JP2007045922A - Method for producing polymer compound for photoresist and photoresist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple method for efficiently producing a polymer compound useful for photoresist and extremely easily soluble in a solvent for resist. <P>SOLUTION: The method for producing the polymer compound for photoresist comprises the polymerization of a monomer mixture at least containing a monomer having a group to become alkali-soluble with an acid and a monomer having a group containing an alicyclic skeleton containing a polar group by drop polymerization. The solution to be dropped into the polymerization system is directly introduced into the system without flowing along the wall surface of the polymerization vessel. The production method may be performed by using a nozzle attached to an end of a feeding line of the solution to be dropped into the polymerization system and extending toward the liquid surface of the system and directly introducing the dropping solution through the nozzle into the polymerization system without flowing the solution along the wall surface of the polymerization vessel. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a photoresist polymer compound useful for preparing a photoresist composition for use in microfabrication of a semiconductor, the photoresist composition containing the photoresist polymer compound, and the photoresist composition. The present invention relates to a method for manufacturing a semiconductor using an object.

  The positive photoresist used in the semiconductor manufacturing process must have properties such as the property that the irradiated part changes to alkali-soluble by light irradiation, adhesion to the silicon wafer, plasma etching resistance, transparency to the light used, etc. Don't be. The positive photoresist is generally used as a solution containing a main polymer, a photoacid generator, and several additives for adjusting the above characteristics. On the other hand, lithography exposure light sources used for semiconductor manufacturing have become shorter in wavelength year by year, and ArF excimer lasers having a wavelength of 193 nm are promising as next-generation exposure light sources. As a resist polymer used in this ArF excimer laser exposure machine, there is a polymer containing a repeating unit containing a group that is partly eliminated by acid and becomes alkali-soluble and a repeating unit containing an alicyclic skeleton having a polar group. Various proposals have been made (for example, Patent Documents 1 and 2).

  These polymers are usually isolated by polymerizing the monomer mixture and then subjecting the polymerization solution to a precipitation operation. And this resin is dissolved in a resist solvent together with a photoacid generator to prepare a resin composition for photoresist.

  On the other hand, the method of polymerizing a monomer and a polymerization initiator while dropping them in a solvent heated to the polymerization temperature (drop polymerization method) has an advantage that the polymerization temperature is easy to control. This can be said to be a suitable polymerization method for the synthesis of molecular compounds (for example, Patent Document 3). However, when a monomer mixture containing at least a monomer having a group that becomes alkali-soluble by an acid and a monomer having a group containing a polar group-containing alicyclic skeleton is subjected to drop polymerization, a polymerization solution is obtained after the polymerization. When a polymer obtained by subjecting to a precipitation operation is dissolved in a resist solvent, most of the polymer is dissolved but partially insoluble (turbidity) exists. Since this insoluble matter causes trouble in the semiconductor manufacturing process, it must be removed by filtration. However, since the particles are fine, the filtration speed is slow, and the filtration operation requires a lot of time and labor.

JP 2000-26446 A JP-A-9-73137 JP 2004-269855 A

  Accordingly, an object of the present invention is to provide a method for efficiently producing a photoresist polymer compound that is very easily dissolved in a resist solvent by simple means, and a photoresist composition comprising the photoresist polymer compound obtained by the production method. And a semiconductor manufacturing method using the photoresist composition.

  As a result of intensive investigations to achieve the above object, the present inventors have found that a monomer having at least a monomer having an alkali-soluble group by an acid and a monomer having a group having a polar group-containing alicyclic skeleton are included. When the monomer mixture is subjected to dripping polymerization, the solution dripped into the polymerization system is dropped directly into the polymerization system (reaction solution) without being transmitted to the wall of the polymerization vessel, and the resulting polymer is dissolved in the resist solvent. As a result, the inventors found that the insoluble content is extremely reduced and the operation can be completed in a short time even when the filtration operation is performed, and the present invention has been completed.

  That is, the present invention is a method in which a monomer mixture containing at least a monomer having an alkali-soluble group by an acid and a monomer having a group containing a polar group-containing alicyclic skeleton is polymerized by a dropping polymerization method. A method for producing a polymer compound for photoresist, comprising introducing a solution to be dripped into the polymerization system directly into the polymerization system without being transmitted to the wall of the polymerization vessel. A manufacturing method is provided.

  In this manufacturing method, a nozzle extending toward the polymerization system liquid surface is provided at the tip of a supply line of a solution to be dripped into the polymerization system, and the solution to be dripped into the polymerization system is transmitted to the wall of the polymerization vessel through the nozzle. Alternatively, it may be introduced directly into the polymerization system.

（式中、環Ｚは置換基を有していてもよい炭素数６〜２０の脂環式炭化水素環を示す。Ｒは水素原子又は置換基を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ¹〜Ｒ³は、同一又は異なって、置換基を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ⁴は環Ｚに結合している置換基であって、同一又は異なって、オキソ基、アルキル基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、又は保護基で保護されていてもよいカルボキシル基を示す。但し、ｎ個のＲ⁴のうち少なくとも１つは、−ＣＯＯＲ^a基を示す。前記Ｒ^aは置換基を有していてもよい第３級炭化水素基、テトラヒドロフラニル基、テトラヒドロピラニル基、又はオキセパニル基を示す。ｎは１〜３の整数を示す。Ｒ⁵、Ｒ⁶は、同一又は異なって、水素原子又は置換基を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ⁷は水素原子又は有機基を示す。Ｒ⁵、Ｒ⁶、Ｒ⁷のうち少なくとも２つが互いに結合して隣接する原子とともに環を形成していてもよい）
から選択された少なくとも１種の化合物を使用できる。 Examples of the monomer having a group that becomes alkali-soluble by an acid include the following formulas (1a) to (1d):

(In the formula, ring Z represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent. R represents a hydrogen atom or an optionally substituted substituent having 1 to 6 carbon atoms. R ^{1 to} R ³ are the same or different and each represents an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ⁴ is a substituent bonded to ring Z. And may be the same or different and may be protected with an oxo group, an alkyl group, a hydroxyl group that may be protected with a protecting group, a hydroxyalkyl group that may be protected with a protecting group, or a protecting group. Represents a carboxyl group, provided that at least one of n R ⁴ groups represents ^a —COOR ^a group, wherein R ^a represents ^a tertiary hydrocarbon group which may have ^a substituent, a tetrahydrofuranyl group, A tetrahydropyranyl group or an oxepanyl group, where n is an integer of 1 to 3. R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R ⁷ represents a hydrogen atom or an organic group. ⁵ , R ⁶ , or R ⁷ may be bonded to each other to form a ring with adjacent atoms.
At least one compound selected from can be used.

（式中、Ｒは水素原子又は置換基を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ⁸〜Ｒ¹⁰は、同一又は異なって、水素原子、アルキル基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、又は保護基で保護されていてもよいカルボキシル基を示し、Ｖ¹〜Ｖ³は、同一又は異なって、−ＣＨ₂−、−ＣＯ−又は−ＣＯＯ−を示す。但し、（ｉ）Ｖ¹〜Ｖ³のうち少なくとも１つは−ＣＯ−若しくは−ＣＯＯ−であるか、又は（ii）Ｒ⁸〜Ｒ¹⁰のうち少なくとも１つは、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、又は保護基で保護されていてもよいカルボキシル基である。Ｒ¹¹〜Ｒ¹⁵は、同一又は異なって、水素原子、アルキル基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、保護基で保護されていてもよいカルボキシル基を示す。Ｒ¹⁶〜Ｒ²⁴は、同一又は異なって、水素原子、アルキル基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、保護基で保護されていてもよいカルボキシル基を示す。Ｒ²⁵〜Ｒ³³は、同一又は異なって、水素原子、アルキル基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、保護基で保護されていてもよいカルボキシル基を示す。ｐは０又は１、ｑは１又は２を示す）
から選択された少なくとも１種の化合物を使用できる。 Examples of the monomer having a group containing a polar group-containing alicyclic skeleton include the following formulas (2a) to (2e)

(In the formula, R represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. R ^{8 to} R ¹⁰ are the same or different and each represents a hydrogen atom, an alkyl group, or a protecting group. A hydroxyl group which may be protected, a hydroxyalkyl group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group, V ^{1 to} V ³ are the same or different, and CH _2- , -CO- or -COO-, provided that (i) at least one of V ^{1 to} V ³ is -CO- or -COO-, or (ii) R ^{8 to} R ¹⁰ at least one of the, optionally protected hydroxyl group, a protected or unprotected hydroxyalkyl group with a protecting group, or be protected by a protecting group is also a carboxyl group which .R ¹¹ ~ R ¹⁵ is the same or different and is a hydrogen atom , An alkyl group, a hydroxyl group that may be protected with a protecting group, a hydroxyalkyl group that may be protected with a protecting group, and a carboxyl group that may be protected with a protecting group, R ^{16 to} R ²⁴ represent It is the same or different and represents a hydrogen atom, an alkyl group, a hydroxyl group that may be protected with a protecting group, a hydroxyalkyl group that may be protected with a protecting group, or a carboxyl group that may be protected with a protecting group. R ^{25 to} R ³³ are the same or different and are protected by a hydrogen atom, an alkyl group, a hydroxyl group which may be protected with a protecting group, a hydroxyalkyl group which may be protected with a protecting group, or a protecting group. (P represents 0 or 1, q represents 1 or 2)
At least one compound selected from can be used.

  The present invention also provides a photoresist composition comprising a polymer compound for photoresist produced by the above method and a photoacid generator.

  The present invention further provides a method for producing a semiconductor comprising a step of applying the photoresist composition to a substrate or a base material to form a resist coating film.

  According to the method for producing a photoresist polymer compound of the present invention, when a monomer mixture composed of a combination of a plurality of specific monomers is polymerized by drop polymerization, a solution to be dripped into the polymerization system is added to the polymerization vessel. The polymer is introduced directly into the polymerization system (reaction solution) without being transmitted to the vessel wall and polymerized, so there is no local increase in monomer concentration, or the molecular weight of the polymer produced and the monomer composition in the polymer are uniform. Thus, the production of a resist solvent-insoluble component is suppressed, and a photoresist polymer compound that is very easily dissolved in a resist solvent can be efficiently produced by simple means. Moreover, according to the photoresist composition prepared from the polymer compound for photoresist thus obtained, since the polymer uniformity is excellent, troubles are unlikely to occur in semiconductor manufacturing, and sensitivity and resolution are improved. A pattern can be formed with high accuracy.

  In the present invention, a monomer having a group that is alkali-soluble by an acid (sometimes referred to as “monomer a”) and a monomer having a group containing a polar group-containing alicyclic skeleton (“monomeric” A polymer solution for photoresist is produced by dropping and polymerizing a monomer solution containing at least "body b") to a polymerization system (reaction solution).

  Monomer a is a polymerizable compound having a group that is partially dissolved by the action of an acid generated from a photoacid generator upon exposure and introduced into a resin by polymerization and is soluble in an alkaline developer. (Monomer having an acid leaving group) No particular limitation, for example, having an alicyclic hydrocarbon group having 6 to 20 carbon atoms and having a group capable of leaving by the action of an acid (Meth) acrylic acid ester and the like. “A (meth) acrylic acid ester containing a alicyclic hydrocarbon group having 6 to 20 carbon atoms and having a group capable of leaving by the action of an acid” includes an alicyclic group having 6 to 20 carbon atoms. A (meth) acrylic acid ester having a hydrocarbon group and a tertiary carbon atom at the bonding site with an oxygen atom constituting the ester bond of the (meth) acrylic acid ester is included. The alicyclic hydrocarbon group may be directly bonded to an oxygen atom constituting the ester bond of (meth) acrylic acid ester, or may be bonded via a linking group such as an alkylene group. The alicyclic hydrocarbon group having 6 to 20 carbon atoms may be a monocyclic hydrocarbon group or a polycyclic (bridged cyclic) hydrocarbon group. Representative examples of such (meth) acrylic acid esters include compounds represented by the formulas (1a) and (1b).

In addition, “(meth) acrylic acid ester having a group having 6 to 20 carbon atoms and having a group capable of leaving by the action of an acid” includes an aliphatic group having 6 to 20 carbon atoms. A cyclic hydrocarbon group and a -COOR ^a group (R ^a is an optionally substituted tertiary hydrocarbon group, tetrahydrofuranyl group, tetrahydropyranyl group, Or a (meth) acrylic acid ester to which an oxepanyl group is bonded directly or via a linking group. Examples of the tertiary hydrocarbon group in R ^a of the —COOR ^a group include t-butyl, t-amyl, 2-methyl-2-adamantyl, (1-methyl-1-adamantyl) ethyl group, and the like. . Examples of the substituent that the tertiary hydrocarbon group may have include, for example, a halogen atom, an alkyl group (eg, a C _1-4 alkyl group), a hydroxyl group optionally protected by a protecting group, oxo And a carboxyl group which may be protected with a protecting group. In addition, the tetrahydrofuranyl group in R ^a includes a 2-tetrahydrofuranyl group, the tetrahydropyranyl group includes a 2-tetrahydropyranyl group, and the oxepanyl group includes a 2-oxepanyl group. Examples of the linking group include an alkylene group (for example, a linear or branched alkyl group having 1 to 6 carbon atoms). The alicyclic hydrocarbon group may be directly bonded to an oxygen atom constituting the ester bond of (meth) acrylic acid ester, or may be bonded via a linking group such as an alkylene group. The alicyclic hydrocarbon group having 6 to 20 carbon atoms may be a monocyclic hydrocarbon group or a polycyclic (bridged cyclic) hydrocarbon group. A typical example of such a (meth) acrylic acid ester is a compound represented by the formula (1c).

  Another example of monomer a is (meth) acrylic acid hemiacetal ester. Specifically, the compound represented by the formula (1d) is exemplified.

  In addition, as monomer a, a (meth) acrylic acid ester containing a lactone ring in which an oxygen atom constituting an ester bond is bonded to the β-position of the lactone ring and has at least one hydrogen atom in the α-position of the lactone ring It is also possible to use. Monomers having a group that becomes alkali-soluble by the acid can be used alone or in combination of two or more.

The monomer a is preferably at least one compound selected from the formulas (1a) to (1d). In formulas (1a) to (1d), the alicyclic hydrocarbon ring having 6 to 20 carbon atoms in ring Z may be a single ring or a polycyclic ring such as a condensed ring or a bridged ring. 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, 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} ] Undecane ring, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane ring and the like. The alicyclic hydrocarbon ring includes an alkyl group such as a methyl group (eg, a C _1-4 alkyl group), a halogen atom such as a chlorine atom, a hydroxyl group optionally protected by a protecting group, an oxo group, a protected group It may have a substituent such as a carboxyl group which may be protected with a group. The ring Z is preferably a polycyclic alicyclic hydrocarbon ring (bridged hydrocarbon ring) such as an adamantane ring.

Formula (1a) ~ (1d) in the R, and the formula (1a), (1b), R 1 ~R 3, R 5, R carbon atoms, which may have a substituent at ⁶ in (1d) Examples of the alkyl group having 1 to 6 include linear or branched alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and hexyl groups. A haloalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or a methyl group. In the formula (1c), examples of the alkyl group represented by R ⁴ include linear or methyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl, and dodecyl groups. Examples include branched chain alkyl groups having about 1 to 20 carbon atoms. Examples of the hydroxyl group that may be protected with a protecting group for R ⁴ include a hydroxyl group and a substituted oxy group (for example, a C _1-4 alkoxy group such as a 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. Examples of the carboxyl group that may be protected with a protecting group include a —COOR ^b group. R ^b represents a hydrogen atom or an alkyl group, and examples of the alkyl group include linear or branched carbon such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and hexyl groups. Examples thereof include alkyl groups of 1 to 6. In R ^4, R ^a of -COOR ^a group is the same as above.

Examples of the organic group in R ⁷ include a group containing a hydrocarbon group and / or a heterocyclic group. The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded. Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, and octyl groups (C _{1- 8} alkyl groups); linear or branched alkenyl groups such as allyl groups (C _2-8 alkenyl groups, etc.); linear or branched alkynyl groups such as propynyl groups (C _2-8 alkynyl) Group, etc.). Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl groups (3 to 8 membered cycloalkyl groups); cycloalkenyl groups such as cyclopentenyl and cyclohexenyl groups (3 to 8 members). Cycloalkenyl groups and the like); bridged carbocyclic groups such as adamantyl and norbornyl groups (C _4-20 bridged carbocyclic groups and the like) and the like. Examples of the aromatic hydrocarbon group include C _6-14 aromatic hydrocarbon groups such as phenyl and naphthyl groups. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include benzyl and 2-phenylethyl groups. These hydrocarbon groups are protected with alkyl groups (C _1-4 alkyl groups, etc.), haloalkyl groups (C _1-4 haloalkyl groups, etc.), halogen atoms, hydroxyl groups that may be protected with protecting groups, and protecting groups. It may have a substituent such as a hydroxymethyl group which may be protected, a carboxyl group which may be protected with a protecting group, or an oxo group. As the protecting group, a protecting group conventionally used in the field of organic synthesis can be used.

  Examples of the heterocyclic group include heterocyclic groups containing at least one heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom.

Preferred organic groups include C _1-8 alkyl groups, organic groups containing a cyclic skeleton, and the like. The “ring” constituting the cyclic skeleton includes a monocyclic or polycyclic non-aromatic or aromatic carbocyclic or heterocyclic ring. Of these, monocyclic or polycyclic non-aromatic carbocycles and lactone rings (which may be condensed with non-aromatic carbocycles) are particularly preferable. Examples of the monocyclic non-aromatic carbocycle include a cycloalkane ring having about 3 to 15 members such as a cyclopentane ring and a cyclohexane ring.

Examples of the polycyclic non-aromatic carbocycle (bridged carbocycle) include, for example, an adamantane ring, norbornane ring, norbornene ring, bornane ring, isobornane ring, adamantane ring; norbornane ring, norbornene ring, bornane ring, isobornane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] ring containing norbornane ring or norbornene ring such as dodecane ring; perhydroindene ring, decalin ring (perhydronaphthalene ring), perhydrofluorene ring (tricyclo [7.4.0.0 ^3,8 ] Tridecane ring), a ring in which a polycyclic aromatic condensed ring such as perhydroanthracene ring is hydrogenated (preferably a fully hydrogenated ring); a tricyclo [4.2.2.1 ^2,5 ] undecane ring, etc. And a bridged carbocyclic ring (for example, a bridged carbocyclic ring having about 6 to 20 carbon atoms). Examples of the lactone ring include a γ-butyrolactone ring, 4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-5-one ring, and 4-oxatricyclo [4.2.1.0 ^{3. , 7} ] nonan-5-one ring, 4-oxatricyclo [5.2.1.0 ^2,6 ] decan-5-one ring, and the like.

The ring constituting the cyclic skeleton includes an alkyl group such as a methyl group (eg, a C _1-4 alkyl group), a haloalkyl group such as a trifluoromethyl group (eg, a C _1-4 haloalkyl group), a chlorine atom Or a halogen atom such as a fluorine atom, a hydroxyl group that may be protected with a protective group, a hydroxyalkyl group that may be protected with a protective group, a mercapto group that may be protected with a protective group, or a protective group. It may have a substituent such as a carboxyl group which may be protected, an amino group which may be protected with a protecting group, and a sulfonic acid group which may be protected with a protecting group. As the protecting group, a protecting group conventionally used in the field of organic synthesis can be used.

The ring constituting the cyclic skeleton may be directly bonded to an oxygen atom (oxygen atom adjacent to R ⁷ ) shown in the formula (1d) or may be bonded via a linking group. . Examples of the linking group include a linear or branched alkylene group such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene group; a carbonyl group; an oxygen atom (ether bond; —O—); an oxycarbonyl group ( An ester bond; —COO—); an aminocarbonyl group (amide bond; —CONH—); and a group in which a plurality of these are bonded.

At least two of R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring together with adjacent atoms. Examples of the ring include cycloalkane rings such as cyclopropane ring, cyclopentane ring and cyclohexane ring; oxygen-containing rings such as tetrahydrofuran ring, tetrahydropyran ring and oxepane ring; bridged ring and the like.

  In the compounds represented by the formulas (1a) to (1d), stereoisomers may exist, but they can be used alone or as a mixture of two or more.

Although the following compound is mentioned as a typical example of a compound represented by Formula (1a), It is not limited to these.
[1-1] 2- (Meth) acryloyloxy-2-methyladamantane (R = H or CH ₃ , R ¹ = CH ₃ , Z = adamantane ring)
[1-2] 1-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (R = H or CH ₃ , R ¹ = CH ₃ , adamantane ring having a hydroxyl group at the 1-position)
[1-3] 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (R = H or CH ₃ , R ¹ = CH ₃ , Z = 5 adamantane ring having a hydroxyl group at the 5-position)
[1-4] 1,3-Dihydroxy-2- (meth) acryloyloxy-2-methyladamantane (R = H or CH ₃ , R ¹ = CH ₃ , Z = 1- and adamantane having hydroxyl groups at the 3-position ring)
[1-5] 1,5-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane (R = H or CH ₃ , R ¹ = CH ₃ , Z = 1- and adamantane having hydroxyl groups at the 5-position ring)
[1-6] 1,3-dihydroxy-6- (meth) acryloyloxy-6-methyladamantane (R = H or CH ₃ , R ¹ = CH ₃ , Z = 1 adamantane having hydroxyl groups at the 1-position and 3-position ring)
[1-7] 2- (Meth) acryloyloxy-2-ethyladamantane (R = H or CH ₃ , R ¹ = CH ₂ CH ₃ , Z = adamantane ring)
[1-8] 1-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R = H or CH ₃ , R ¹ = CH ₂ CH ₃ , Z = 1 adamantane ring having a hydroxyl group at the 1-position)
[1-9] 5-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R = H or CH ₃ , R ¹ = CH ₂ CH ₃ , Z = 5 adamantane ring having a hydroxyl group at the 5-position)
[1-10] 1,3-Dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R = H or CH ₃ , R ¹ = CH ₂ CH ₃ , Z = 1 and hydroxyl groups at the 3-position Adamantane ring)
[1-11] 1,5-Dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R = H or CH ₃ , R ¹ = CH ₂ CH ₃ , Z = 1 and hydroxyl groups at the 5-position Has an adamantane ring)
[1-12] 1,3-dihydroxy-6- (meth) acryloyloxy-6-ethyladamantane (R = H or CH ₃ , R ¹ = CH ₂ CH ₃ , Z = 1 and hydroxyl groups at the 1 and 3 positions Adamantane ring)

  The compound represented by the above formula (1a) is, for example, a conventional esterification method using a corresponding cyclic alcohol and (meth) acrylic acid or a reactive derivative thereof using an acid catalyst, a transesterification catalyst, a base or the like. It can obtain by making it react according to.

Although the following compound is mentioned as a typical example of a compound represented by Formula (1b), It is not limited to these.
[1-13] 1- (1- (Meth) acryloyloxy-1-methylethyl) adamantane (R = H or CH ₃ , R ² = R ³ = CH ₃ , Z = adamantane ring)
[1-14] 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R = H or CH ₃ , R ² = R ³ = CH ₃ , Z = 1-hydroxyl group at position 1 Adamantane ring)
[1-15] 1- (1-ethyl-1- (meth) acryloyloxy propyl) adamantane (R = H or ^{_{CH 3, R 2 = R 3}} = CH 2 CH 3, Z = adamantane ring)
[1-16] 1-hydroxy-3- (1-ethyl-1- (meth) acryloyloxypropyl) adamantane (R = H or CH ₃ , R ² = R ³ = CH ₂ CH ₃ , Z = 1 position) Adamantane ring having a hydroxyl group)
[1-17] 1- (1- (Meth) acryloyloxy-1-methylpropyl) adamantane (R = H or CH ₃ , R ² = CH ₃ , R ³ = CH ₂ CH ₃ , Z = adamantane ring)
[1-18] 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylpropyl) adamantane (R = H or CH ₃ , R ² = CH ₃ , R ³ = CH ₂ CH ₃ , Z = Adamantane ring having a hydroxyl group at the 1-position)
[1-19] 1- (1- (Meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R = H or CH ₃ , R ² = CH ₃ , R ³ = CH (CH ₃ ) ₂ , Z = Adamantane ring)
[1-20] 1-hydroxy-3- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R = H or CH ₃ , R ² = CH ₃ , R ³ = CH (CH ₃ ) ₂ , Z = adamantane ring having a hydroxyl group at the 1-position)
[1-21] 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R = H or CH ₃ , R ² = R ³ = CH ₃ , Z = 1 position) An adamantane ring having a hydroxyl group at the 3-position)
[1-22] 1- (1-Ethyl-1- (meth) acryloyloxypropyl) -3,5-dihydroxyadamantane (R = H or CH ₃ , R ² = R ³ = CH ₂ CH ₃ , Z = 3 Adamantane ring with hydroxyl groups at the 5 and 5 positions)
[1-23] 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylpropyl) adamantane (R = H or CH ₃ , R ² = CH ₃ , R ³ = CH ₂ CH ₃ , Z = adamantane ring having hydroxyl groups at the 1- and 3-positions)
[1-24] 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R = H or CH ₃ , R ² = CH ₃ , R ³ = CH (CH ₃ ) ₂ , Z = 1 adamantane ring having hydroxyl groups at the 1- and 3-positions)

  The compound represented by the above formula (1b) includes, for example, a methanol derivative having an alicyclic group at the corresponding 1-position and (meth) acrylic acid or a reactive derivative thereof, an acid catalyst, a transesterification catalyst, a base, etc. It can obtain by making it react according to the conventional esterification method using.

Typical examples of the compound represented by the formula (1c) include, but are not limited to, the following compounds.
[1-25] 1-t-Butoxycarbonyl-3- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ⁴ = t-butoxycarbonyl group, n = 1, Z = adamantane ring)
[1-26] 1,3-bis (t-butoxycarbonyl) -5- (meth) acryloyloxyadamantane [R = H or CH ₃ , R ⁴ = t-butoxycarbonyl group, n = 2, Z = adamantane ring ]
[1-27] 1-t-Butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ⁴ = OH, t-butoxycarbonyl group, n = 2, Z = adamantane ring)
[1-28] 1- (2-Tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ⁴ = 2-tetrahydropyranyloxycarbonyl group, n = 1, Z = Adamantane ring)
[1-29] 1,3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane (R = H or CH ₃ , R ⁴ = 2-tetrahydropyranyloxycarbonyl group, n = 2, Z = adamantane ring)
[1-30] 1-hydroxy-3- (2-tetrahydropyranyloxy carbonyl) -5- (meth) acryloyloxy adamantane (R = H or ^{_{CH 3, R 4 = OH,}} 2- tetrahydropyranyloxy group , N = 2, Z = adamantane ring)

  The compound represented by the above formula (1c) is, for example, a conventional esterification method using a corresponding cyclic alcohol and (meth) acrylic acid or a reactive derivative thereof using an acid catalyst, a transesterification catalyst, a base, or the like. It can obtain by making it react according to.

Typical examples of the compound represented by the formula (1d) include the following compounds, but are not limited thereto.
[1-31] 1-adamantyloxy-1-ethyl (meth) acrylate (R = H or CH ₃ , R ⁵ = CH ₃ , R ⁶ = H, R ⁷ = 1-adamantyl group)
[1-32] 1-adamantylmethyloxy-1-ethyl (meth) acrylate (R = H or CH ₃ , R ⁵ = CH ₃ , R ⁶ = H, R ⁷ = 1-adamantylmethyl group)
[1-33] 2- (1-adamantyl) oxy-1-ethyl (meth) acrylate (R = H or ^{_{CH 3, R 5 = CH 3}} , R 6 = H, R 7 = 1- adamantyl ethyl group)
[1-34] 1-bornyloxy-1-ethyl (meth) acrylate (R = H or CH ₃ , R ⁵ = CH ₃ , R ⁶ = H, R ⁷ = 1-bornyl group)
[1-35] 2-norbornyloxy-1-ethyl (meth) acrylate (R = H or CH ₃ , R ⁵ = CH ₃ , R ⁶ = H, R ⁷ = 2-norbornyl group)
[1-36] 2-Tetrahydropyranyl (meth) acrylate (R = H or CH ₃ , R ⁵ and R ⁷ combine to form a ⁶ -membered ring together with the carbon atom and oxygen atom in the formula, R ⁶ = H )
[1-37] 2-tetrahydrofuranyl (meth) acrylate (R = H or CH ₃ , R ⁵ and R ⁷ combine to form a 5-membered ring with carbon and oxygen atoms in the formula, R ⁶ = H)

  The compound represented by the above formula (1d) can be obtained, for example, by reacting the corresponding vinyl ether compound and (meth) acrylic acid by a conventional method using an acid catalyst. For example, 1-adamantyloxy-1-ethyl (meth) acrylate can be produced by reacting 1-adamantyl-vinyl-ether with (meth) acrylic acid in the presence of an acid catalyst.

The monomer (monomer b) having a group containing a polar group-containing alicyclic skeleton includes (1) an alicyclic hydrocarbon group having 6 to 20 carbon atoms containing a lactone ring [lactone ring and simple group. (Meth) acrylic acid ester (monomer b1) in which a group having a structure in which a ring or a polycyclic (bridged) alicyclic carbocyclic ring is condensed] is bonded to an oxygen atom constituting an ester bond Is included. As a typical example of such a monomer b1, in the formula (2a), at least one of V ^{1 to} V ³ is —COO—, and (2b), (2c), (2d), The compound represented by (2e) is exemplified.

The monomer b includes (2) an alicyclic hydrocarbon group having 6 to 20 carbon atoms having a polar group such as a hydroxyl group, a carboxyl group, or an oxo group (particularly, a bridged cyclic hydrocarbon group). A (meth) acrylic acid ester (monomer b2) bonded to an oxygen atom constituting an ester bond is also included. As a typical example of such a monomer b2, at least one of V ^{1 to} V ^{3 in} the formula (2a) is —CO—, or at least one of R ^{8 to} R ¹⁰ is protected. Examples thereof include a hydroxyl group which may be protected with a group, a hydroxyalkyl group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group.

  When the monomer b is introduced into the resin by polymerization, the monomer b provides adhesion to a substrate such as a silicon wafer by a polar group, and imparts dry etching resistance by an alicyclic skeleton. Monomer b can be used alone or in combination of two or more. The monomer b is preferably at least one monomer selected from the formulas (2a) to (2e). Moreover, when the monomer b1 and the monomer b2 are used in combination as the monomer b, a resin having a good balance of properties such as substrate adhesion, dry etching resistance, and solubility in a resist solvent can be obtained. In addition, a great advantage is obtained that the polymer is excellent in homogeneous reactivity during polymerization (a polymer having high uniformity in molecular weight and molecular structure is produced).

R in the formulas (2a) to (2e) is the same as R in the above (1a) to (1d). In formulas (2a) to (2e), examples of the alkyl group represented by R ^{8 to} R ³³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl, dodecyl group, and the like. And a linear or branched alkyl group having 1 to 13 carbon atoms. Among these, a C1-C4 alkyl group is preferable. Examples of the hydroxyl group that may be protected with a protecting group include a hydroxyl group and a substituted oxy group (for example, a C _1-4 alkoxy group such as a methoxy, ethoxy, and propoxy group). 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. Examples of the carboxyl group that may be protected with a protecting group include a —COOR ^b group. R ^b is the same as described above.

  In the compounds represented by the formulas (2a) to (2e), stereoisomers may exist, but they can be used alone or as a mixture of two or more.

Although the following compound is mentioned as a typical example of a compound represented by Formula (2a), It is not limited to these.
[2-1] 1- (Meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-5-one (R = H or CH ₃ , R ⁸ = R ⁹ = R ¹⁰ = H, V ² = —CO—O— (the carbon atom side to which R ⁹ is bonded on the left side), V ¹ = V ³ = —CH ₂ —)
[2-2] 1- (Meth) acryloyloxy-4,7-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-5,8-dione (R = H or CH ₃ , R ^{8 = R 9 = R 10 = H} , V 1 = -CO-O- ( left bonded to the carbon atom side of the ^{R 8), V 2 = -CO} -O- ( left is bonded to R ⁹ Carbon atom side), V ³ = -CH _2- )
[2-3] 1- (Meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-5,7-dione (R = H or CH ₃ , R ^{8 = R 9 = R 10 = H} , V 1 = -O-CO- ( left bonded to that carbon atom side of the ^{R 8), V 2 = -CO} -O- ( left is bonded to R ⁹ Carbon atom side), V ³ = -CH _2- )
[2-4] 1- (Meth) acryloyloxy-5,7-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-4,8-dione (R = H or CH ₃ , R ^{8 = R 9 = R 10 = H} , V 1 = -CO-O- ( carbon atoms side the left is attached to ^{R 8), V 2 = -O} -CO- ( left is bonded to R ⁹ Carbon atom side), V ³ = -CH _2- )
[2-5] 1- (meth) acryloyloxy-3-hydroxyadamantane (R = H or ^{_{CH 3, R 8 = OH,}} R 9 = R 10 = H, V 1 = V 2 = V 3 = -CH 2 −)
[2-6] 1- (meth) acryloyloxy-3,5-dihydroxyadamantane (R = H or _{^{CH 3, R 8 = R 9}} = OH, R 10 = H, V 1 = V 2 = V 3 = - CH ₂ −)
[2-7] 1- (Meth) acryloyloxy-3,5,7-trihydroxyadamantane (R = H or CH ₃ , R ⁸ = R ⁹ = R ¹⁰ = OH, V ¹ = V ² = V ³ = —CH ₂ —)
[2-8] 1- (meth) acryloyloxy-3-hydroxy-5,7-dimethyl adamantane (R = H or ^{_{CH 3, R 8 = OH,}} R 9 = R 10 = CH 3, V 1 = V 2 = V ³ = -CH _2- )
[2-9] 1- (meth) acryloyloxy-3-carboxyadamantane (R = H or CH ₃ , R ⁸ = COOH, R ⁹ = R ¹⁰ = H, V ¹ = V ² = V ³ = -CH ₂ −)

  The compound represented by the above formula (2a) is obtained by subjecting a corresponding cyclic alcohol derivative and (meth) acrylic acid or a reactive derivative thereof to a conventional esterification method using an acid catalyst, a transesterification catalyst, a base or the like. It can be obtained by reacting.

Typical examples of the compound represented by the formula (2b) include the following compounds, but are not limited thereto.
[2-10] 5- (meth) acryloyloxy-3-oxatricyclo [4.2.1.0 ^{4, 8]} nonane-2-one (= 5- (meth) acryloyloxy-2,6-norbornane (Carbolactone) (R = H or CH ₃ , R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = R ¹⁵ = H)
[2-11] 5- (Meth) acryloyloxy-5-methyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (R = H or CH ₃ , R ¹¹ = CH ₃ , R ¹² = R ¹³ = R ¹⁴ = R ¹⁵ = H)
[2-12] 5- (meth) acryloyloxy-1-methyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (R = H or CH ₃ , R ¹² = CH ₃ , R ¹¹ = R ¹³ = R ¹⁴ = R ¹⁵ = H)
[2-13] 5- (Meth) acryloyloxy-9-methyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (R = H or CH ₃ , R ¹³ = CH ₃ , R ¹¹ = R ¹² = R ¹⁴ = R ¹⁵ = H)
[2-14] 5- (Meth) acryloyloxy-9-carboxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (R = H or CH ₃ , R ¹¹ = R ¹² = R ¹⁴ = R ¹⁵ = H, R ¹³ = COOH)
[2-15] 5- (meth) acryloyloxy-9-methoxycarbonyl-3-oxa-tricyclo [4.2.1.0 ^{4, 8]} nonan-2-(R = H or CH _3, R ^{11 = R 12 = R 14 = R} 15 = H, R 13 = methoxy group)
[2-16] 5- (Meth) acryloyloxy-9-ethoxycarbonyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (R = H or CH ₃ , R ^{11 = R 12 = R 14 = R} 15 = H, R 13 = ethoxycarbonyl group)
[2-17] 5- (meth) acryloyloxy-9-t-butoxycarbonyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (R = H or CH ₃ , R ¹¹ = R ¹² = R ¹⁴ = R ¹⁵ = H, R ¹³ = t-butoxycarbonyl group)

  The compound represented by the above formula (2b) is obtained by subjecting a corresponding cyclic alcohol derivative and (meth) acrylic acid or a reactive derivative thereof to a conventional esterification method using an acid catalyst, a transesterification catalyst, a base or the like. Can be obtained by reaction. In addition, the cyclic alcohol derivative used as a raw material in that case is, for example, a corresponding 5-norbornene-2-carboxylic acid derivative or an ester thereof peracid (peracetic acid, m-chloroperbenzoic acid, etc.) or peroxide ( It can be obtained by reaction (epoxidation and cyclization reaction) with hydrogen peroxide, hydrogen peroxide + metal compound such as tungsten oxide or tungstic acid).

Typical examples of the compound represented by the formula (2c) include the following compounds, but are not limited thereto.
[2-18] 8- (Meth) acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-5-one (R = H or CH ₃ )
[2-19] 9- (Meth) acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-5-one (R = H or CH ₃ )

  The compound represented by the above formula (2c) is obtained by subjecting a corresponding cyclic alcohol derivative and (meth) acrylic acid or a reactive derivative thereof to a conventional esterification method using an acid catalyst, a transesterification catalyst, a base or the like. It can be obtained by reacting.

Typical examples of the compound represented by the formula (2d) include the following compounds, but are not limited thereto.
[2-20] 4- (Meth) acryloyloxy-6-oxabicyclo [3.2.1] octane-7-one (R = H or CH ₃ , R ¹⁶ = R ¹⁷ = R ¹⁸ = R ¹⁹ = R ^{20 = R 21 = R 22 =} R 23 = R 24 = H)
[2-21] 4- (meth) acryloyloxy-4-methyl-6-oxabicyclo [3.2.1] octan-7-one (R = H or ^{_{CH 3, R 17 = R 18}} = R 19 = R ²⁰ = R ²¹ = R ²² = R ²³ = R ²⁴ = H, R ¹⁶ = CH ₃ )
[2-22] 4- (Meth) acryloyloxy-5-methyl-6-oxabicyclo [3.2.1] octane-7-one (R = H or CH ₃ , R ¹⁶ = R ¹⁸ = R ¹⁹ = R ²⁰ = R ²¹ = R ²² = R ²³ = R ²⁴ = H, R ¹⁷ = CH ₃ )
[2-23] 4- (Meth) acryloyloxy-4,5-dimethyl-6-oxabicyclo [3.2.1] octane-7-one (R = H or CH ₃ , R ¹⁸ = R ¹⁹ = R ^{20 = R 21 = R 22 =} R 23 = R 24 = H, R 16 = R 17 = CH 3)

Typical examples of the compound represented by the formula (2e) include the following compounds, but are not limited thereto.
[2-24] 6- (Meth) acryloyloxy-2-oxabicyclo [2.2.2] octane-3-one (R = H or CH ₃ , R ²⁵ = R ²⁶ = R ²⁷ = R ²⁸ = R ^{29 = R 30 = R 31 =} R 32 = R 33 = H)
[2-25] 6- (Meth) acryloyloxy-6-methyl-2-oxabicyclo [2.2.2] octane-3-one (R = H or CH ₃ , R ²⁵ = R ²⁷ = R ²⁸ = R ²⁹ = R ³⁰ = R ³¹ = R ³² = R ³³ = H, R ²⁶ = CH ₃ )
[2-26] 6- (meth) acryloyloxy-1-methyl-2-oxabicyclo [2.2.2] octan-3-one (R = H or ^{_{CH 3, R 26 = R 27}} = R 28 = R ²⁹ = R ³⁰ = R ³¹ = R ³² = R ³³ = H, R ²⁵ = CH ₃ )
[2-27] 6- (Meth) acryloyloxy-1,6-dimethyl-2-oxabicyclo [2.2.2] octane-3-one (R = H or CH ₃ , R ²⁷ = R ²⁸ = R ^{29 = R 30 = R 31 =} R 32 = R 33 = H, R 25 = R 26 = CH 3)

  The compounds represented by the above formulas (2d) and (2e) are prepared by combining a corresponding cyclic alcohol derivative with (meth) acrylic acid or a reactive derivative thereof using an acid catalyst, a transesterification catalyst, a base or the like. It can be obtained by reacting according to an esterification method.

  In the present invention, a simple substance other than the monomers a and b is used as long as it does not impair properties such as alkali solubility (acid detachability), substrate adhesion, dry etching resistance, and solubility in a resist solvent of the obtained resin. A monomer may be used as a comonomer. Such a monomer is not particularly limited as long as it is a monomer copolymerizable with monomer a and monomer b and does not impair the resist characteristics. Examples thereof include (meth) acrylic acid or a derivative thereof, maleic acid or a derivative thereof, fumaric acid or a derivative thereof, and cyclic olefins. Examples of the (meth) acrylic acid or derivatives thereof include α- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-α-methyl-γ-butyrolactone, α- (meth) acryloyloxy- and (meth) acrylic acid esters having a lactone ring (γ-butyrolactone ring, δ-valerolactone ring, etc.) such as γ, γ-dimethyl-γ-butyrolactone. The (meth) acrylic acid ester having this lactone ring can impart substrate adhesion to the polymer.

  The usage-amount of the monomer a is 5-90 mol% with respect to the monomer total amount, Preferably it is 10-80 mol%, More preferably, it is 20-70 mol%. When the amount of monomer a used is less than 5 mol%, when the obtained resin is used as a resin for photoresist, the solubility of the resist film during alkali development becomes insufficient, and the resolution is lowered. It becomes difficult to form a fine pattern with high accuracy. In addition, when the amount of the monomer a used exceeds 90 mol%, when the obtained resin is used as a resin for a photoresist, the substrate adhesion and dry etching resistance are reduced, and the pattern is peeled off by development. The problem of not being easy to occur.

  The usage-amount of the monomer b is 10-95 mol%, for example, Preferably it is 20-90 mol%, More preferably, it is 30-80 mol%. When the amount of the monomer b used is less than 10 mol%, the substrate adhesion and dry etching resistance are liable to decrease when the resin is used as a photoresist resin. Therefore, the solubility of the resist film during alkali development tends to be insufficient. When the monomer b1 and the monomer b2 are combined as the monomer b, the ratio of the two is not particularly limited, but generally the former / the latter (molar ratio) = 5/95 to 95/5, preferably 10 / It is about 90 to 90/10, more preferably about 30/70 to 70/30.

  Specifically, for example, (i) a monomer solution in which a monomer is previously dissolved in an organic solvent and a polymerization initiator solution in which a polymerization initiator is dissolved in an organic solvent are prepared, respectively. A method in which the monomer solution and the polymerization initiator solution are separately dropped from separate containers in an organic solvent maintained at a temperature; and (ii) a mixed solution in which the monomer and the polymerization initiator are dissolved in an organic solvent. (Iii) a monomer solution in which a monomer is previously dissolved in an organic solvent and a polymerization initiator solution in which the monomer is dissolved in an organic solvent. It is carried out by a method such as a method of dropping a polymerization initiator solution into the monomer solution maintained at a temperature. Of these, the method (i) or (ii) is preferred.

  Examples of the polymerization solvent include glycol solvents, ester solvents, ketone solvents, ether solvents, amide solvents, sulfoxide solvents, monohydric alcohol solvents, hydrocarbon solvents, and mixed solvents thereof. . Examples of glycol solvents include propylene glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene Ethylene glycol solvents such as glycol monobutyl ether and ethylene glycol monobutyl ether acetate are included. Examples of ester solvents include lactic acid ester solvents such as ethyl lactate; propionate solvents such as methyl 3-methoxypropionate; acetate solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate. . Ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and the like. The ether solvent includes diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like. The amide solvent includes N, N-dimethylformamide and the like. Examples of the sulfoxide solvent include dimethyl sulfoxide. The monohydric alcohol solvent includes methanol, ethanol, propanol, butanol and the like. Hydrocarbon solvents include toluene, xylene, hexane, cyclohexane and the like.

  Preferred polymerization solvents include glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ester solvents such as ethyl lactate, ketone solvents such as methyl isobutyl ketone and methyl amyl ketone, and mixed solvents thereof. . In particular, a solvent containing at least propylene glycol monomethyl ether acetate, such as a propylene glycol monomethyl ether acetate single solvent, a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether, a mixed solvent of propylene glycol monomethyl ether acetate and ethyl lactate, etc. preferable.

  The polymerization initiator is not particularly limited. For example, azo, peroxydicarbonate, peroxyester, diacyl peroxide, hydroperoxide, dialkyl peroxide, peroxyketal, ketone peroxide Any polymerization initiator such as can be used. Among these, azo polymerization initiators are particularly preferable. Examples of the azo polymerization initiator include azobisisobutyronitrile, dimethyl 2,2'-azobis (2-methylpropionate), diethyl 2,2'-azobis (2-methylpropionate), and dibutyl. Examples include 2,2'-azobis (2-methylpropionate) and 2,2'-azobisdimethylvaleronitrile.

  The amount of the polymerization initiator used may be an amount necessary for obtaining a polymer having a desired weight average molecular weight, for example, 0.001 to 1 mol, preferably 0 to 1 mol of the monomer mixture. About 0.01 to 0.1 mol.

  In the drop polymerization, the ratio of the amount of the solvent (or solution) charged in advance and the total amount of the dropped solution (monomer solution, polymerization initiator solution) takes into consideration productivity, economy, workability, operability, etc. However, it can be appropriately set within the range not impairing the quality of the resin. Generally, the former / the latter (weight ratio) = 5/95 to 90/10, preferably 10/90 to 70/30, more preferably 20 /. It is in the range of 80-60 / 40. The total amount of the polymerization solvent to be used (the amount of the solvent charged in advance or the amount of the solvent in the solution + the amount of the solvent in the solution to be dropped) takes into consideration the workability, operability, reaction efficiency, solubility of the polymer to be produced, etc. Although it can select suitably, generally it is 100-2000 weight part with respect to the total amount of a monomer of 100 weight part, Preferably it is 200-1000 weight part, More preferably, it is about 300-800 weight part.

  An important feature of the present invention is that the solution to be dripped into the polymerization system is directly introduced into the polymerization system without being transmitted to the wall of the polymerization vessel. By adopting such a method, it is possible to remarkably suppress the generation of insoluble matter (turbidity) that does not dissolve in the resist solvent, and it is possible to filter the solution in which the polymer is dissolved in the resist solvent in a short time. Therefore, the resist composition can be prepared efficiently. Further, since the molecular weight of the produced polymer and the uniformity of the monomer composition are excellent, a desired pattern can be obtained with high precision in semiconductor manufacturing. The reason why the above-described effects are achieved is not necessarily clear, but when a solution to be dripped into the polymerization system is transmitted to the polymerization vessel wall and supplied to the polymerization system, a general polymerization container (especially industrial In the polymerization vessel used in production), since the solution supply line is joined to the opening above the polymerization vessel with a flange or the like, the supply solution usually reaches the reaction solution through the wall of the polymerization solution. The monomer stays hard to diffuse near the vessel wall, and the monomer concentration becomes higher compared to other places. As a result, the molecular weight of the polymer and the uniformity of the monomer composition are reduced. When the solution to be introduced is introduced directly into the polymerization system without being transmitted to the vessel wall of the polymerization vessel, it is assumed that the monomer concentration does not increase locally and the polymerization reaction proceeds uniformly throughout the system. The In addition, when there is much content of the polymer exceeding molecular weight 40000, it is easy to produce an insoluble part (turbidity) when making it melt | dissolve in a resist solvent.

  In the production method of the present invention, in the case of (i), at least one (preferably at least the monomer solution) of the monomer solution and the polymerization initiator solution is directly dropped into the polymerization system. In the case of (ii), a mixed solution in which a monomer and a polymerization initiator are dissolved in an organic solvent is directly added dropwise to the polymerization system. In the case of (iii), the polymerization initiator solution is directly dropped into the polymerization system.

  As a means for introducing the solution to be dripped into the polymerization system directly into the polymerization system without being transmitted to the vessel wall of the polymerization vessel, for example, toward the polymerization system liquid level at the tip of the supply line of the solution to be dripped into the polymerization system For example, an extended nozzle is provided, and the solution to be dripped into the polymerization system is directly introduced into the polymerization system through the nozzle without being transmitted to the wall of the polymerization vessel. The tip of this nozzle may be inserted into the polymerization solution (reaction liquid), but it should be placed so that it is located above the liquid level of the polymerization solution (particularly the liquid level at the end of dropping). More preferred.

  The total dropping time of the monomer solution or the polymerization initiator solution varies depending on the polymerization temperature and the kind of the monomer, but is generally 1 to 24 hours, preferably 2 to 12 hours, more preferably about 3 to 8 hours. It is. The polymerization temperature (reaction liquid temperature at the time of dropping) is usually from 50 to 150 ° C, preferably from 60 to 130 ° C. When the polymerization temperature is less than 50 ° C., the polymerization time becomes long and it is not economical. When the polymerization temperature exceeds 130 ° C., the chain transfer reaction becomes remarkable, leading to a decrease in molecular weight.

  After completion of dropping of the monomer solution and the polymerization initiator solution, an appropriate time (for example, 0.1 to 10 hours, preferably 1 to 6 hours, more preferably about 1 to 4 hours), an appropriate temperature (for example, 60 to Aging at 130 ° C.).

  Polymerization produces a photoresist polymer compound containing at least a repeating unit corresponding to the monomer a and a repeating unit corresponding to the monomer b. The weight average molecular weight (Mw) of the produced polymer is, for example, in the range of 2000 to 20000, preferably 4000 to 17000, and more preferably 6000 to 15000. The molecular weight distribution (Mw / Mn) is, for example, about 1.1 to 3.5, preferably about 1.5 to 3.0. Mn represents the number average molecular weight of the polymer. Both Mw and Mn are values in terms of polystyrene. The weight average molecular weight and molecular weight distribution of the polymer can be determined by the GPC method.

  The repeating units corresponding to the monomers represented by the formulas (1a) to (1d) are represented by the following formulas (Ia) to (Id), respectively. Each code | symbol in a type | formula is the same as that of said Formula (1a)-(1d). The repeating units corresponding to the monomers represented by the formulas (2a) to (2e) are represented by the following formulas (IIa) to (IIe), respectively. Each symbol in the formula is the same as that in the formulas (2a) to (2e).

  In the production method of the present invention, when producing a photoresist polymer compound on an industrial production scale, for example, the polymer compound for photoresist is produced by a batch polymerization reaction in which the amount of the polymer to be produced is 10 kg or more (particularly 20 kg or more). It is particularly useful when manufacturing.

  The polymer obtained by polymerization can be isolated by precipitation or reprecipitation. For example, the polymerization solution (polymer dope) is added to a solvent (precipitation solvent) to precipitate the polymer, or the polymer is dissolved again in a suitable solvent, and this solution is added to the solvent (reprecipitation solvent). The desired polymer can be obtained by reprecipitation. The precipitation or reprecipitation solvent may be either an organic solvent or water, or 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; aromatics such as benzene, toluene, and xylene. Aromatic hydrocarbons), halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.) , Nitrile (acetonitrile, benzonitrile, etc.), ether (chain ether such as diethyl ether, diisopropyl ether, dimethoxyethane; cyclic ether such as tetrahydrofuran, dioxane), ketone (acetone, methyl ethyl ketone) Diisobutyl ketone, etc.), ester (ethyl acetate, butyl acetate, etc.), carbonate (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohol (methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acid (acetic acid, etc.) Etc.), and mixed solvents containing these solvents.

  Among these, as the organic solvent used as the precipitation or reprecipitation solvent, a solvent containing at least a hydrocarbon (particularly, an aliphatic hydrocarbon such as hexane or heptane) is preferable. In such a solvent containing at least hydrocarbon, the ratio of hydrocarbon (for example, aliphatic hydrocarbon such as hexane and heptane) and other solvent (for example, esters such as ethyl acetate) is, for example, the former / the latter (Volume ratio; 25 ° C.) = 10/90 to 99/1, preferably the former / the latter (volume ratio; 25 ° C.) = 30/70 to 98/2, more preferably the former / the latter (volume ratio; 25 ° C.) = About 50/50 to 97/3.

  The polymer obtained by precipitation or reprecipitation is subjected to repulping or rinsing as necessary. A rinse treatment may be applied after the repulping treatment. By repulping the polymer produced by polymerization with a solvent or rinsing, residual monomers and low molecular weight oligomers adhering to the polymer can be efficiently removed. In addition, because the high-boiling solvent having affinity for the polymer is removed, the surface of the polymer particles can be hardened in the subsequent drying step or the like, and fusion between the polymer particles can be prevented. Therefore, the solubility of the polymer in the resist solvent is remarkably improved, and the resin composition for photoresist can be easily and efficiently prepared.

  As the solvent used for the repulping treatment (solvent for repulping) and the solvent used for the rinsing treatment (solvent for rinsing), a poor solvent for the polymer used for precipitation or reprecipitation is preferred. Of these, hydrocarbon solvents are particularly preferred. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene. You may use these in mixture of 2 or more types. Among these, aliphatic hydrocarbons, particularly hexane or heptane, or a mixed solvent containing hexane or heptane is preferable. In order to remove metal components and the like, water (for example, ultrapure water) may be used as a rinsing solvent.

  The amount of the repulping solvent used is, for example, about 1 to 200 times by weight, preferably about 5 to 100 times by weight with respect to the polymer. On the other hand, the usage-amount of a rinse solvent is 1-100 weight times with respect to a polymer, Preferably it is about 2-20 weight times. Although the temperature at the time of performing a repulping process and a rinse process changes with kinds etc. of the solvent to be used, generally it is 0-100 degreeC, Preferably it is about 10-60 degreeC. The repulping process and the rinsing process are performed in a suitable container. You may perform a repulping process and a rinse process in multiple times, respectively. The treated liquid (repulp liquid, rinse liquid) is removed by decantation, filtration or the like.

  The wet polymer obtained through precipitation or reprecipitation, or further repulping and rinsing as necessary is subjected to a drying treatment. A drying temperature is 20-120 degreeC, for example, Preferably it is about 40-100 degreeC. Drying is preferably performed under reduced pressure, for example, 200 mmHg (26.6 kPa) or less, particularly 100 mmHg (13.3 kPa) or less.

  The photoresist composition of the present invention contains at least a photoresist polymer compound produced by the above method and a photoacid generator. The photoresist composition may be prepared by dissolving the polymer compound for photoresist isolated by precipitation or reprecipitation as described above in a resist solvent together with a photoacid generator, or obtained by polymerization. The polymer dope thus obtained may be prepared by performing operations such as filtration, dilution, concentration, solvent substitution (substitution with a resist solvent) and the like, if necessary, and adding a photoacid generator. In many cases, a filtration operation is performed at an appropriate stage of the preparation process of the photoresist composition in order to remove a minute amount of the applied component. For example, a photoresist polymer compound is dissolved in a resist solvent and then filtered, and a photoacid generator and, if necessary, additives are added to the filtrate to prepare a photoresist composition. When the polymer compound for photoresist produced by the method of the present invention is used, the insoluble content is extremely small, so that this filtration operation can be carried out simply and efficiently.

  Examples of the photoacid generator include conventional or known compounds that efficiently generate acid upon exposure, such as diazonium salts, iodonium salts (for example, diphenyliodohexafluorophosphate), sulfonium salts (for example, triphenylsulfonium hexafluoroantimony). Nates, triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonate esters [eg 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, 1,2,3-tri Sulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl) -1-hydroxy-1-benzo Rumetan etc.], oxathiazole derivatives, s- triazine derivatives, disulfone derivatives (diphenyl sulfone) imide compound, an oxime sulfonate, a diazonaphthoquinone, and benzoin tosylate. These photoacid generators can be used alone or in combination of two or more.

  The amount of the photoacid generator used can be appropriately selected according to the strength of the acid generated by light irradiation or the ratio of each repeating unit in the polymer (polymer compound for photoresist), for example, with respect to 100 parts by weight of the polymer It can be selected from the range of 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably about 2 to 20 parts by weight.

  Examples of the resist solvent include glycol solvents, ester solvents, ketone solvents, and mixed solvents exemplified as the polymerization solvent. Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl isobutyl ketone, methyl amyl ketone, and a mixed solution thereof are preferable, and in particular, propylene glycol monomethyl ether acetate alone solvent, propylene glycol monomethyl ether acetate and A solvent containing at least propylene glycol monomethyl ether acetate such as a mixed solvent of propylene glycol monomethyl ether and a mixed solvent of propylene glycol monomethyl ether acetate and ethyl lactate is preferably used.

  The polymer concentration in the photoresist composition is, for example, about 10 to 40% by weight. The photoresist composition may contain an alkali-soluble component such as an alkali-soluble resin (for example, a novolac resin, a phenol resin, an imide resin, a carboxyl group-containing resin), a colorant (for example, a dye), and the like.

  The photoresist composition thus obtained is applied onto a substrate or a substrate, dried, and then exposed to light on a coating film (resist film) through a predetermined mask (or further subjected to post-exposure baking). By forming the latent image pattern and then developing it, a fine pattern can be formed with high accuracy.

  Examples of the base material or the substrate include a silicon wafer, metal, plastic, glass, and ceramic. The photoresist composition can be applied using a conventional application means such as a spin coater, a dip coater, or a roller coater. The thickness of the coating film is, for example, about 0.1 to 20 μm, preferably about 0.3 to 2 μm.

For exposure, light of various wavelengths such as ultraviolet rays and X-rays can be used. For semiconductor resists, g-rays, i-rays, and excimer lasers (eg, XeCl, KrF, KrCl, ArF, ArCl, etc.) are usually used. Etc. are used. The exposure energy is, for example, about 1 to 1000 mJ / cm ² , preferably about 10 to 500 mJ / cm ² .

  An acid is generated from the photoacid generator by light irradiation, and this acid, for example, a carboxyl group of a repeating unit (a repeating unit having an acid-eliminable group) that becomes alkali-soluble by the action of an acid of a polymer compound for photoresist, etc. This protecting group (leaving group) is rapidly eliminated, and a carboxyl group and the like that contribute to solubilization are generated. Therefore, a predetermined pattern can be accurately formed by development with water or an alkali developer.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

撹拌機、温度計、還流冷却管、モノマー溶液滴下ノズル（ノズルは、モノマー溶液が反応器の器壁を伝わらずに直接反応液に入るように設置されている）、及び窒素導入管を備えたセパラブルフラスコに、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）を３３００ｇ導入し、７５℃に昇温後、１−ヒドロキシ−３−メタクリロイルオキシアダマンタン（ＨＭＡ）５００ｇ、５−メタクリロイルオキシ−２，６−ノルボルナンカルボラクトン（ＭＮＢＬ）５００ｇ、２−メタクリロイルオキシ−２−メチルアダマンタン（２ＭＭＡ）５００ｇと、ジメチル−２，２´−アゾビス（２−メチルプロピオネート）（重合開始剤；和光純薬工業製、商品名「Ｖ−６０１」）９３ｇと、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）４１００ｇの混合溶液を６時間かけて、フラスコ器壁に付着しないように、直接反応液まで達するように、モノマー溶液滴下ノズルから滴下した。滴下後、２時間同温度で熟成した。得られた反応溶液（ポリマードープ）（３５℃）を６５６００ｇのヘプタンと２１９００ｇの酢酸エチルの混合液（３５℃）中に滴下し、滴下終了後、６０分間撹拌し、９０分間静置することにより沈殿精製を行った。上澄み液６４０００ｇを抜き取り、その残渣にヘプタン６４０００ｇを加え、３５℃でリパルプ操作を実施した。リパルプ操作は、ヘプタン仕込み後、３０分間撹拌し、９０分間静置し、上澄み液を抜き取ることにより行った。このリパルプ操作を併せて２回実施した。上澄み液を抜き取った後の残渣を遠心分離機に移し、６００Ｇの遠心力により脱液を行い、湿ポリマーを得た。この湿ポリマーに６５００ｇのヘプタンを加え、６００Ｇの遠心力によりリンスを行い、リンス液を除去した。次いで、１００００ｇの超純水（Ｎａ分０．９重量ｐｐｂ）を加えて、６００Ｇの遠心力によりリンスを行い、リンス液を除去した。
得られた湿ポリマーを取り出し、棚段乾燥機に入れ、２０ｍｍＨｇ（２．６６ｋＰａ）、７０℃で３０時間乾燥することにより、フォトレジスト用高分子化合物（ＡｒＦレジスト樹脂）１０５０ｇが得られた。このフォトレジスト用高分子化合物をＰＧＭＥＡ４２００ｇに１時間溶解させてフォトレジスト用ポリマー溶液を得た。得られたフォトレジスト用ポリマー溶液には未溶解分がなく、清澄な溶液であった。その溶液を孔径０．０２μｍのフィルターに通したところ、濾過開始から濾過終了まで、１００ｇ毎の濾過速度は変わらず、濾過性は非常に良好であった。
なお、得られたフォトレジスト用高分子化合物の重量平均分子量は８２５０、分子量分布は１．７４であった。 Example 1
Preparation of polymer compound for photoresist with the following structure

A stirrer, thermometer, reflux condenser, monomer solution dropping nozzle (nozzle is installed so that the monomer solution enters the reaction solution directly without going through the reactor wall), and a nitrogen introduction tube Into a separable flask, 3300 g of propylene glycol monomethyl ether acetate (PGMEA) was introduced. After raising the temperature to 75 ° C., 500 g of 1-hydroxy-3-methacryloyloxyadamantane (HMA), 5-methacryloyloxy-2,6-norbornanecarbox Lactone (MNBL) 500 g, 2-methacryloyloxy-2-methyladamantane (2MMA) 500 g, dimethyl-2,2′-azobis (2-methylpropionate) (polymerization initiator; manufactured by Wako Pure Chemical Industries, Ltd., trade name) “V-601”) 93 g and propylene glycol monomethyl ether Over Tate a (PGMEA) mixed solution of 4100 g 6 hours, so as not to adhere to the flask unit wall, so as to reach directly the reaction mixture was added dropwise a monomer solution dropping nozzle. After dropping, the mixture was aged at the same temperature for 2 hours. The obtained reaction solution (polymer dope) (35 ° C.) was dropped into a mixed solution (35 ° C.) of 65600 g of heptane and 21900 g of ethyl acetate, stirred for 60 minutes, and allowed to stand for 90 minutes. Precipitation purification was performed. 64,000 g of the supernatant was extracted, 64000 g of heptane was added to the residue, and repulping operation was performed at 35 ° C. The repulping operation was carried out by stirring for 30 minutes after leaving heptane, allowing to stand for 90 minutes, and removing the supernatant. This repulping operation was performed twice. After removing the supernatant, the residue was transferred to a centrifuge and drained by a 600 G centrifugal force to obtain a wet polymer. 6500 g of heptane was added to this wet polymer, and rinsing was performed with a centrifugal force of 600 G to remove the rinse solution. Next, 10000 g of ultrapure water (Na content: 0.9 wt ppb) was added, and rinsing was performed with a centrifugal force of 600 G to remove the rinse solution.
The obtained wet polymer was taken out, put into a shelf dryer, and dried at 20 mmHg (2.66 kPa) and 70 ° C. for 30 hours, to obtain 1050 g of a polymer compound for photoresist (ArF resist resin). This polymer compound for photoresist was dissolved in 4200 g of PGMEA for 1 hour to obtain a polymer solution for photoresist. The obtained photoresist polymer solution had no undissolved content and was a clear solution. When the solution was passed through a filter having a pore size of 0.02 μm, the filtration rate did not change every 100 g from the start of filtration to the end of filtration, and the filterability was very good.
The resulting polymer compound for photoresist had a weight average molecular weight of 8,250 and a molecular weight distribution of 1.74.

Comparative Example 1
Preparation of polymer compound for photoresist having same structure as Example 1 Propylene glycol monomethyl ether acetate (PGMEA) was placed in a separable flask equipped with a stirrer, thermometer, reflux condenser, monomer solution dropping port, and nitrogen inlet tube. 3300 g was introduced, the temperature was raised to 75 ° C., 1-hydroxy-3-methacryloyloxyadamantane (HMA) 500 g, 5-methacryloyloxy-2,6-norbornanecarbolactone (MNBL) 500 g, 2-methacryloyloxy-2- 500 g of methyl adamantane (2MMA), 93 g of dimethyl-2,2′-azobis (2-methylpropionate) (polymerization initiator; Wako Pure Chemical Industries, trade name “V-601”), and propylene glycol monomethyl ether Mixing 4100 g of acetate (PGMEA) It was added dropwise a monomer solution dropping inlet over the liquid 6 hours. At that time, a monomer solution entering the reaction solution directly from the monomer solution dropping port and a solution entering the reaction solution through the wall of the flask were observed. After dropping, the mixture was aged for 2 hours and purified in the same manner as in Example 1.
The obtained wet polymer was taken out, put into a shelf dryer, and dried at 20 mmHg (2.66 kPa) and 70 ° C. for 30 hours, to obtain 1050 g of a polymer compound for photoresist (ArF resist resin). This polymer compound for photoresist was dissolved in 4200 g of PGMEA for 1 hour to obtain a polymer solution for photoresist. The resulting polymer solution for photoresist was a solution with some undissolved content. When the solution was passed through a filter having a pore size of 0.02 μm, the filtration rate per 100 g was extremely slow from the start of filtration to the end of filtration, the filterability was very poor, and the filtration operation required a lot of time and labor. did.

Claims (6)

  Polymer compound for photoresist obtained by polymerizing monomer mixture containing at least monomer having alkali-soluble group by acid and monomer having polar group-containing alicyclic skeleton by dropping polymerization method A method for producing a polymer compound for photoresist, wherein a solution to be dripped into the polymerization system is introduced directly into the polymerization system without being transmitted to the wall of the polymerization vessel.   A nozzle extending toward the polymerization system liquid surface is provided at the tip of the supply line of the solution to be dripped into the polymerization system, and the solution to be dripped into the polymerization system is directly passed through the nozzle without being transmitted to the vessel wall of the polymerization vessel. The manufacturing method of the high molecular compound for photoresists of Claim 1 introduce | transduced in. Monomers having groups that become alkali-soluble by acid are represented by the following formulas (1a) to (1d):

(In the formula, ring Z represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent. R represents a hydrogen atom or an optionally substituted substituent having 1 to 6 carbon atoms. R ^{1 to} R ³ are the same or different and each represents an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ⁴ is a substituent bonded to ring Z. And may be the same or different and may be protected with an oxo group, an alkyl group, a hydroxyl group that may be protected with a protecting group, a hydroxyalkyl group that may be protected with a protecting group, or a protecting group. Represents a carboxyl group, provided that at least one of n R ⁴ groups represents ^a —COOR ^a group, wherein R ^a represents ^a tertiary hydrocarbon group which may have ^a substituent, a tetrahydrofuranyl group, A tetrahydropyranyl group or an oxepanyl group, where n is an integer of 1 to 3. R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R ⁷ represents a hydrogen atom or an organic group. ⁵ , R ⁶ , or R ⁷ may be bonded to each other to form a ring with adjacent atoms.
The method for producing a photoresist polymer compound according to claim 1, wherein the compound is at least one compound selected from the group consisting of: Monomers having a group containing a polar group-containing alicyclic skeleton are represented by the following formulas (2a) to (2e)

(In the formula, R represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. R ^{8 to} R ¹⁰ are the same or different and each represents a hydrogen atom, an alkyl group, or a protecting group. A hydroxyl group which may be protected, a hydroxyalkyl group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group, V ^{1 to} V ³ are the same or different, and CH _2- , -CO- or -COO-, provided that (i) at least one of V ^{1 to} V ³ is -CO- or -COO-, or (ii) R ^{8 to} R ¹⁰ at least one of the, optionally protected hydroxyl group, a protected or unprotected hydroxyalkyl group with a protecting group, or be protected by a protecting group is also a carboxyl group which .R ¹¹ ~ R ¹⁵ is the same or different and is a hydrogen atom , An alkyl group, a hydroxyl group that may be protected with a protecting group, a hydroxyalkyl group that may be protected with a protecting group, and a carboxyl group that may be protected with a protecting group, R ^{16 to} R ²⁴ represent It is the same or different and represents a hydrogen atom, an alkyl group, a hydroxyl group that may be protected with a protecting group, a hydroxyalkyl group that may be protected with a protecting group, or a carboxyl group that may be protected with a protecting group. R ^{25 to} R ³³ are the same or different and are protected by a hydrogen atom, an alkyl group, a hydroxyl group which may be protected with a protecting group, a hydroxyalkyl group which may be protected with a protecting group, or a protecting group. (P represents 0 or 1, q represents 1 or 2)
The method for producing a photoresist polymer compound according to claim 1, wherein the compound is at least one compound selected from the group consisting of:   The photoresist composition containing the high molecular compound for photoresists manufactured by the method of any one of Claims 1-4, and a photo-acid generator.   A method for producing a semiconductor comprising a step of applying a photoresist composition according to claim 5 to a substrate or a base material to form a resist coating film.