JP2007154080A - Method for producing resin for photoresist - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin for photoresist, extremely easily soluble in a solvent for resist and having extremely low metal content. <P>SOLUTION: A resin for photoresist at least containing a repeating unit derived from a monomer (a) containing a group to become alkali-soluble by dissociating a part of the group with an acid and a repeating unit derived from a monomer (b) containing an alicyclic skeleton having a polar group is produced by polymerizing a monomer mixture at least containing the monomer (a) and the monomer (b) by drop polymerization using a production apparatus having a liquid-contacting part made of glass and dropping the monomer solution stored in a light-shielded state into a solvent having controlled temperature. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a photoresist resin useful for preparing a photoresist resin composition for use in semiconductor microfabrication and the like, and a photoresist resin composition using a photoresist resin obtained by the production method. The present invention relates to a manufacturing method and a semiconductor manufacturing method using a photoresist resin composition obtained by the manufacturing method.

  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. However, when the polymer thus obtained is dissolved in the resist solvent, most of the polymer is dissolved, but a part of the polymer is insoluble (turbidity). Since this insoluble matter causes trouble in the semiconductor manufacturing process, it is necessary to remove it by filtration. However, since the particles are fine, filtration requires a lot of time and labor.

  On the other hand, a 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 easily controlled. In Japanese Patent Application Laid-Open No. 2004-269855 (Patent Document 3), in this dropping polymerization method, when the monomer solution and the initiator solution are divided and dropped separately, compared with the case where the monomer solution and the initiator solution are mixed and dropped. It is described that generation of high molecular weight components of the produced polymer can be suppressed, and as a result, the solubility of the polymer in the solvent can be improved. However, even in this method, it is not always possible to reliably suppress the occurrence of turbidity when dissolved in a resist solvent.

  Moreover, in order for metal, especially iron content, to deteriorate the electrical characteristics of the manufactured semiconductor, it is desired that the metal content in the photoresist resin composition be as low as possible. Although it is possible to reduce the metal content by the metal adsorption treatment, if the metal content in the solution before the treatment is large, the adsorption capacity is immediately reduced and the adsorbent needs to be renewed. Since the dismantling of the equipment increases the possibility of external contaminants, a photoresist resin with a low metal content is desired even without an adsorption treatment.

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

  An object of the present invention is to produce a photoresist resin that is extremely soluble in a resist solvent and has a very low metal content, and a photoresist resin composition that uses the photoresist resin obtained by the production method. It is in providing the method and the manufacturing method of the semiconductor using this resin composition.

  As a result of intensive studies to achieve the above object, the inventors of the present invention can obtain a polymer having a relatively narrow molecular weight distribution by synthesizing and purifying a photoresist resin for ArF by a dropping polymerization method. Even if a polymer is dissolved in a resist solvent, it causes turbidity (insoluble matter), has a high metal content, and uses a manufacturing facility in which the wetted part is glass during dripping polymerization, and also shields it from light. When the monomer solution stored in this state is dropped and polymerized, a polymer with extremely low metal content is obtained without causing turbidity (insoluble content) when dissolved in a resist solvent. I found out. The present invention has been completed based on these findings.

  That is, the present invention provides a monomer mixture containing at least a monomer a containing a group that is partially eliminated by an acid and becomes alkali-soluble, and a monomer b containing an alicyclic skeleton having a polar group. Is a method of producing a photoresist resin containing at least a repeating unit corresponding to monomer a and a repeating unit corresponding to monomer b, wherein the wetted part is glass. Provided is a method for producing a resin for photoresist, which comprises using equipment and polymerizing a monomer solution stored in a light-shielded state by dropping it into a temperature-controlled solvent.

  In this production method, it is more preferable to drop the monomer solution stored at a temperature of 20 ° C. or less into the reaction vessel.

  In addition, this production method also comprises the steps of precipitating a photoresist resin obtained by polymerization in a poor solvent, separating the precipitated photoresist resin as wet crystals, and removing the wet crystals from at least one type of coating film forming solvent. A step of re-dissolving in the solvent to be contained and distilling the obtained re-dissolved solution to distill off low-boiling impurities contained in the wet crystal may be included.

（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。 As the monomer a, for example, 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。 As the monomer b, for example, 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 resin composition obtained by mixing a photoresist resin obtained by the above-described method for producing a photoresist resin with a photoacid generator and a resist solvent. A method for producing a resin composition is provided.

  The present invention further includes a method for producing a semiconductor comprising a step of applying a photoresist resin composition obtained by the above-described method for producing a photoresist resin composition to a substrate or a substrate to form a resist coating film. provide.

  According to the production method of the present invention, the formation of a high molecular weight polymer is remarkably suppressed, the solubility in a resist solvent is extremely good, and a resin with a very low metal content such as iron can be easily obtained. . For this reason, the complicated filtration process of a solvent insoluble part and a metal content removal process can be omitted or simplified, and the resin composition for photoresists can be prepared efficiently. Further, by using the photoresist resin composition thus obtained, it is possible to avoid various troubles and problems caused by insoluble components and metal components in the semiconductor manufacturing process.

  In the present invention, the monomer a containing a group that is partly eliminated by an acid and becomes alkali-soluble is caused by the action of an acid generated from a photoacid generator upon exposure to a resin when introduced into a resin by polymerization. The compound is not particularly limited as long as it is a compound that is partially eliminated and is soluble in an alkali developer (a monomer having an acid-eliminable group). For example, an alicyclic hydrocarbon group having 6 to 20 carbon atoms may be used. Examples thereof include (meth) acrylic acid esters that contain a group that can be removed by the action of an acid. “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. As a typical example of such a (meth) acrylic acid ester, a unit represented by the formula (1c) is exemplified.

  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. The monomer a containing a group that is partly eliminated by the acid and becomes alkali-soluble may be one kind or a combination of two or more kinds.

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 b containing an alicyclic skeleton having a polar group includes (1) a C6-C20 alicyclic hydrocarbon group containing a lactone ring [lactone ring and monocyclic or polycyclic (bridged) (Meth) acrylic acid ester (monomer b1) in which a group having a structure in which an alicyclic carbocyclic ring is condensed is bonded to an oxygen atom constituting an ester bond. 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 (1c). 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.

  An important feature of the present invention is that a monomer comprising at least a monomer a containing a group that is partly eliminated by acid and becomes alkali-soluble, and a monomer b containing an alicyclic skeleton having a polar group When the body mixture is polymerized by drop polymerization, a manufacturing facility in which the liquid contact part is glass is used, and the monomer solution stored in a light-shielded state is dropped into a temperature-controlled solvent for polymerization. is there. In this way, when using a manufacturing facility in which the wetted part is glass and dripping and polymerizing the monomer solution stored in a light-shielded state, it is possible to prevent the elution of the metal component and the high molecular weight polymer. It is possible to obtain a resin in which the formation is remarkably suppressed, the metal content such as iron is extremely small, and turbidity (insoluble matter) does not occur when dissolved in a resist solvent. In addition, since the monomer solution is dropped into a temperature-controlled solvent for polymerization, a resin having a uniform molecular weight and composition can be obtained. Therefore, a complicated solvent-insoluble filtration step and a metal removal step can be omitted or simplified, and a photoresist resin composition can be efficiently prepared. In addition, by using the photoresist resin composition, it is possible to avoid various troubles and troubles due to insoluble components and metal components in the semiconductor manufacturing process, and to form a uniform coating film, An extremely fine pattern can be formed with high accuracy.

  Examples of the production equipment in which the wetted part is made of glass include a reaction apparatus, a purification apparatus such as a distillation apparatus, and piping. Examples of the reaction apparatus include a monomer solution storage container (such as a dropping funnel), a reaction container, a stirrer (stirring blade), a heating medium coil, and the like. The purification apparatus includes, for example, a distillation can, a stirrer (stirring blade), a heating medium coil, and the like. In addition, even if the material is other than glass such as stainless steel, the liquid contact portion only needs to be glass-lined. By making the wetted part glass, it is possible to prevent metal components such as iron from being mixed into the generated resin. There is no particular limitation on the light shielding method. Examples of the glass container include a metal foil such as an aluminum foil, a black bag, and a method of covering the container with a light shielding material. In addition, although it is not necessary for all of the wetted parts of the manufacturing equipment to be glass, it is preferable that the glass part occupies as much as possible. In particular, at least one of the monomer solution storage container, the reaction container, and a distillation apparatus (particularly a distillation can) used for distillation of the resin redissolved liquid described later, the liquid contact portion is made of glass in at least two apparatuses. Is preferable.

  The monomer solution for shielding light may be a solution containing at least a monomer, and may contain a polymerization solvent or a polymerization initiator. In the case where the monomer solution is shielded from light, even if the monomer solution contains a polymerization initiator, the formation of a high molecular weight polymer is suppressed. For example, the content of a high molecular weight polymer having a molecular weight of 100,000 or more is 0.1 weight. % Or less of resin can be obtained.

  The monomer solution to be dropped is preferably stored at a temperature of 20 ° C. or lower. When the monomer solution is maintained at a temperature exceeding 20 ° C., a high molecular weight polymer is easily generated. Moreover, since a monomer solution may crystallize if it cools too much, as the temperature of a monomer solution, the range of -10 degreeC-20 degreeC is more preferable.

  Specifically, for example, (i) a monomer solution in which a monomer mixture is previously dissolved in an organic solvent, and a polymerization initiator solution in which a radical initiator (polymerization initiator) is dissolved in an organic solvent. A method in which the monomer solution and the polymerization initiator solution are dropped independently from each other in an organic solvent maintained at a constant temperature, and (ii) a monomer and a radical initiator (polymerization initiation) The mixture solution in which the agent is dissolved in an organic solvent is dropped into an organic solvent kept at a constant temperature. Of these, the method (i) is more 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.

  A known polymerization initiator can be used as the radical initiator. 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 1 mol to 1 mol of the monomer mixture. Is about 0.01 to 0.1 mol.

  In the drop polymerization, the ratio of the amount of the solvent charged in advance and the total amount of the solution to be dropped (monomer solution, polymerization initiator solution) is a resin in consideration of productivity, economy, workability, operability, etc. However, in general, the former / the latter (weight ratio) = 5/95 to 90/10, preferably 10/90 to 70/30, more preferably 20/80 to 60 /. A range of 40. The total amount of the polymerization solvent to be used (the amount of the solvent charged in advance + the amount of the solvent in the solution to be dropped) can be appropriately selected in consideration of workability, operability, reaction efficiency, solubility of the polymer to be produced, etc. It is generally 100 to 2000 parts by weight, preferably 200 to 1000 parts by weight, and more preferably about 300 to 700 parts by weight with respect to 100 parts by weight of the total amount of monomers.

  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.

  In the drop polymerization, it is desirable to control the temperature so as to minimize the fluctuation width of the polymerization temperature (reaction liquid temperature). For example, the polymerization temperature (reaction solution temperature) is within ± 5 ° C. (preferably between 93% or more (preferably between 95% or more) of the total dropping time of the monomer and polymerization initiator solution (preferably between 95% or more). Is preferably controlled within ± 3 ° C.). 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 3000 to 15000, preferably 4000 to 14000, and more preferably 5000 to 13000. According to the present invention, it is possible to obtain a photoresist resin in which the content of the polymer having a molecular weight exceeding 40000 is 4% by weight or less (preferably 3% by weight or less, more preferably 2% by weight or less) of the whole polymer. In addition, as described above, even when a solution containing both a monomer and a polymerization initiator is added dropwise, the formation of a high molecular weight polymer is suppressed. For example, the content of a high molecular weight polymer having a molecular weight of 100,000 or more is 0.00. A resin of 1% by weight or less can be obtained. The molecular weight distribution (Mw / Mn) is, for example, 1.1 to 3.5, preferably 1.1 to 3.0, and more preferably about 1.1 to 2.5. Mn represents the number average molecular weight of the polymer, and both Mw and Mn are values in terms of polystyrene. The weight average molecular weight of the resin, the content of a polymer having a molecular weight exceeding 40000, the content of a high molecular weight polymer having a molecular weight of 100,000 or more, and the molecular weight distribution can be measured by GPC (gel permeation chromatography).

  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).

  The polymer produced by polymerization can be isolated by precipitation (including 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 (including 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.

  As the solvent used for the repulping treatment (solvent for repulping) and the solvent used for the rinsing treatment (rinsing solvent), a poor polymer solvent used for precipitation (including reprecipitation) is preferable. 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.

  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.

  After completion of the polymerization step, the polymerization solution is dropped into a poor solvent as described above to precipitate the resin, and after performing operations such as repulping as necessary, the precipitated resin is solid-liquid separated with a centrifuge or the like. The The separated resin (wet crystal) contains low-boiling impurities such as a solvent used in the precipitation operation. If such low-boiling impurities are present in the resist film, the resist performance deteriorates and must be removed. Examples of the method for removing low boiling point impurities include a method of drying the wet crystal, a method of re-dissolving the wet crystal in a solvent for forming a coating film (resist solvent), and distilling off the low boiling point impurity by distillation. Is mentioned. However, in the method of drying wet crystals to remove low-boiling impurities, once the resin is dried, the adhesion between the particles becomes stronger due to drying, or when dissolved in a coating film forming solvent (resist solvent). , Very difficult to dissolve. Further, there is a problem that a part of the acid leaving group in the photoresist resin is decomposed by heat applied during drying. Therefore, in order to obtain a resin having good solubility, the wet crystals are redissolved in a solvent containing at least one solvent for forming a coating film, and the resulting redissolved solution is distilled and contained in the wet crystals. It is preferable to distill off the low boiling impurities. According to this method, decomposition of the resin can also be suppressed.

  As a solvent for forming a coating film, a solvent that dissolves a resin and has high transparency to light used for exposure is preferable. For example, glycol solvents (propylene glycol solvents, ethylene glycol solvents) exemplified as the polymerization solvent. Etc.), ester solvents (such as lactic acid ester solvents), ketone solvents (such as methyl isobutyl ketone and methyl amyl ketone), and mixed solvents thereof. Further, as preferred coating film forming solvents, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether pro Propylene glycol monoalkyl ether carboxylates such as pionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate; propylene glycol mono such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether A Kill ether; and mixtures thereof.

  Among the above-mentioned solvents, propylene glycol monomethyl ether acetate (PGMEA) has an advantage that it has an excellent function as a solvent in terms of evaporation rate at the time of forming a coating film, and has low toxicity. However, PGMEA tends to be inferior in solubility characteristics, and there remains a problem in dissolving a highly polar resin (in order to improve substrate adhesion, it is essential to introduce a polar group into the resin). About this, a solvent power can be improved significantly by adding propylene glycol monomethyl ether (PGME) to PGMEA. Therefore, it can be said that a mixed solvent of PGMEA and PGME is a particularly preferable solvent for forming a coating film (resist solvent).

  When a mixed solvent of PGMEA and PGME is used as a solvent for forming a coating film, the total proportion of PGMEA and PGME in the total solvent is usually 70% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more. In particular, a mixed solvent consisting essentially of PGMEA and PGME is preferred. Moreover, the range of 40 / 60-95 / 5 is normally used for the mixing ratio of PGMEA / PGME when using the mixed solvent of PGMEA and PGME as a solvent for film formation. Preferably, it is 50/50 to 90/10, and particularly preferably about 60/40 to 85/15. If the ratio of PGMEA is less than 40% by weight, it is difficult to form a uniform coating film because there is a problem with the evaporation rate at the time of coating film formation. Moreover, when the ratio of PGME is less than 5% by weight, the solubility of the resin tends to deteriorate.

  The solvent used to redissolve the wet crystal of the photoresist resin only needs to contain at least one solvent for forming a coating film. That is, for example, when a mixed solvent of two kinds of solvents is used as a solvent for forming a coating film, the wet crystals may be redissolved using one kind of solvent, and the wet crystals may be formed using a mixed solvent of two kinds of solvents. It may be redissolved. Alternatively, the wet crystals may be redissolved using a coating film forming solvent and other solvent (a solvent having a boiling point lower than that of the coating film forming solvent). When a solvent other than the solvent for forming the coating film is used as the solvent for re-dissolution, the amount of the solvent other than the solvent for forming the coating film can be appropriately selected according to the solubility of the resin, etc. The amount is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less of the total solvent for re-dissolution. In addition, when using 2 or more types of mixed solvents as a solvent for film formation, the solvent which was not used for the re-dissolution of the said wet crystal can be added during or after distillation.

  The distillation of the redissolved solution thus obtained is preferably carried out by circulating a heating medium or steam at 140 ° C. or lower through a heating jacket and / or a tube (coiled tube or the like) of the distillation can. As the distillation column, a conventional distillation column such as a single distillation column, a plate column, or a packed column can be used. By setting the temperature of the heat medium or steam (preferably both temperatures when both the heat medium and steam are used) to 140 ° C. or less, the photoresist resin is decomposed (decomposition at the acid-eliminable group). Remarkably suppressed. The temperature of the heat medium or steam is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower. The lower limit of the temperature is, for example, about 40 ° C, preferably about 50 ° C. When a heating medium or steam having a temperature exceeding 140 ° C. is circulated through the heating jacket or tube, the resin decomposes on the wall surface of the heating jacket or tube even if the liquid temperature in the distillation can is lowered. If the temperature of the heating medium or steam used for heating is lower than 40 ° C., it is necessary to make the degree of vacuum considerably low, and the temperature of the cooling water for cooling and condensing the solvent to be distilled becomes too low, which is disadvantageous in terms of cost. Prone.

  During distillation, it is preferable to distill while stirring the inside of the distillation can with a stirrer. Distilling while stirring is particularly effective when the viscosity of the solution increases, that is, when the concentration of the dissolved resin increases. The reason is considered to be that the solution is renewed smoothly on the surface of the jacket or coil by stirring, and the overheating of the solution can be prevented. The strength of stirring is not particularly limited as long as the internal solution can be stirred and mixed.

  As described above, in order to prevent the mixing of the metal component into the resin, the wetted part is made of glass, such as distillation equipment, for example, a distillation column (particularly a distillation can), a stirrer (stirring blade) for the distillation can, and a coil. It is preferable that

  The pressure at the time of distillation varies depending on the kind of the redissolving solvent and the like, but is generally 500 to 1 torr (66.5 to 0.133 kPa), preferably 400 to 2 torr (53.2 to 0.266 kPa). If the pressure is high, the distillation temperature becomes high and there is a concern about the thermal decomposition of the resin. If the pressure is too low, the temperature of the refrigerant required for condensing the evaporated solvent needs to be lowered, which is not economical. The liquid temperature (can liquid temperature) in the distillation can is preferably 100 ° C. or lower, more preferably 80 ° C. or lower.

  In distillation, in order to completely remove low-boiling impurities, a part of the solvent for forming a coating film together with the low-boiling impurities (in the case of using a solvent other than the solvent for forming a coating film, the solvent and the solvent for forming a coating film). A part of the solvent. The distillation rate in distillation [(distillation amount / charge amount) × 100 (% by weight)] depends on the content of low-boiling impurities in the wet crystal of the photoresist resin, the type and composition of the solvent for re-dissolution, and the like. Generally, it is about 30 to 90% by weight, preferably about 50 to 87% by weight.

  The resin concentration of the resin solution finally concentrated in the distillation is, for example, about 10 to 70% by weight, preferably about 20 to 60% by weight, and particularly preferably about 30 to 50% by weight.

  After removing low-boiling impurities by distillation, a solvent for forming a coating film is added to the residual liquid as necessary to prepare a photoresist resin solution having a desired concentration. The resin concentration in the final photoresist resin solution is, for example, 5 to 50% by weight, preferably 10 to 30% by weight.

  In a preferred embodiment of the present invention, the separated wet crystal of the photoresist resin is redissolved in propylene glycol monomethyl ether (PGME), and the resulting redissolved solution is preferably placed in a heating jacket and / or tube of a distillation can. Distilling while circulating a heating medium or steam at 140 ° C. or lower to distill low-boiling impurities contained in the wet crystals of the photoresist resin under reduced pressure, and at the time of and / or after distillation, propylene glycol Monomethyl ether acetate (PGMEA) is added to obtain a photoresist resin solution using a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether as a solvent for forming a coating film. In this aspect, since PGME having excellent resin solubility and a relatively low boiling point is used as the solvent for re-dissolving the resin, the wet crystals can be reliably dissolved in a short time and the distillation temperature can be lowered. For this reason, decomposition | disassembly, a quality change, etc. of resin can be suppressed further, and a highly transparent solution without an insoluble content is obtained. Therefore, a complicated filtering operation can be omitted or simplified, and contamination of foreign matters can be prevented. In addition, when the PGME single solvent is used, it becomes extremely easy to accurately achieve the mixing ratio of PGMEA and PGME in the final resist solvent. From these points, the PGME used for dissolving the wet crystal is preferably substantially 100% by weight. However, a PGME containing a small amount of other solvent is used as long as the effect of suppressing the decomposition of the resin is not impaired. Also good. The content of such other solvents is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. In addition, when the wet crystal is dissolved in PGMEA alone or in a mixed solvent with PGMEA containing a large amount of PGMEA and then subjected to a distillation operation, it takes time to dissolve the wet crystal and the distillation temperature increases. It is easy to produce a solvent insoluble component. In the said preferable aspect, after removing a low boiling-point impurity by distillation, PGMEA and PGME as needed are added to a residual liquid, and the resin solution for photoresists of desired density | concentration is prepared.

  The resin composition for photoresist can be prepared by mixing the resin for photoresist obtained by the production method of the present invention with a photoacid generator and a solvent for resist. For example, by dissolving a photoresist resin and a photoacid generator obtained by drying the wet crystal in a resist solvent, a redissolved solution obtained by re-dissolving the wet crystal in a resist solvent It can be obtained by adding a resist solvent for concentration adjustment and a photoacid generator to the distilled residual liquid as necessary.

  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 use amount of the photoacid generator can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each repeating unit in the polymer (resin for photoresist), and the like. It can be selected from a range of about 1 to 30 parts by weight, preferably 1 to 25 parts by weight, and more preferably about 2 to 20 parts by weight.

  The resin composition for a photoresist 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), or the like. Good. The concentration of the photoresist resin in the photoresist resin composition is, for example, 5 to 50% by weight, preferably 10 to 30% by weight.

  The photoresist resin 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. Perform) By forming a 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 application of the photoresist resin composition can be performed 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 the acid causes, 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 photoresist resin. The protecting group (leaving group) is rapidly removed to generate a carboxyl group that contributes to solubilization. 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. The resin (polymer) concentration was obtained from 1 g of a resin solution collected in an evaporating dish, dried under reduced pressure at 100 ° C., and the weight loss.

The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer, the content of the polymer having a molecular weight of more than 40000, and the content of a high molecular weight polymer having a molecular weight of 100,000 or more are measured using a refractometer (RI) as a detector. It was determined in terms of standard polystyrene by GPC measurement using tetrahydrofuran (THF) as an eluent. GPC measurement was performed using three columns “Shodex KF-806L” (trade name) connected in series by Showa Denko KK, sample concentration 0.5%, sample injection volume 35 μl, column temperature 40 ° C., RI The analysis was performed under the conditions of a temperature of 40 ° C., an eluent flow rate of 0.8 ml / min, and an analysis time of 60 minutes. As a GPC measuring apparatus, “GPCLC-10A” manufactured by Shimadzu Corporation was used. Note that the content of molecular weight of 100,000 or more high molecular weight polymers, a sample of 1% sample concentration was prepared to obtain the peak area S _p of the polymer of interest in the sample injection volume 15 [mu] l, then the molecular weight in the sample injection volume 150μl 100000 the peak area S _h of the above high molecular weight polymer, was calculated content of molecular weight of 100,000 or more high molecular weight polymer a (%) by the following equation.
A (%) = S _h / {(S _p × 10) + S _h } × 100

ガラス製撹拌機、温度計、還流冷却管、滴下ロート及び窒素導入管を備えたガラス製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３３０ｇ導入し、７５℃に昇温した。一方、１−メタクリロイルオキシ−３−ヒドロキシアダマンタン（ＨＭＡ）６０ｇ（０．２５４モル）、５−メタクリロイルオキシ−２，６−ノルボルニルカルボラクトン（ＭＮＢＬ）３０ｇ（０．１３５モル）及び２−メタクリロイルオキシ−２−メチルアダマンタン（２ＭＭＡ）６０ｇ（０．２５６モル）を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）４１０ｇに溶解して単量体溶液を調製し、アルミ箔で遮光したガラス製滴下ロートに入れ、５℃に冷却した。また、ジメチル−２，２´−アゾビス（２−メチルプロピオネート）（開始剤；和光純薬工業製、商品名「Ｖ−６０１」）９．３ｇを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）５０ｇに溶解して開始剤溶液を調製し別の滴下ロートに入れた。単量体溶液と開始剤溶液を６時間かけてフラスコ内に滴下した。その間、フラスコ内の温度を７５℃にコントロールした。滴下終了後、同温度で２時間熟成した。得られた反応溶液（ポリマードープ）を冷却後、９０００ｇのへプタン／酢酸エチル混合液（重量比７５／２５）に撹拌しながら滴下し、滴下終了後、さらに３０分撹拌した。析出した沈殿を遠心分離機により遠心分離した。得られた湿結晶を２０００ｇのプロピレングリコールモノメチルエーテル（ＰＧＭＥ）に添加し、撹拌して溶解した。得られた溶液を、熱媒用ジャケット及び撹拌機付きガラス製単蒸留装置の蒸留缶に仕込み、蒸留缶内を撹拌しながら熱媒用ジャケットに１００℃（ジャケット入り口温度）のオイルを流通しつつ、減圧下で濃縮を行った。蒸留缶内の液温を約７５℃に制御した。液量がおよそ３００ｍｌになった時点で蒸留を停止した。濃縮されたポリマー濃度を測定したところ４０重量％であった。ＰＧＭＥＡ及びＰＧＭＥを添加して、ポリマー濃度２０重量％のＰＧＭＥＡ／ＰＧＭＥ（重量比６／４）溶液を調製した。この溶液は０．１μｍのフィルターで濾過したが、最後まで順調に濾過できた。
また、濾過後の樹脂溶液をサンプリングし、ＧＰＣ分析したところ、重量平均分子量（Ｍｗ）は８０００、分子量分布（Ｍｗ／Ｍｎ）は２．０であった。また、分子量４００００を超えるポリマーの含有率は１．０重量％であり、分子量１０００００以上の高分子量ポリマーは検出されなかった。また、樹脂溶液の鉄分含有量は１０重量ｐｐｂであった。 Example 1
Manufacture of resin solution for photoresist containing resin of the following structure

330 g of propylene glycol monomethyl ether acetate (PGMEA) was introduced into a glass separable flask equipped with a glass stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, and the temperature was raised to 75 ° C. Meanwhile, 1-methacryloyloxy-3-hydroxyadamantane (HMA) 60 g (0.254 mol), 5-methacryloyloxy-2,6-norbornylcarbolactone (MNBL) 30 g (0.135 mol) and 2-methacryloyl A monomer solution was prepared by dissolving 60 g (0.256 mol) of oxy-2-methyladamantane (2MMA) in 410 g of propylene glycol monomethyl ether acetate (PGMEA), and placed in a glass dropping funnel shielded with aluminum foil. Cooled to 5 ° C. Further, 9.3 g of dimethyl-2,2′-azobis (2-methylpropionate) (initiator; manufactured by Wako Pure Chemical Industries, trade name “V-601”) was added to 50 g of propylene glycol monomethyl ether acetate (PGMEA). An initiator solution was prepared by dissolution and placed in a separate dropping funnel. The monomer solution and the initiator solution were dropped into the flask over 6 hours. Meanwhile, the temperature in the flask was controlled at 75 ° C. After completion of dropping, the mixture was aged at the same temperature for 2 hours. The obtained reaction solution (polymer dope) was cooled and then added dropwise to 9000 g of a heptane / ethyl acetate mixture (weight ratio 75/25) with stirring. After completion of the addition, the mixture was further stirred for 30 minutes. The deposited precipitate was centrifuged with a centrifuge. The obtained wet crystal was added to 2000 g of propylene glycol monomethyl ether (PGME) and dissolved by stirring. The obtained solution was charged into a heating medium jacket and a distillation can of a glass single distillation apparatus with a stirrer, and oil at 100 ° C. (jacket inlet temperature) was distributed to the heating medium jacket while stirring the inside of the distillation can. The solution was concentrated under reduced pressure. The liquid temperature in the distillation can was controlled at about 75 ° C. Distillation was stopped when the liquid volume reached approximately 300 ml. The concentration of the concentrated polymer was measured and found to be 40% by weight. PGMEA and PGME were added to prepare a PGMEA / PGME (weight ratio 6/4) solution having a polymer concentration of 20% by weight. This solution was filtered through a 0.1 μm filter, but could be smoothly filtered to the end.
Moreover, when the resin solution after filtration was sampled and analyzed by GPC, the weight average molecular weight (Mw) was 8000, and molecular weight distribution (Mw / Mn) was 2.0. The content of the polymer having a molecular weight exceeding 40000 was 1.0% by weight, and a high molecular weight polymer having a molecular weight of 100,000 or more was not detected. The iron content of the resin solution was 10 wt ppb.

Comparative Example 1
The same operation as in Example 1 was performed except that the glass dropping funnel containing the monomer solution was not shielded from light. The obtained resin solution having a concentration of 20% by weight was filtered with a 0.1 μm filter. However, the filtration rate was slow in the latter half, and the used filter had to be replaced. Moreover, when the resin solution after filtration was sampled and analyzed by GPC, the weight average molecular weight (Mw) was 8000, and molecular weight distribution (Mw / Mn) was 2.0. Further, the content of the polymer having a molecular weight exceeding 40000 was 4.3% by weight, and the high molecular weight polymer having a molecular weight of 100,000 or more was 0.15% by weight.

Example 2
Production of Resin Resin Solution Containing Resin with Same Structure as Example 1 In a glass separable flask equipped with a glass stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, propylene glycol monomethyl ether 330 g of acetate (PGMEA) was introduced, and the temperature was raised to 75 ° C. Meanwhile, 1-methacryloyloxy-3-hydroxyadamantane (HMA) 60 g (0.254 mol), 5-methacryloyloxy-2,6-norbornylcarbolactone (MNBL) 30 g (0.135 mol), 2-methacryloyl 60 g (0.256 mol) of oxy-2-methyladamantane (2MMA) and dimethyl-2,2′-azobis (2-methylpropionate) (initiator; manufactured by Wako Pure Chemical Industries, trade name “V-601” ) 9.3 g was dissolved in 410 g of propylene glycol monomethyl ether acetate (PGMEA) to prepare a monomer / initiator solution, which was placed in a glass dropping funnel shielded with aluminum foil and cooled to 5 ° C. This monomer / initiator solution was dropped into the flask over 6 hours. Meanwhile, the temperature in the flask was controlled at 75 ° C. After completion of dropping, the mixture was aged at the same temperature for 2 hours. The obtained reaction solution (polymer dope) was cooled and then added dropwise to 9000 g of a heptane / ethyl acetate mixture (weight ratio 75/25) with stirring. After completion of the addition, the mixture was further stirred for 30 minutes. The deposited precipitate was centrifuged with a centrifuge. The obtained wet crystal was added to 2000 g of propylene glycol monomethyl ether (PGME) and dissolved by stirring. The obtained solution was charged into a heating medium jacket and a distillation can of a glass single distillation apparatus equipped with a stirrer, and oil at 100 ° C. (jacket inlet temperature) was distributed to the heating medium jacket while stirring the inside of the distillation can. The solution was concentrated under reduced pressure. The liquid temperature in the distillation can was controlled at about 75 ° C. Distillation was stopped when the liquid volume reached approximately 300 ml. The concentration of the concentrated polymer was measured and found to be 40% by weight. PGMEA and PGME were added to prepare a PGMEA / PGME (weight ratio 6/4) solution having a polymer concentration of 20% by weight. This solution was filtered through a 0.1 μm filter, but could be smoothly filtered to the end.
Moreover, when the resin solution after filtration was sampled and analyzed by GPC, the weight average molecular weight (Mw) was 8000, and molecular weight distribution (Mw / Mn) was 2.0. The content of the polymer having a molecular weight exceeding 40000 was 1.0% by weight, and a high molecular weight polymer having a molecular weight of 100,000 or more was not detected. The iron content of the resin solution was 10 wt ppb.

Comparative Example 2
The same operation as in Example 2 was carried out except that a stainless steel manufacturing apparatus was used, and finally a PGMEA / PGME (weight ratio 6/4) solution having a polymer concentration of 20% by weight was prepared. The iron content of the resin solution was 150 wt ppb.

Claims (7)

  A monomer mixture containing at least a monomer a containing a group that is partially eliminated by an acid and becomes alkali-soluble and a monomer b containing an alicyclic skeleton having a polar group is polymerized by drop polymerization. And a method for producing a photoresist resin containing at least a repeating unit corresponding to the monomer a and a repeating unit corresponding to the monomer b, wherein the wetted part is made of glass. A method for producing a photoresist resin, comprising: dropping a monomer solution stored in a light-shielded state into a temperature-controlled solvent for polymerization.   The method for producing a photoresist resin according to claim 1, wherein the monomer solution stored at a temperature of 20 ° C. or less is dropped into the reaction vessel.   The photoresist resin obtained by polymerization is precipitated in a poor solvent, the precipitated photoresist resin is separated as wet crystals, and the wet crystals are redissolved in a solvent containing at least one coating film forming solvent, The method for producing a photoresist resin according to claim 1, further comprising a step of distilling the obtained redissolved solution to distill off low-boiling impurities contained in the wet crystals. Monomer a is 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 resin according to claim 1, wherein the method is at least one compound selected from the group consisting of: The monomer b is 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 resin according to claim 1, wherein the method is at least one compound selected from the group consisting of:   A photoresist resin composition obtained by mixing a photoresist resin obtained by the production method according to claim 1 with a photoacid generator and a resist solvent. For producing a resin composition for use.   The manufacturing method of the semiconductor including the process of apply | coating the resin composition for photoresists obtained by the manufacturing method of the resin composition for photoresists of Claim 6 to a board | substrate or a base material, and forming a resist coating film.