14). On the other hand, 3-hydroxy-1-oxaspiro [4.5] decan-2-one represented by the formula (13) is selected from cyclohexanol and methyl acrylate, which are described in Chem. Commun., 7, 613-614 (2000)] and synthesized by the method described in silica gel column chromatography were used.

[Spectral data of 3-vinyloxy-1-oxaspiro [4.5] decan-2-one]

¹ H-NMR (CDCl ₃ ) 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)

17.1 g (87 mmol) of 3-vinyloxy-1-oxaspiro [4.5] decan-2-one obtained, 37.4 g (435 mmol) of methacrylic acid, 0.85 g (8.7 mmol) of phosphoric acid, and 17.1 mg of 4-methoxyphenol (0.14 mmol) and a mixture of 170 ml of toluene were put into a reaction vessel, and the mixture was stirred at 50 ° C. for 4.5 hours under a dry air atmosphere. After the reaction was completed, the reaction solution was washed with 170 ml of water, 170 ml of a 10% by weight aqueous sodium carbonate solution (twice), and 170 ml of water, and the organic layer was concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography, and 3- (1-methacryloyloxyethoxy) -1-oxaspiro [4.5] decan-2-one [= 3- (1) represented by the following formula (15): 17.3 g (61 mmol, yield 70%) of a colorless liquid of -methacryloyloxyethoxy) -2-oxo-1-oxaspiro [4.5] decane] were obtained. This substance was a mixture of Isomer A and Isomer B, and its abundance ratio was approximately A: B = 3: 1.

[Spectral data of 3- (1-methacryloyloxyethoxy) -1-oxaspiro [4.5] decan-2-one]

Isomer A

¹ H-NMR (CDCl ₃ ) δ: 1.34-1.84 (m, 13H), 1.92-1.97 (m, 4H), 2.40 (dd, 1H), 4.76 (t, 1H), 5.64 (m, 1H), 6.16 (m, 1 H), 6.28 (q, 1 H)

Isomer B

¹ H-NMR (CDCl ₃ ) 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

A mixture of 43.2 g of adamantaneethanol, 48.1 g of vinyl propionate, 15.3 g of sodium carbonate, 120 ml of toluene, and 1.62 g of di-μ-chlorobis (1,5-cyclooctadiene) 2iridium (I) was placed in a sand dune flask, It stirred for 4 hours, heating at 100 degreeC by nitrogen atmosphere. The precipitate in the reaction solution was filtered off, and the filtrate was concentrated under reduced pressure. The concentrate was distilled off under reduced pressure to obtain 34.8 g of 2- (adamantan-1-yl) ethylvinyl ether represented by the following formula (16).

[Spectral data of 2- (adamantan-1-yl) ethylvinyl ether]

¹ H-NMR (CDCl ₃ ) 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)

Preparation Example 4

A mixture of 32.8 g of 2- (adamantan-1-yl) ethylvinyl ether, 68.4 g of methacrylic acid, 0.16 g of phosphoric acid, 0.164 g of 4-methoxyphenol, and 290 ml of toluene was placed in a sand dune flask, under a nitrogen atmosphere, It stirred at 20 degreeC for 6 hours. After completion of the reaction, the reaction solution was washed twice with 500 ml of 10 wt% aqueous sodium carbonate solution and once with 500 ml of 10 wt% saline, and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography to obtain 386 g of 1- [2- (adamantan-1-yl) ethoxy] ethyl (meth) acrylate represented by the following formula (17).

[Spectral data of [1- [2- (adamantan-1-yl) ethoxy] ethyl (meth) acrylate]

¹ H-NMR (CDCl 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), 3.72 (m, 1H), 5.60 (m, 1H), 5.97 (m, 1H), 6.16 (m, 1H)

Preparation Example 5

Borylvinyl ether represented by the formula (18) 18.0 g (0.1 mol), methacrylic acid 43.0 g (0.5 mol), phosphoric acid 98 mg (1 mmol), 4-methoxyphenol 12 mg (0.1 mmol), toluene 180 ml Was added to 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 10 wt% aqueous sodium carbonate solution and once with 200 ml of 10 wt% saline solution, and the organic layer was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography to obtain 22.8 g (85 mmol, yield 85%) of 1- (bornyloxy) ethyl methacrylate represented by the following formula (19). In addition, bornyl vinyl ether was synthesize | combined from (-)-borneneol and vinyl propionate using the method of Unexamined-Japanese-Patent No. 2003-73321, and the distillation refinement was used.

[Spectral data of 1- (bornyloxy) ethyl methacrylate]

¹ H-NMR (CDCl ₃ ) 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

Resin Synthesis of the Following Structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were respectively introduced into a separate flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introduction tube, and heated to 85 ° C. Methacryloyloxy-4- ^oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one 4.93 g, 1-hydroxy-3-methacryloyloxyadamantane 4.66 g, 2- (1- 5.41 g of methacryloyloxyethoxy) -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one and dimethyl-2,2'-azobis (2-methylpropionate) (initiator 0.60 g of Wako Pure Chemical Industries, Ltd. brand name "V-601") was added dropwise over 4 hours as a mixed solution of 34.2 g each of PGMEA and PGME. Aged 2 hours after dropping. The obtained reaction liquid was dripped in the mixture liquid of 733 g of heptanes and 81 g of ethyl acetate, and the precipitated polymer was collect | recovered with the suction filter. The obtained polymer was dried under reduced pressure to obtain 13.8 g of the target product. The weight average molecular weight of the resulting polymer (M _w) is 9800, and the molecular weight distribution (M _w / M _n) was 1.88 (GPC measurement, polystyrene).

Example 2

Resin Synthesis of the Following Structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were respectively introduced into a separate flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introduction tube, and heated to 85 ° C. 4.13 g of hydroxy-3-methacryloyloxyadamantane, 10.87 g of 2- (1-methacryloyloxyethoxy) -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one; , 0.60 g of dimethyl-2,2'-azobis (2-methylpropionate) (initiator; Wako Pure Chemical Industries, Ltd., trade name "V-601") as a mixed solution of 34.2 g each of PGMEA and PGME These were dripped over 4 hours. Aged 2 hours after dropping. The obtained reaction liquid was dripped in the mixture liquid of 733 g of heptanes and 81 g of ethyl acetate, and the precipitated polymer was collect | recovered with the suction filter. The obtained polymer was dried under reduced pressure to obtain 13.5 g of the target product. The weight average molecular weight of the resulting polymer (M _w) was 10100, and the molecular weight distribution (M _w / M _n) was 1.90 is (GPC measurement, polystyrene).

Example 3

Resin Synthesis of the Following Structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were respectively introduced into a separate flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introduction tube, and heated to 85 ° C. 4.44 g of hydroxy-3-methacryloyloxyadamantane, 10.02 g of 2- (1-methacryloyloxyethoxy) -4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, 0.54 g of methacrylic acid and 0.60 g of dimethyl-2,2'-azobis (2-methylpropionate) (initiator; Wako Pure Chemical Industries, Ltd., trade name "V-601") were 34.2 each of PGMEA and PGME. They were dripped over 4 hours as g mixed solution. Aged 2 hours after dropping. The obtained reaction liquid was dripped in the mixture liquid of 733 g of heptanes and 81 g of ethyl acetate, and the precipitated polymer was collect | recovered with the suction filter. The obtained polymer was dried under reduced pressure to obtain 13.5 g of the target product. The weight average molecular weight of the resulting polymer (M _w) is 10,000, and the molecular weight distribution (M _w / M _n) was 1.90 is (GPC measurement, polystyrene).

Example 4

Resin Synthesis of the Following Structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were respectively introduced into a separate flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introduction tube, and heated to 85 ° C. 4.88 g of methacryloyloxy-4- ^oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one, 4.61 g of 1-hydroxy-3-methacryloyloxyadamantane, 3- (1- 5.51 g of methacryloyloxyethoxy) -1-oxaspiro [4.5] decan-2-one, and dimethyl-2,2'-azobis (2-methylpropionate) (initiator; Wako Pure Chemical Industries, Ltd.) 0.60 g of manufacture and the brand name "V-601" were used as the mixed solution of 34.2 g each of PGMEA and PGME, and these were dripped over 4 hours. Aged 2 hours after dropping. The obtained reaction liquid was dripped at the mixture liquid of 733 g of hexane and 81 g of ethyl acetate, and the precipitated polymer was collect | recovered with the suction filter. The obtained polymer was dried under reduced pressure to obtain 12.6 g of the target product. The weight average molecular weight of the resulting polymer (M _w) is 9900, and the molecular weight distribution (M _w / M _n) was 1.91 (GPC measurement, in terms of polystyrene).

Example 5

Resin Synthesis of the Following Structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were respectively introduced into a separate flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introduction tube, and heated to 85 ° C. 3.96 g of hydroxy-3-methacryloyloxyadamantane, 11.04 g of 3- (1-methacryloyloxyethoxy) -1-oxaspiro [4.5] decane-2-one, and dimethyl-2,2 0.60 g of '-azobis (2-methylpropionate) (initiator; Wako Pure Chemical Industries, Ltd., trade name "V-601") was added dropwise over 4 hours using a mixture solution of 34.2 g each of PGMEA and PGME. It was. Aged 2 hours after dropping. The obtained reaction liquid was dripped at 733 g of hexane and 81 g of ethyl acetate, and the precipitated polymer was collect | recovered with the suction filter. The obtained polymer was dried under reduced pressure to obtain 12.8 g of the target product. The weight average molecular weight of the resulting polymer (M _w) is 9800, and the molecular weight distribution (M _w / M _n) was 1.89 (GPC measurement, in terms of polystyrene).

Example 6

Resin Synthesis of the Following Structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were respectively introduced into a separate flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introduction tube, and heated to 85 ° C. 4.27 g of hydroxy-3-methacryloyloxyadamantane, 10.21 g of 3- (1-methacryloyloxyethoxy) -1-oxaspiro [4.5] decane-2-one, and 0.52 g of methacrylic acid , 0.60 g of dimethyl-2,2'-azobis (2-methylpropionate) (initiator; Wako Pure Chemical Industries, Ltd., trade name "V-601") as a mixed solution of 34.2 g each of PGMEA and PGME These were dripped over 4 hours. Aged 2 hours after dropping. The obtained reaction liquid was dripped at the mixture liquid of 733 g of hexane and 81 g of ethyl acetate, and the precipitated polymer was collect | recovered with the suction filter. The obtained polymer was dried under reduced pressure to obtain 12.5 g of the target product. The weight average molecular weight of the resulting polymer (M _w) was 10100, and the molecular weight distribution (M _w / M _n) was 1.88 (GPC measurement, polystyrene).

Example 7

Resin Synthesis of the Following Structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were respectively introduced into a separate flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introduction tube, and heated to 85 ° C. 4.77 g of methacryloyloxy-4- ^oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one, 4.50 g of 1-hydroxy-3-methacryloyloxyadamantane, 1- [2- 5.74 g of (adamantan-1-yl) ethoxy] ethyl methacrylate and dimethyl-2,2'-azobis (2-methylpropionate) (initiator; manufactured by Wako Pure Chemical Industries, Ltd., trade name "V -601 ") were added dropwise over 4 hours using a mixed solution of 34.2 g each of PGMEA and PGME. Aged 2 hours after dropping. The obtained reaction liquid was dripped in the mixed liquid of 733 g of heptanes and 81 g of ethyl acetate, and the precipitated polymer was collect | recovered with the suction filter. The obtained polymer was dried under reduced pressure to obtain 13.5 g of the target product. The weight average molecular weight of the resulting polymer (M _w) is 9300, and the molecular weight distribution (M _w / M _n) was 1.92 (GPC measurement, in terms of polystyrene).

Example 8

Resin Synthesis of the Following Structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were respectively introduced into a separate flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introduction tube, and heated to 85 ° C. Methacryloyloxy-4- ^oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one 4.93 g, 1-hydroxy-3-methacryloyloxyadamantane 4.66 g, 1- (bornyl 5.41 g of oxy) ethyl methacrylate and 0.60 g of dimethyl-2,2'-azobis (2-methylpropionate) (initiator; Wako Pure Chemical Industries, Ltd., trade name "V-601") 34.2 g of mixed solution of PGME each was added dropwise over 4 hours. Aged 2 hours after dropping. The obtained reaction liquid was dripped in the mixture liquid of 733 g of heptanes and 81 g of ethyl acetate, and the precipitated polymer was collect | recovered with the suction filter. The obtained polymer was dried under reduced pressure to obtain 13.2 g of the target product. The weight average molecular weight of the resulting polymer (M _w) is 9400, and the molecular weight distribution (M _w / M _n) was 1.90 is (GPC measurement, polystyrene).

Comparative Example 1

Resin Synthesis of the Following Structure

16.5 g of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were respectively introduced into a separate flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introduction tube, and heated to 85 ° C. 5.16 g of methacryloyloxy-4- ^oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one, 4.87 g of 1-hydroxy-3-methacryloyloxyadamantane, 2-methacrylo 4.97 g of yloxy-2-methyladamantane and 0.60 g of dimethyl-2,2'-azobis (2-methylpropionate) (initiator; Wako Pure Chemical Industries, Ltd. make, brand name "V-601") , 34.2 g of PGMEA and PGME, respectively, were added dropwise over 4 hours. Aged 2 hours after dropping. The obtained reaction liquid was dripped at the mixture liquid of heptane 733 g and ethyl acetate 81g, and the precipitated polymer was collect | recovered with the suction filter. The obtained polymer was dried under reduced pressure to obtain 13.5 g of the target product. The weight average molecular weight of the resulting polymer (M _w) is 9800, and the molecular weight distribution (M _w / M _n) is 1 was 88 (in terms of GPC measurement, polystyrene).

Evaluation test

For each polymer obtained in Examples and Comparative Examples, 100 parts by weight of the polymer and 10 parts by weight of triphenylsulfonium hexafluoroantimonate were mixed with propylene glycol monomethyl ether (PGME) as a solvent to obtain a polymer concentration of 17% by weight. A resin composition for photoresist was prepared. This composition was applied onto a silicon wafer by spin coating to form a photosensitive layer having a thickness of 1.0 mu m. After prebaking at a temperature of 100 ° C. for 150 seconds by a hot plate, a KrF excimer laser having a wavelength of 247 nm was used and exposed at an irradiation dose of 30 mJ / cm 2 through a mask, followed by postbaking at a temperature of 100 ° C. for 60 seconds. Subsequently, it developed for 60 second by 0.3 M tetramethylammonium hydroxide aqueous solution, and rinsed with pure water. As a result, when the polymer of the Example was used, the line and space pattern of 0.20 micrometer was all obtained clearly and with high precision, but when the polymer of the comparative example was used, the precision of the said pattern was bad and it lacked clearness.

Claims (8)

An unsaturated carboxylic hemiacetal ester represented by the following formula (1). <Formula 1>

[Wherein, R ^a represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 3 carbon atoms or a fluoroalkyl group of 1 to 3 carbon atoms, R ^b represents an alkyl group of 1 to 3 carbon atoms, R ^c represents a hydrogen atom or carbon number An alkyl group of 1 to 3 is represented, and R ^d represents an organic group including a lactone skeleton, an adamantane ring skeleton or a bornan ring skeleton represented by the following formulas (6b) and (6g).

(Wherein R ⁴ to R ⁶ , R ³² to R ³⁶ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a hydroxyl group which may be protected with a protecting group, a hydroxy that may be protected with a protecting group An alkyl group, a mercapto group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group, X represents an alkylene group, an oxygen atom, a sulfur atom or a non-bonding, and in Formula 6g, 2 of R ³² to R ³⁶ Two or more groups may combine to form a ring with a carbon atom or carbon-carbon bond)] The compound of claim 1, wherein R ^a is a hydrogen atom or a methyl group, R ^b is a methyl group, R ^c is a hydrogen atom, and R ^d is

,

,

or

(Wherein * represents a bond) unsaturated carboxylic hemiacetal ester. Of an unsaturated carboxylic acid hemiacetal ester characterized by reacting an unsaturated carboxylic acid represented by the following formula (3) with a vinyl ether compound represented by the following formula (4) to obtain an unsaturated carboxylic hemiacetal ester represented by the following formula (5): Recipe. <Formula 3>

(Wherein R ^a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms) <Formula 4>

[In formula, R <^c> represents a hydrogen atom or a C1-C3 alkyl group, R <^d> represents the organic group containing a lactone skeleton, adamantane ring skeleton, or bornan ring skeleton represented by following formula (6b) or 6g, R ^e And R ^f each represent a hydrogen atom or a methyl group.

(Wherein R ⁴ to R ⁶ , R ³² to R ³⁶ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a hydroxyl group which may be protected with a protecting group, a hydroxy that may be protected with a protecting group An alkyl group, a mercapto group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group, X represents an alkylene group, an oxygen atom, a sulfur atom or a non-bonding, and in Formula 6g, 2 of R ³² to R ³⁶ Two or more groups may combine to form a ring with a carbon atom or carbon-carbon bond)] <Formula 5>

(Wherein R ^a , R ^c , R ^d , R ^e , R ^f are the same as above) A polymer compound comprising a repeating unit represented by the following formula (I). <Formula I>

[Wherein, R ^a represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 3 carbon atoms or a fluoroalkyl group of 1 to 3 carbon atoms, R ^b represents an alkyl group of 1 to 3 carbon atoms, R ^c represents a hydrogen atom or carbon number An alkyl group of 1 to 3 is represented, and R ^d represents an organic group including a lactone skeleton, an adamantane ring skeleton or a bornan ring skeleton represented by the following formula (6b) or (6g).

(Wherein R ⁴ to R ⁶ , R ³² to R ³⁶ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a hydroxyl group which may be protected with a protecting group, a hydroxy that may be protected with a protecting group An alkyl group, a mercapto group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group, X represents an alkylene group, an oxygen atom, a sulfur atom or a non-bonding, and in Formula 6g, 2 of R ³² to R ³⁶ Two or more groups may combine to form a ring with a carbon atom or carbon-carbon bond)] The polymer compound according to claim 4, further comprising repeating units corresponding to the lactone skeleton-containing monomer represented by the following formula (8a), excluding repeating units represented by the formula (I).

(Wherein R represents a hydrogen atom or a methyl group, R ¹ to R ³ are the same or different, and may be protected with a hydroxyl group, a protecting group which may be protected with a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a protecting group) Hydroxyalkyl group, a mercapto group which can be protected by a protecting group, or a carboxyl group which can be protected by a protecting group, and V ¹ to V ³ are the same or different and represent -CH _2- , -CO- or -COO-. Provided that at least one of V ¹ to V ³ is -COO-) The polymer compound according to claim 4 or 5, further comprising a repeating unit corresponding to at least one monomer selected from a hydroxyl group-containing monomer represented by the following formula (9) or a carboxyl group-containing monomer which is acrylic acid or methacrylic acid. <Formula 9>

(Wherein, ring Z ² represents an adamantane ring, R represents a hydrogen atom or a methyl group, R ³⁷ is a substituent bonded to ring Z ² and is the same or different and is protected from an oxo group, an alkyl group, a protecting group) A hydroxyl group which can be protected, a hydroxyalkyl group which can be protected by a protecting group, a carboxyl group which can be protected by a protecting group, an amino group which can be protected by a protecting group, or a sulfonic acid group which can be protected by a protecting group, wherein only n of R ³⁷ At least one is an oxo group, a hydroxyl group protected by a protecting group, a hydroxyalkyl group protected by a protecting group, a carboxyl group protected by a protecting group, an amino group protected by a protecting group, or a protecting group Sulfonic acid group, n represents an integer of 1 to 3) The resin composition for photoresists containing at least the high molecular compound of Claim 4 or 5, and a photo-acid generator. The manufacturing method of the semiconductor which includes the process of apply | coating the resin composition for photoresists of Claim 7 on a base material or a board | substrate, forming a resist coating film, and forming a pattern through exposure and image development.