JP2006335777A - Method for producing polymer compound for photoresist - Google Patents

Abstract

An object of the present invention is to provide an appropriate method for producing an acrylic polymer used in a photoresist involved in an ArF excimer laser.
According to the present invention, a monomer including a monomer A having an alkali-soluble group by elimination by an acid and a monomer B having a polar group-containing alicyclic skeleton and a polymerization initiator are dissolved in a solvent. Then, the polymer is polymerized while dropping into a solvent heated to the polymerization temperature, the polymerization solution is added to a poor solvent (precipitation solvent), the polymer is precipitated, and the solvent is removed by centrifuging the precipitate with a centrifuge. Thereafter, in a method of dissolving a wet crystal in a solvent and concentrating by distillation under reduced pressure to produce a solution of a photoresist polymer compound, the molar ratio of the methacrylic acid ester is 60 mol with respect to all monomers used for polymerization. It is an object of the present invention to provide a method for producing a high molecular compound for a photoresist, which is characterized by being at least%.
[Selection figure] None

Description

  The present invention relates to a method for producing a photoresist polymer compound useful for the preparation of a photoresist resin composition for use in semiconductor microfabrication and the like.

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. The resist polymer used in this ArF excimer laser exposure machine has a repeating unit containing a polar group-containing alicyclic skeleton having high adhesion to the substrate and a repeating unit containing a group that becomes alkali-soluble by detachment with an acid. Various polymers have been proposed. (For example, Patent Documents 1 to 3)
Further, Patent Document 4 proposes a combination of various monomers, but the method for producing a polymer usable for a photoresist is not sufficient. Furthermore, Patent Document 5 proposes the advantage of polymerizing by dropping a monomer or a polymerization initiator at the time of polymerization. However, a proposal regarding a detailed polymer treatment after polymerization, or problems, etc. There is no discussion on
JP 07-252324 A JP 09-073173 A Japanese Patent Laid-Open No. 2000-026446 JP 2000-109154 A JP 2004-269855 A

  Accordingly, an object of the present invention is to provide an appropriate method for producing an acrylic polymer compound used for a photoresist involved in an ArF excimer laser.

  As a result of diligent studies to achieve the above-mentioned object, the present invention makes a photoresist polymer compound into an appropriate composition, and adopts an appropriate polymer processing method corresponding thereto, as a photoresist resin. The present inventors have completed the present invention by finding a method for producing a polymer compound having usable quality.

  That is, an object of the present invention is to dissolve in a solvent a monomer and a polymerization initiator that include at least a monomer A having a group that becomes alkali-soluble upon removal by an acid and a monomer B having a polar group-containing alicyclic skeleton. Then, it is polymerized while dropping into a solvent heated to the polymerization temperature, the polymerization solution is added to a poor solvent (precipitation solvent), the polymer is precipitated, and the solvent is removed by centrifuging the precipitate with a centrifuge. Thereafter, in a method of dissolving a wet crystal in a solvent and concentrating by distillation under reduced pressure to produce a solution of a photoresist polymer compound, the molar ratio of the methacrylic acid ester is 60 mol with respect to all monomers used for polymerization. It is an object of the present invention to provide a method for producing a high molecular compound for a photoresist, which is characterized by being at least%.

  Another object of the present invention is to provide a monomer A having the following formulas (1a) to (1c)

（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、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）から選択された少なくとも１種のモノマーであることを特徴とする前記記載のフォトレジスト用高分子化合物の製造方法を提供することにある。

(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 alkyl group having 1 to 6 carbon atoms. R ¹ to R ³ is the same or different and represents an alkyl group having 1 to 6 carbon atoms, R ⁴ is a substituent bonded to the ring Z, and is the same or different and represents an oxo group, 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, provided that at least one of n R ⁴ is And —COOR ^a group, wherein R ^a represents an optionally substituted tertiary hydrocarbon group, tetrahydrofuranyl group, tetrahydropyranyl group, or oxepanyl group, n is an integer of 1 to 3. At least one monomer selected from An object of the present invention is to provide a method for producing a polymer compound for photoresists as described above.

  Furthermore, the object of the present invention is that the monomer B is represented by the following formulas (2a) to (2e):

（式中、Ｒは水素原子又は炭素数１〜６のアルキル基を示す。Ｒ⁵〜Ｒ⁷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）Ｒ⁵〜Ｒ⁷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。Ｒ⁸〜Ｒ¹²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。Ｒ¹³〜Ｒ²¹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。Ｒ²²〜Ｒ³⁰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）から選択された少なくとも１種のモノマーであることを特徴とする前記記載のフォトレジスト用高分子化合物の製造方法を提供することにある。

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^{5 to} R ⁷ are the same or different and are a hydrogen atom, an alkyl group, or a hydroxyl group optionally protected by a protecting group, 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 represent —CH ₂ —, —CO— or —; COO— provided that (i) at least one of V ^{1 to} V ³ is —CO— or —COO—, or (ii) at least one of R ^{5 to} R ⁷ is a protecting group A hydroxyl group which may be protected with, a hydroxyalkyl group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group, R ^{8 to} R ¹² may be the same or different; Protected with hydrogen atom, alkyl group, protecting group A hydroxyl group that may be protected, a hydroxyalkyl group that may be protected with a protecting group, and a carboxyl group that may be protected with a protecting group, R ^{13 to} R ²¹ may be the same or different and each 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 ^{22 to} R ³⁰ are the same. Or 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) It is an object of the present invention to provide a method for producing a polymer compound for photoresist as described above, which is at least one selected monomer.

  Another object of the present invention is to provide a polymer for a photoresist as described above, wherein the solvent for dissolving the wet crystals after centrifugation is one solvent selected from glycol ether solvents or ester solvents. A method for producing a compound is provided.

  Furthermore, an object of the present invention is to provide a method for producing a polymer compound for photoresists as described above, wherein the poor solvent (precipitation solvent) is a mixture of a hydrocarbon solvent and a polar solvent.

  Furthermore, the object of the present invention is to dissolve in a solvent a monomer and a polymerization initiator that contain at least a monomer A having a group that becomes alkali-soluble upon elimination by an acid and a monomer B having a polar group-containing alicyclic skeleton. Then, it is polymerized while dropping into a solvent heated to the polymerization temperature, the polymerization solution is added to a poor solvent, the polymer is precipitated, the precipitate is centrifuged by a centrifuge, the solvent is removed, and then the moisture is removed. This is a method for producing a photoresist resin solution by dissolving crystals in a glycol solvent and concentrating by distillation under reduced pressure, and further characterized in that it is described in any of the above objects of the present invention. Another object of the present invention is to provide a photoresist resin composition containing at least a polymer compound for photoresist and a photoacid generator.

  Another object of the present invention is to provide a method for producing a semiconductor, wherein the photoresist resin composition described above is applied onto a substrate and exposed to light having a wavelength of 193 nm.

  According to the method for producing a photoresist polymer compound of the present invention, a solution of a polymer compound having a sufficiently low level of moisture and low-boiling organic components can be produced by a simple production method. This makes it possible to provide a simple method for producing a resist composition (in solution).

  The present invention relates to the production of a special polymer compound used in the production of next-generation semiconductors capable of latent images of fine resist patterns by using an ArF excimer laser as an exposure light source. is there. The polymer compound has as essential components a repeating unit (unit) having a group that is partly eliminated by acid and becomes alkali-soluble, and a repeating unit (unit) having a polar group-containing alicyclic skeleton. Therefore, in the production of the polymer compound, copolymerization of a monomer including at least a monomer A having a group that becomes alkali-soluble by elimination by an acid and a monomer B having a polar group-containing alicyclic skeleton. Is applied.

  The monomer A is polymerized so that its repeating unit is partly eliminated by the action of an acid generated from the photoacid generator upon exposure and is soluble in an alkali developer (having an acid-eliminable group). Monomer), for example, (meth) acrylic acid having an alicyclic hydrocarbon group having 6 to 20 carbon atoms and a group capable of leaving by the action of an acid. Can be mentioned. “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. As typical examples of such (meth) acrylic acid esters, monomers represented by the above formulas (1a) and (1b) are exemplified.

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. 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 monomer represented by the formula (1c).

  In addition, as a monomer A that is partly eliminated by acid and becomes alkali-soluble, the oxygen atom constituting the 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 (meth) acrylic acid ester containing a lactone ring. The monomer A may be only one type or a combination of two or more types.

The monomer A is preferably at least one monomer selected from the formulas (1a) to (1c). In formulas (1a) to (1c), 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.

Examples of R ^{1 to} R ³ in formulas (1a) to (1c) and R ^{1 to} R ³ in formulas (1a) and (1b) include methyl, ethyl, propyl, isopropyl, Examples thereof include linear or branched alkyl groups having 1 to 6 carbon atoms such as butyl, isobutyl, s-butyl, t-butyl and hexyl groups. 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 for 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.

The monomer B containing an alicyclic skeleton having a polar group includes (1) an alicyclic hydrocarbon group having 6 to 20 carbon atoms containing a lactone ring [lactone ring and monocyclic or polycyclic (bridged ring) (Meth) acrylic acid ester B1 in which a group having a structure condensed with an alicyclic carbocycle of the like] is bonded to an oxygen atom constituting an ester bond. As a representative example of such a monomer B1, a monomer in which at least one of V ^{1 to} V ^{3 in} the formula (2a) is —COO—, and (2b), (2c), (2d), (2e) The monomer represented by this is illustrated.

In addition, the monomer B including an alicyclic skeleton having a polar group includes (2) an alicyclic hydrocarbon group having 6 to 20 carbon atoms having a polar group such as a hydroxyl group, a carboxyl group, and an oxo group (in particular, a bridge). (Meth) acrylic acid ester B2 in which the (cyclic hydrocarbon group) is bonded to the oxygen atom constituting the ester bond is also included. As a representative 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 ^{5 to} R ⁷ is a protecting group. Examples are a unit which is 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.

  The monomer B imparts adhesion to a substrate such as a silicon wafer by a polar group and imparts dry etching resistance by an alicyclic skeleton. The monomer B may be only one type or a combination of two or more types. The monomer B is preferably at least one monomer selected from the formulas (2a) to (2e). In addition, when monomer B1 and monomer B2 are combined as monomer B, they not only have well-balanced properties such as substrate adhesion, dry etching resistance, and solubility in a resist solvent, but also have excellent homogeneous reactivity during polymerization ( A great advantage is that a polymer with 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 ^{5 to} R ³⁰ 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.

  The polymer compound for photoresist of the present invention is a monomer other than the monomers A and B within a range not impairing properties such as alkali solubility (acid detachability), substrate adhesion, dry etching resistance, and solubility in a resist solvent. May be included. 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 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 content of the repeating unit corresponding to the monomer A in the photoresist polymer compound of the present invention is, for example, 5 to 90 mol%, preferably 10 to 80 mol%, more preferably 20 to 70 mol%. When the content of the repeating unit corresponding to the monomer A is less than 5 mol%, the solubility of the resist film becomes insufficient during alkali development, the resolution is lowered, and it is difficult to form a fine pattern with high accuracy. It becomes. Moreover, when content of the repeating unit corresponding to the monomer A exceeds 90 mol%, board | substrate adhesiveness and dry-etching tolerance will fall, and the problem that a pattern will not peel off by image development will occur easily.

  The content of the repeating unit corresponding to the monomer B in the photoresist polymer compound of the present invention is, for example, 10 to 95 mol%, preferably 20 to 90 mol%, and more preferably 30 to 80 mol%. When the content of the repeating unit corresponding to the monomer B is less than 10 mol%, the substrate adhesion and dry etching resistance are liable to decrease, and when it exceeds 95 mol%, the amount of alkali-soluble units introduced is reduced. In alkali development, the solubility of the resist film tends to be insufficient. When combining monomer B1 and monomer B2 as monomer B, the ratio of the repeating unit corresponding to each monomer (monomer B1 / monomer B2) is not particularly limited, but generally the former / the latter (molar ratio) = 5 / 95- It is 95/5, preferably 10/90 to 90/10, more preferably about 30/70 to 70/30.

  As a feature of the polymer compound for photoresist of the present invention, the weight average molecular weight (Mw) is in the range of 3000 to 15000. If the weight average molecular weight is less than 3000, a desired coating strength cannot be obtained when a resist film is formed. When the weight average molecular weight exceeds 15,000, the solution viscosity becomes high when preparing a resin composition for photoresist, workability is lowered, and a uniform and good coating film cannot be obtained. A weight average molecular weight becomes like this. Preferably it is 4000-14000, More preferably, it is about 5000-13000. The molecular weight distribution (Mw / Mn) of the photoresist polymer compound of the present invention is, for example, about 1.1 to 3.5, preferably about 1.5 to 3.0. In addition, said Mn shows a number average molecular weight, and both Mn and Mw are values of polystyrene conversion.

  The monomer A used in the production of the polymer compound of the present invention has a group that is eliminated by an acid and becomes alkali-soluble, and is represented by the above formulas (1a) to (1c). The monomer B having a polar group-containing alicyclic skeleton is represented by the above formulas (2a) to (2e).

[Monomer represented by formula (1a)]
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 Has an 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 Has an adamantane ring)
The compound represented by the formula (1a) is obtained by, for example, reacting a corresponding cyclic alcohol with (meth) acrylic acid or a reactive derivative thereof according to a conventional esterification method using an acid catalyst or a transesterification catalyst. Can be obtained.

Typical examples of the compound represented by the formula (1b) include the following compounds, but are not limited thereto.
[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 formula (1b) is, for example, a methanol derivative having an alicyclic group at the corresponding 1-position and (meth) acrylic acid or a reactive derivative thereof, using an acid catalyst or a transesterification catalyst. It can be obtained by reacting according to a conventional esterification method.

Although the following compound is mentioned as a typical example of a compound represented by Formula (1c), It is not limited to these.
[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 obtained by, for example, reacting a corresponding cyclic alcohol with (meth) acrylic acid or a reactive derivative thereof according to a conventional esterification method using an acid catalyst or a transesterification catalyst. Can be obtained.

[Monomers Represented by Formulas (2a) to (2e)]
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 ⁵ = R ⁶ = R ⁷ = H, V ² = —CO—O— (the carbon atom side to which R ⁶ 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 ^{5 = R 6 = R 7 = H} , V 1 = -CO-O- ( left bonded to the carbon atom side of the ^{R 5), V 2 = -CO} -O- ( on the left are attached to R ⁶ 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 ^{5 = R 6 = R 7 = H} , V 1 = -O-CO- ( left bonded to the carbon atom side of the ^{R 5), V 2 = -CO} -O- ( on the left are attached to R ⁶ 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 ^{5 = R 6 = R 7 = H} , V 1 = -CO-O- ( left bonded to the carbon atom side of the ^{R 5), V 2 = -O} -CO- ( left is bonded to R ⁶ Carbon atom side), V ³ = -CH _2- )
[2-5] 1- (meth) acryloyloxy-3-hydroxyadamantane (R = H or ^{_{CH 3, R 5 = OH,}} R 6 = R 7 = H, V 1 = V 2 = V 3 = -CH 2 −)
[2-6] 1- (meth) acryloyloxy-3,5-dihydroxyadamantane (R = H or _{^{CH 3, R 5 = R 6}} = OH, R 7 = H, V 1 = V 2 = V 3 = - CH ₂ −)
[2-7] 1- (Meth) acryloyloxy-3,5,7-trihydroxyadamantane (R = H or CH ₃ , R ⁵ = R ⁶ = R ⁷ = 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 5 = OH,}} R 6 = R 7 = CH 3, V 1 = V 2 = V ³ = -CH _2- )
[2-9] 1- (meth) acryloyloxy-3-carboxyadamantane (R = H or CH ₃ , R ⁵ = COOH, R ⁶ = R ⁷ = H, V ¹ = V ² = V ³ = -CH ₂ −)
The compound represented by the above formula (2a) is obtained by reacting a corresponding cyclic alcohol derivative with (meth) acrylic acid or a reactive derivative thereof according to a conventional esterification method using an acid catalyst or a transesterification catalyst. Can be obtained.

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 ] nonan-2-one (= 5- (meth) acryloyloxy-2,6-norbornane (Carbolactone) (R = H or CH ₃ , R ⁸ = R ⁹ = R ¹⁰ = R ¹¹ = R ¹² = 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 ⁸ = CH ₃ , R ⁹ = R ¹⁰ = R ¹¹ = R ¹² = 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 ⁹ = CH ₃ , R ⁸ = R ¹⁰ = R ¹¹ = R ¹² = 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 ¹⁰ = CH ₃ , R ⁸ = R ⁹ = R ¹¹ = R ¹² = 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 ⁸ = R ⁹ = R ¹¹ = R ¹² = H, R ¹⁰ = COOH)
[2-15] 5- (Meth) acryloyloxy-9-methoxycarbonyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (R = H or CH ₃ , R ^{8 = R 9 = R 11 = R} 12 = H, R 10 = 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 ⁸ = R ⁹ = R ¹¹ = R ¹² = H, R ¹⁰ = 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 ⁸ = R ⁹ = R ¹¹ = R ¹² = H, R ¹⁰ = t-butoxycarbonyl group)
The compound represented by the above formula (2b) reacts a corresponding cyclic alcohol derivative with (meth) acrylic acid or a reactive derivative thereof according to a conventional esterification method using an acid catalyst or a transesterification catalyst. Can be obtained. 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 reacting a corresponding cyclic alcohol derivative with (meth) acrylic acid or a reactive derivative thereof according to a conventional esterification method using an acid catalyst or a transesterification catalyst. Can be obtained.

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 ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ^{17 = R 18 = R 19 =} R 20 = R 21 = H)
[2-21] 4- (Meth) acryloyloxy-4-methyl-6-oxabicyclo [3.2.1] octane-7-one (R = H or CH ₃ , R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = R ¹⁸ = R ¹⁹ = R ²⁰ = R ²¹ = H, R ¹³ = CH ₃ )
[2-22] 4- (meth) acryloyloxy-5-methyl-6-oxabicyclo [3.2.1] octan-7-one (R = H or ^{_{CH 3, R 13 = R 15}} = R 16 = R ¹⁷ = R ¹⁸ = R ¹⁹ = R ²⁰ = R ²¹ = H, R ¹⁴ = CH ₃ )
[2-23] 4- (Meth) acryloyloxy-4,5-dimethyl-6-oxabicyclo [3.2.1] octane-7-one (R = H or CH ₃ , R ¹⁵ = R ¹⁶ = R ^{17 = R 18 = R 19 =} R 20 = R 21 = H, R 13 = R 14 = 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 ²² = R ²³ = R ²⁴ = R ²⁵ = R ²⁶ = R ²⁷ = R ²⁸ = R ²⁹ = R ³⁰ = H)
[2-25] 6- (Meth) acryloyloxy-6-methyl-2-oxabicyclo [2.2.2] octane-3-one (R = H or CH ₃ , R ²² = R ²⁴ = R ²⁵ = R ²⁶ = R ²⁷ = R ²⁸ = R ²⁹ = R ³⁰ = H, R ²³ = CH ₃ )
[2-26] 6- (Meth) acryloyloxy-1-methyl-2-oxabicyclo [2.2.2] octane-3-one (R = H or CH ₃ , R ²³ = R ²⁴ = R ²⁵ = R ²⁶ = R ²⁷ = R ²⁸ = R ²⁹ = R ³⁰ = H, R ²² = CH ₃ )
[2-27] 6- (Meth) acryloyloxy-1,6-dimethyl-2-oxabicyclo [2.2.2] octane-3-one (R = H or CH ₃ , R ²⁴ = R ²⁵ = R ^{26 = R 27 = R 28 =} R 29 = R 30 = H, R 22 = R 23 = CH 3)
The compounds represented by the above formulas (2d) and (2e) are prepared by a conventional esterification method using a corresponding cyclic alcohol derivative and (meth) acrylic acid or a reactive derivative thereof using an acid catalyst or a transesterification catalyst. It can obtain by making it react according to.

  In this specification, a methacrylic acid ester and an acrylic acid ester may be collectively referred to as a (meth) acrylic acid ester or a (meth) acryloyl group, and the generic resin may be referred to as an acrylic resin. The methacrylic acid ester is a compound in which R is a methyl group in the formulas (1a) to (1c) and (2a) to (2e), and the acrylate ester is a compound in which R is a hydrogen atom.

  In the present invention, the molar ratio of methacrylic acid ester to all monomers used for polymerization, which is an important element, is usually 60 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more. . Moreover, more preferable crystallinity is shown as the molar ratio of methacrylic acid is 99% or more. If the molar ratio of the methacrylic acid ester is less than 60 mol%, the precipitated crystals are likely to condense and adhere to a tank or equipment, making operation difficult.

  Monomers other than methacrylic acid esters are mainly acrylic acid esters, but monomers other than acrylic monomers can also be used. Examples of the non-acrylic monomer include a vinyl ether monomer having an alicyclic skeleton that may have a substituent, a vinyl monomer having an alicyclic skeleton that may have a substituent, and the like. Examples of the vinyl ether monomer include cyclohexyl vinyl ether and adamantyl vinyl ether. Examples of the vinyl monomer include vinylcyclohexane and 1-vinyladamantane. Examples of the substituent include an alkyl group such as a methyl group, a halogen atom such as chlorine and a fluorine atom, a hydroxyl group that may have a protecting group, a carbonyl group that may have a protecting group, and a protecting group. Examples thereof include a carboxyl group which may have, a hydroxymethyl group which may have a protecting group, an amino group which may have a protecting group, an amide group which may have a protecting group, and the like. Examples of the substituent include those known in the field of organic synthesis.

  The polymer obtained by polymerization can be isolated by precipitation or reprecipitation. For example, the polymer solution (polymer dope) is added in a poor solvent (precipitation solvent) to precipitate the polymer, or the polymer is dissolved again in a suitable solvent, and this solution is dissolved in the poor solvent (reprecipitation solvent). The target polymer can be obtained by addition and 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 mixed solvent containing a hydrocarbon (particularly, an aliphatic hydrocarbon such as hexane or heptane) and a polar solvent is preferable. The polar solvent means a solvent other than hydrocarbon among those listed as the precipitation or reprecipitation solvent. In such a mixed solvent, the ratio of the hydrocarbon (for example, an aliphatic hydrocarbon such as hexane and heptane) and the polar solvent (for example, an ester such as ethyl acetate) is, for example, the former / the latter (volume ratio; 25 ° C) = 50/50 to 99/1, preferably the former / the latter (volume ratio; 25 ° C.) = 55/45 to 98/2, more preferably the former / the latter (volume ratio; 25 ° C.) = 60/40 to 97/3, particularly preferably the former / the latter (volume ratio; 25 ° C.) = 65/35 to 95/5. When the polar solvent is 50 (volume ratio) or more, it becomes easy to form a block after centrifugation, or the liquid removal property by centrifugation also deteriorates. On the other hand, if it is smaller than 1, removal of the monomer used for the polymerization tends to be insufficient.

  In the present specification, precipitation and reprecipitation are sometimes collectively referred to as precipitation. Similarly, the precipitation solvent or reprecipitation solvent may be collectively referred to as the precipitation solvent, and the poor solvent is used for precipitation or reprecipitation, and there is no particular distinction between them.

As the centrifuge used in the present invention, any centrifuge having a mechanism for solid-liquid separation by centrifugal force can be used. There are batch and continuous centrifuges, but both can be used. The batch method is preferable for increasing the dehydrating effect.
It is also preferable to wash with water in order to remove the metal content in the polymerization solution after the polymerization. Since the specific gravity of the polymerization solution is often close to 1, it is also preferable to add a solvent having a low specific gravity to the polymerization solution and wash with water. Of the above-described polymerization solvents, those having a low specific gravity are preferred.

  The slurry concentration of the slurry liquid to be centrifuged is usually 0.3 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably about 0.7 to 4% by weight. The slurry concentration is a value obtained by dividing the weight of the wet crystal (solid content: about 35% by weight) after centrifugation by the total amount of the slurry solution. If the slurry concentration is less than 0.3% by weight, it will cause trouble in the preparation of filter cake (pre-coating) in the centrifuge. On the other hand, when the slurry concentration is higher than 10% by weight, the uniformity of the filter cake in the basket in the centrifuge is deteriorated, leading to the cause of vibration and the decrease in liquid removal.

  As the centrifuge, both a batch centrifuge and a continuous centrifuge can be used, but a batch centrifuge is preferable because the liquid content is reduced. The batch centrifuge feeds the slurry to a rotating basket and circulates the filtrate while pre-coating. When a cake is formed to some extent, the filtrate is switched to waste liquid and the filtration is terminated. Further, in order to lower the liquid content after the filtration is completed, this is a so-called liquid removal step in which the rotation speed of the basket, that is, the centrifugal force is increased to shake off the liquid to be impregnated. The liquid removal step is usually performed at 300G to 700G (G: centrifugal force), and the liquid content is high at 300G, and the subsequent step of reducing the poor solvent (the main component of the liquid impregnated in the wet crystal) is burdensome and preferable. Absent. If it exceeds 700G, the cake will stick and it will be difficult to redissolve.

  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 an affinity for the polymer is removed, or when a drying step is employed later, the surface of the polymer particles can be hardened, or 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.
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 poor solvent used in the present invention is an organic solvent having a low boiling point such as heptane. When the work is performed in a state opened to the atmosphere after centrifugation, the centrifugal separation is performed due to the risk of ignition. It is also preferable to rinse with water, particularly pure water, after the liquid is removed.

  The content of low-boiling substances including moisture in the case of a photoresist solution is usually 1.5% by weight or less, preferably 1.3% by weight or less, and more preferably about 1.0% by weight or less. When the low boiling point component is more than 1.5% by weight, a uniform coating film cannot be obtained and a semiconductor pattern is not preferable when a resist film is formed in the semiconductor manufacturing process.

  The photoresist resin composition of the present invention contains a photoacid generator together with the photoresist resin of the present invention. 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 photoresist includes alkali-soluble components such as alkali-soluble resins (for example, novolak resins, phenol resins, imide resins, carboxyl group-containing resins), colorants (for example, dyes), organic solvents (for example, Hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents thereof, etc.) .

  The photoresist resin composition of the present invention can be prepared by dissolving the photoresist resin of the present invention in a solvent (photoresist solvent). More specifically, the photoresist resin of the present invention is used as it is or after being subjected to an appropriate purification treatment as necessary, and then placed in an organic solvent and stirred and mixed with a photoacid generator and the like. A resin composition can be obtained.

  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. In particular, the photoresist resin of the present invention is effective for an ArF excimer laser. 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 detail based on examples, but the present invention is not limited to the examples.

The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined in terms of standard polystyrene by GPC measurement using a refractometer (RI) as a detector and 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. About 1 g of wet crystals were collected and weighed, and the liquid content of wet crystals was calculated from the remaining amount after drying under reduced pressure. The moisture and low boiling point solvent contents were determined by Karl Fischer and gas chromatography. The slurry concentration of the slurry was obtained by collecting about 100 g of the mixed slurry, filtering the precipitate, and vacuum drying at 50 ° C. for 2 hours, and dividing the dry weight by the total amount of the collected slurry.
Example 1
Manufacture of resin solution for photoresist containing resin of the following structure

撹拌機、温度計、還流冷却管及び窒素導入管を備えたガラスライニングの反応器に、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４０ｋｇ導入し、７５℃に昇温後、２−メタクリロイルオキシ−２−メチルアダマンタン（２ＭＭＡ）１１．７ｋｇ（５０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）６．７ｋｇ（３０モル）、１−アクリロイルオキシ−３−ヒドロキシアダマンタン（ＨＡＡ）４．４ｋｇ（２０モル）と、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」）１．５ｋｇ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）７０ｋｇの混合溶液を６時間かけて添加した。添加後、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、これにメチルイソブチルケトン（ＭＩＢＫ）８０ｋｇを加えて混合し、さらに水３００Ｌを添加し、よく撹拌を行った後、３０分静置して分液させた。下層（水層）を除去した後、上層（有機層）を１５００ｋｇ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。生成したスラリーのスラリー濃度は１．３重量％であった。析出した沈殿を遠心分離機（回分式遠心分離機）により遠心分離した。遠心分離機は、ヘプタン／酢酸エチルのポリマースラリー溶液を給液するときは、３００Ｇとなるように、回転数を設定し、２００Ｌ／分で給液した。５分間はプレコートのために濾液はスラリーの原料タンクに戻し、その後濾液は廃液タンクに切り替えて、濾過を実施した。給液終了後、６００Ｇとなるような回転数に上昇させ、２分間脱液を実施した。更に、回転数を３００Ｇとなるような回転数に落として、純水３００Ｌでリンスし、更に回転数６００Ｇ相当に上昇させ、２分間の脱液を行なった。得られた湿結晶は含液率６５重量％（液体６５重量％、固体３５重量％）であった。得られた湿結晶を固形分１０重量％となるように約２５０ｋｇ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。得られた溶液を単蒸留装置に仕込み、２０ｔｏｒｒ（＝２．６６ｋＰａ）の圧力で濃縮を行った。固形分が約４０重量％となった時点で蒸留を停止し、ＰＧＭＥＡ及びＰＧＭＥを添加して、ポリマー濃度２０重量％のＰＧＭＥＡ／ＰＧＭＥ（重量比７／３）溶液を調製した。この溶液はフォトレジスト用樹脂溶液として使用されるが、水分０．６重量％、ヘプタンと酢酸エチルの合計が０．２重量％であった。また、湿結晶を一部採取して、乾燥後、分子量及び分子量分布の測定を実施したところ、分子量は８０００で、分子量分布は２．１であった。
実施例２
下記構造の樹脂を含むフォトレジスト用樹脂溶液の製造

40 kg of propylene glycol monomethyl ether acetate (PGMEA) was introduced into a glass-lined reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, heated to 75 ° C., and then 2-methacryloyloxy-2- Methyladamantane (2MMA) 11.7 kg (50 mol), 5-methacryloyloxy-2,6-norbornylcarbolactone (MNBL) 6.7 kg (30 mol), 1-acryloyloxy-3-hydroxyadamantane (HAA) 4.4 kg (20 mol), 1.5 kg of dimethyl-2,2′-azobis (2-methylpropionate) (initiator: Wako Pure Chemical Industries, trade name “V-601”), and propylene glycol A mixed solution of 70 kg of monomethyl ether acetate (PGMEA) was added over 6 hours. After the addition, the mixture was aged at the same temperature for 2 hours. After cooling the obtained reaction solution (polymer dope), 80 kg of methyl isobutyl ketone (MIBK) was added thereto and mixed. Further, 300 L of water was added, and after stirring well, the mixture was allowed to stand for 30 minutes to separate the liquid. I let you. After removing the lower layer (aqueous layer), the upper layer (organic layer) was added dropwise to 1500 kg of heptane / ethyl acetate mixture (weight ratio 75/25) with stirring, and after completion of the addition, the mixture was further stirred for 30 minutes. The slurry concentration of the produced slurry was 1.3% by weight. The deposited precipitate was centrifuged with a centrifuge (batch centrifuge). When supplying the polymer slurry solution of heptane / ethyl acetate, the centrifuge was set at a rotational speed of 300 L and supplied at 200 L / min. The filtrate was returned to the slurry raw material tank for pre-coating for 5 minutes, and then the filtrate was switched to the waste liquid tank for filtration. After completion of the liquid supply, the number of revolutions was increased to 600 G, and liquid removal was performed for 2 minutes. Further, the rotational speed was lowered to 300 G, rinsed with 300 L of pure water, further increased to a rotational speed equivalent to 600 G, and liquid removal was performed for 2 minutes. The obtained wet crystals had a liquid content of 65% by weight (liquid 65% by weight, solid 35% by weight). The obtained wet crystals were added to about 250 kg of propylene glycol monomethyl ether (PGME) so as to have a solid content of 10% by weight, and dissolved by stirring. The obtained solution was charged into a simple distillation apparatus and concentrated at a pressure of 20 torr (= 2.66 kPa). When the solid content reached about 40% by weight, the distillation was stopped and PGMEA and PGME were added to prepare a PGMEA / PGME (weight ratio 7/3) solution having a polymer concentration of 20% by weight. This solution was used as a photoresist resin solution, but the water content was 0.6% by weight and the total of heptane and ethyl acetate was 0.2% by weight. A part of the wet crystals was collected and dried, and the molecular weight and molecular weight distribution were measured. The molecular weight was 8000 and the molecular weight distribution was 2.1.
Example 2
Manufacture of resin solution for photoresist containing resin of the following structure

重合に仕込まれたモノマーは、２−メタクリロイルオキシ−２−メチルアダマンタン（２ＭＭＡ）１１．７ｋｇ（５０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）６．７ｋｇ（３０モル）、１−メタクリロイルオキシ−３−ヒドロキシアダマンタン（ＨＭＡ）４．７ｋｇ（２０モル）である以外は実施例１と同様な操作を実施した。遠心分離後、得られた湿結晶の含液率は６５重量％であり、調整されたフォトレジスト用樹脂溶液としては、水分０．５重量％、ヘプタンと酢酸エチルの合計が０．１重量％であった。得られた高分子化合物の分子量は８１００で、分子量分布は２．２であった。
実施例３
下記構造の樹脂を含むフォトレジスト用樹脂溶液の製造

The monomers charged in the polymerization were 2-methacryloyloxy-2-methyladamantane (2MMA) 11.7 kg (50 mol), 5-methacryloyloxy-2,6-norbornylcarbolactone (MNBL) 6.7 kg (30 kg). Mol) and 1-methacryloyloxy-3-hydroxyadamantane (HMA) 4.7 kg (20 mol), and the same operation as in Example 1 was performed. After centrifuging, the liquid content of the obtained wet crystals was 65% by weight, and the adjusted photoresist resin solution had a water content of 0.5% by weight, and the total of heptane and ethyl acetate was 0.1% by weight. Met. The obtained polymer compound had a molecular weight of 8,100 and a molecular weight distribution of 2.2.
Example 3
Manufacture of resin solution for photoresist containing resin of the following structure

重合に仕込まれたモノマーは、２−メタクリロイルオキシ−２−メチルアダマンタン（２ＭＭＡ）１１．７ｋｇ（５０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）６．７ｋｇ（３０モル）、１−メタクリロイルオキシ−３、５−ジヒドロキシアダマンタン（ＤＨＭＡ）５．０ｋｇ（２０モル）である以外は実施例１と同様な操作を実施した。遠心分離後、得られた湿結晶の含液率は６５重量％であり、調整されたフォトレジスト用樹脂溶液としては、水分０．５重量％、ヘプタンと酢酸エチルの合計が０．１重量％であった。得られた高分子化合物の分子量は８０００で、分子量分布は２．０であった。
比較例１
下記構造の樹脂を含むフォトレジスト用樹脂溶液の製造

The monomers charged in the polymerization were 2-methacryloyloxy-2-methyladamantane (2MMA) 11.7 kg (50 mol), 5-methacryloyloxy-2,6-norbornylcarbolactone (MNBL) 6.7 kg (30 kg). Mol), 1-methacryloyloxy-3,5-dihydroxyadamantane (DHMA) 5.0 kg (20 mol), and the same operation as in Example 1 was performed. After centrifuging, the liquid content of the obtained wet crystals was 65% by weight, and the adjusted photoresist resin solution had a water content of 0.5% by weight, and the total of heptane and ethyl acetate was 0.1% by weight. Met. The obtained polymer compound had a molecular weight of 8,000 and a molecular weight distribution of 2.0.
Comparative Example 1
Manufacture of resin solution for photoresist containing resin of the following structure

重合に仕込まれたモノマーは、２−メタクリロイルオキシ−２−メチルアダマンタン（２ＭＭＡ）２．３ｋｇ（１０モル）、２−アクリロイルオキシ−２−メチルアダマンタン（２ＡＭＡ）８．８ｋｇ（４０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）６．７ｋｇ（３０モル）、１−アクリロイルオキシ−３−ヒドロキシアダマンタン（ＨＡＡ）４．４ｋｇ（２０モル）である以外は実施例１と同様な操作を実施した。遠心分離機に沈殿物が付着して、固液分離することが出来なかった。

比較例２
下記構造の樹脂を含むフォトレジスト用樹脂溶液の製造

Monomers charged for polymerization were 2.3 kg (10 mol) of 2-methacryloyloxy-2-methyladamantane (2MMA), 8.8 kg (40 mol) of 2-acryloyloxy-2-methyladamantane (2AMA), 5- Example 1 except that methacryloyloxy-2,6-norbornylcarbolactone (MNBL) is 6.7 kg (30 mol) and 1-acryloyloxy-3-hydroxyadamantane (HAA) is 4.4 kg (20 mol). Similar operations were performed. A precipitate adhered to the centrifuge, and solid-liquid separation could not be performed.

Comparative Example 2
Manufacture of resin solution for photoresist containing resin of the following structure

重合に仕込まれたモノマーは、２−メタクリロイルオキシ−２−メチルアダマンタン（２ＭＭＡ）４．７ｋｇ（２０モル）、２−アクリロイルオキシ−２−メチルアダマンタン（２ＡＭＡ）７．０ｋｇ（３０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）６．７ｋｇ（３０モル）、１−アクリロイルオキシ−３−ヒドロキシアダマンタン（ＨAＡ）４．４ｋｇ（２０モル）である以外は実施例１と同様な操作を実施した。遠心分離機に沈殿物が付着して、固液分離することが出来なかった。

The monomers charged for polymerization were 2-methacryloyloxy-2-methyladamantane (2MMA) 4.7 kg (20 mol), 2-acryloyloxy-2-methyladamantane (2AMA) 7.0 kg (30 mol), 5- Example 1 except that methacryloyloxy-2,6-norbornylcarbolactone (MNBL) is 6.7 kg (30 mol) and 1-acryloyloxy-3-hydroxyadamantane (HAA) is 4.4 kg (20 mol). Similar operations were performed. A precipitate adhered to the centrifuge, and solid-liquid separation could not be performed.

Claims (7)

A monomer including a monomer A having a group that becomes alkali-soluble upon elimination by acid and a monomer B having a polar group-containing alicyclic skeleton and a polymerization initiator are dissolved in a solvent, and the temperature is raised to the polymerization temperature. Add the polymerization solution to a poor solvent (precipitation solvent) to precipitate the polymer, centrifuge the precipitate with a centrifuge to remove the solvent, and then dissolve the wet crystals in the solvent. In the method for producing a solution of a photoresist polymer compound by concentration by distillation under reduced pressure, the molar ratio of methacrylic acid ester is 60 mol% or more with respect to all monomers used for polymerization. Method for producing a high molecular compound for photoresist. Monomer A is represented by the following formulas (1a) to (1c)

(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 alkyl group having 1 to 6 carbon atoms. R ¹ to R ³ is the same or different and represents an alkyl group having 1 to 6 carbon atoms, R ⁴ is a substituent bonded to the ring Z, and is the same or different and represents an oxo group, 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, provided that at least one of n R ⁴ is And —COOR ^a group, wherein R ^a represents an optionally substituted tertiary hydrocarbon group, tetrahydrofuranyl group, tetrahydropyranyl group, or oxepanyl group, n is an integer of 1 to 3. At least one monomer selected from The method for producing a polymer compound for photoresist according to claim 1, wherein: Monomer B is represented by the following formulas (2a) to (2e)

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^{5 to} R ⁷ are the same or different and are a hydrogen atom, an alkyl group, or a hydroxyl group optionally protected by a protecting group, 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 represent —CH ₂ —, —CO— or —; COO— provided that (i) at least one of V ^{1 to} V ³ is —CO— or —COO—, or (ii) at least one of R ^{5 to} R ⁷ is a protecting group A hydroxyl group which may be protected with, a hydroxyalkyl group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group, R ^{8 to} R ¹² may be the same or different; Protected with hydrogen atom, alkyl group, protecting group A hydroxyl group that may be protected, a hydroxyalkyl group that may be protected with a protecting group, and a carboxyl group that may be protected with a protecting group, R ^{13 to} R ²¹ may be the same or different and each 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 ^{22 to} R ³⁰ are the same. Or 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) 2. The method for producing a polymer compound for photoresist according to claim 1, wherein the monomer is at least one selected monomer. 2. The method for producing a photoresist polymer compound according to claim 1, wherein the solvent for dissolving the wet crystal after centrifugation is one solvent selected from glycol ether solvents and ester solvents. The method for producing a photoresist polymer compound according to claim 1, wherein the poor solvent (precipitation solvent) is a mixture of a hydrocarbon solvent and a polar solvent. A monomer including a monomer A having a group that becomes alkali-soluble upon elimination by an acid and a monomer B having a polar group-containing alicyclic skeleton and a polymerization initiator are dissolved in a solvent, and the temperature is raised to the polymerization temperature. The polymer is added dropwise to a poor solvent, the polymer is precipitated, the precipitate is centrifuged by a centrifuge, the solvent is removed, and the wet crystals are dissolved in a glycol solvent. A method for producing a photoresist resin solution by concentrating by distillation under reduced pressure, and further comprising a polymer compound for photoresist and a photoacid produced according to any one of claims 1 to 5 A photoresist resin composition comprising at least a generator. A method for producing a semiconductor, comprising applying the resin composition for a photoresist according to claim 6 on a substrate and exposing the substrate to light with a wavelength of 193 nm.