JP2006199764A - Method for producing macromolecular compound for photoresist - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a macromolecular compound for photoresist, affording good quality in the film-forming step of semiconductor production process when used as a resin component of a resin composition for the photoresist. <P>SOLUTION: The method comprises the following process: Monomers essentially comprising a monomer A bearing such a group as to make the monomer soluble to an alkali on being eliminated by an acid and a monomer B having a polar group-containing alicyclic skeleton and a polymerization initiator are dissolved in a solvent followed by carrying out a polymerization while dripping the resultant solution into a solvent heated to the polymerization temperature. The resultant polymerization solution is added to a poor solvent(precipitating solvent) to precipitate the resultant polymer, which is centrifuged by a centrifugal separator at the centrifugal force of 400-700 G(G: acceleration of gravity) to remove the solvent. The resultant wet crystal is dissolved in a glycol-based solvent followed by distillation at reduced pressures to effect concentration to obtain the objective macromolecular compound in the form of a solution. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a photoresist polymer compound useful for the preparation of a photoresist resin composition used for semiconductor fine processing 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)
These polymers are usually produced by solution polymerization of monomers having respective functions using a radical initiator. In this method, it is difficult to completely polymerize the monomer, and when the remaining monomer is mixed into the resist solution as it is, the light having a wavelength of 193 nm is absorbed because of the double bond in the molecule, and the exposure is accurate. A latent image cannot be drawn. Therefore, after polymerization, unreacted monomers require a precipitation step using a poor solvent (precipitation solvent). In this step, the monomer is easily dissolved in a poor solvent and can be separated from the produced polymer. The precipitated polymer is usually separated by a solid-liquid separation method such as centrifugation. The wet crystal that has been subjected to solid-liquid separation contains an organic solvent mainly composed of a poor solvent, which is a low-boiling component and adversely affects film formation in the semiconductor process. Therefore, drying can be considered in order to remove these low-boiling substances such as organic solvents. However, once the polymer is dried, it is difficult to completely dissolve again because it contains the polar groups. In addition, drying involves a complicated operation, and there is a risk of contamination of impurities such as metals. There has not yet been proposed a simplified method for photoresist polymer compounds with a low content of low-boiling substances.
JP 07-252324 A JP 09-073173 A Japanese Patent Laid-Open No. 2000-026446

  Accordingly, an object of the present invention is to provide a method for producing a photoresist polymer compound having good quality for film formation in a semiconductor production process when used as a resin component of a photoresist resin composition. .

  As a result of intensive studies to achieve the above object, the present invention reprecipitates the solution after polymerization with a poor solvent, and solid-liquid separation converts the obtained wet crystals into a glycol ether solvent having an appropriate amount of solvent. In the process of dissolving, concentrating, and adjusting the concentration, low-boiling components that adversely affect the semiconductor film-forming process are removed by carrying out the centrifugal force in the liquid removal of the centrifuge used for solid-liquid separation within a specific range. As a result, the present invention has been completed.

  That is, the present invention dissolves in a solvent a monomer and a polymerization initiator that include 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, Polymerization while dropping into a solvent heated to the polymerization temperature, adding the polymerization solution to a poor solvent (precipitation solvent), precipitating the polymer, and removing the solvent by centrifugation with a centrifuge, In a method of dissolving a wet crystal in a glycol-based solvent and concentrating by distillation under reduced pressure to produce a solution of a photoresist polymer compound, the liquid is removed at a centrifugal force of 400 to 700 G (G: gravity acceleration). A method for producing a polymer compound for photoresists is provided.

  In the present invention, a monomer A having a group that is eliminated by an acid and becomes alkali-soluble and a monomer B having a polar group-containing alicyclic skeleton and a polymerization initiator are dissolved in a solvent, and polymerization is performed. Polymerize while dropping into a solvent heated to a temperature, add the polymerization solution to a poor solvent, precipitate the polymer, centrifuge the precipitate with a centrifuge, remove the solvent, and then wet the crystals into a glycol system In a method for producing a photoresist polymer solution by dissolving in a solvent and concentrating by distillation under reduced pressure, rinsing with pure water after centrifugation, and further removing the liquid at a centrifugal force of 400 to 700 G. The method for producing a polymer compound for a photoresist as described above is provided.

  In the present invention, the monomer A is further represented by 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法を提供する。

(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 The present invention provides a method for producing a polymer compound for photoresists as described above.

  In the present invention, the monomer B is further 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法を提供する。

(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) The method for producing a polymer compound for photoresist as described above, which is at least one selected monomer.

  The present invention also provides the high molecular weight compound for a photoresist as described above, wherein when the polymer slurry is supplied to the centrifugal separator in the centrifugal separation step, the centrifugal force of the centrifugal separator is 50 to 600 G. Provides a manufacturing method.

  The present invention further provides a high concentration for photoresists as described above, wherein the slurry concentration of the slurry solution to be processed by the centrifuge is 1 to 10 wt% (wt% of the weight of wet crystals with respect to the total slurry solution). A method for producing molecular compounds.

  The present invention also provides a method for producing a polymer compound for photoresists as described above, wherein when the polymerized polymer compound solution is precipitated, a mixture of a hydrocarbon solvent and a polar solvent is used as a poor solvent. provide.

  The present invention further includes dissolving a monomer A having a group which is eliminated by an acid and becomes alkali-soluble, and a monomer B having a polar group-containing alicyclic skeleton and a polymerization initiator in a solvent to perform polymerization. Polymerize while dropping into a solvent heated to a temperature, add the polymerization solution to a poor solvent, precipitate the polymer, centrifuge the precipitate with a centrifuge, remove the solvent, and then wet the crystals into a glycol system A method for producing a photoresist resin solution by dissolving in a solvent and concentrating by distillation under reduced pressure, wherein the photoresist resin comprises at least a polymer compound for photoresist and a photoacid generator produced as described above A composition is provided.

  This invention provides the manufacturing method of the semiconductor characterized by apply | coating the said resin composition for photoresists on a board | substrate, and exposing with the light of wavelength 193nm.

  In the present specification, “acryl” and “methacryl” may be collectively referred to as “(meth) acryl”, “acryloyl” and “methacryloyl” may be collectively referred to as “(meth) acryloyl”, and the like. In addition, as a protecting group such as a hydroxyl group and a carboxyl group, those commonly used in the field of organic synthesis can be used.

  Since the present invention is a high molecular compound corresponding to a monomer containing at least a monomer A having an alkali-soluble group that is eliminated by an acid and a monomer B having a polar group-containing alicyclic skeleton, It is useful as a polymer compound for resist, and furthermore, a high-quality polymer compound for resist can be obtained by specific conditions in the precipitation step and the centrifugation step after polymerization, and thereby uniform resist coating in the semiconductor manufacturing process. The film can be created.

  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 is —COO— in the formula (2a), 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 polymer compound for photoresist of the present invention is, for example, a monomer mixture containing 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 It is also possible to drop the monomer solution containing the polymerization initiator and the polymerization initiator solution containing the polymerization initiator into the reaction vessel in parallel from separate containers, and mixing and dissolving the monomer and the polymerization initiator. It can also be dripped. When the monomer solution and the polymerization initiator solution are charged separately, it is important that the charging speed is accurately controlled. If the balance is lost, the molecular weight and molecular weight distribution of the produced polymer compound are important. Affects. In addition, when the monomer and the polymerization initiator are mixed and dissolved and dropped, it is also preferable to cool the container in order to suppress a small amount of polymerization due to decomposition of the polymerization initiator in the dropping container.

  The polymerization temperature in the production method of the present invention can be selected from a temperature range of 60 to 130 ° C. What is important with respect to the polymerization temperature is that a polymerization process with a small fluctuation width at the set temperature is required. In the polymerization, that is, the dropping time of the monomer / polymerization initiator solution and the aging time after dropping, it is particularly preferable that 90% or more of the total time is temperature controlled at ± 1.0 ° C. or less. If the polymerization temperature varies more than ± 1.0 ° C, it may be due to the compositional variation of the polymer compound to be generated, or a polymer compound with poor solubility in the solvent will be generated. A process is required.

  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 single solvent for propylene glycol monomethyl ether acetate, 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 polymerization initiator. However, those having a low metal content are preferred.

  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 that takes into consideration productivity, economy, workability, operability, etc. In general, the former / the latter (weight ratio) = 5/95 to 90/10, preferably 10/90 to 70/30, and 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 or the amount of the solvent in the solution + the amount of the solvent in the solution to be dropped) takes into consideration the workability, operability, reaction efficiency, solubility of the polymer to be produced, etc. Although it can select suitably, generally it is 100-2000 weight part with respect to the total amount of a monomer of 100 weight part, Preferably it is 200-1000 weight part, More preferably, it is about 300-700 weight part.

  The total dropping time of the monomer solution and the polymerization initiator solution varies depending on the polymerization temperature, the kind of the monomer, and the like, but is generally 1 to 10 hours, preferably about 3 to 8 hours. The polymerization temperature is particularly difficult to control in the first half of the dropping operation of the monomer solution or the polymerization initiator solution (up to 1/2 of the total dropping time), and the temperature fluctuation range tends to increase. Therefore, it is particularly preferable to control the polymerization temperature within ± 5 ° C. (preferably within ± 3 ° C.) with respect to the set temperature for 95% or more of the first half dropping time in the dropping operation of the monomer solution or the polymerization initiator solution. preferable. In addition, after completion | finish of dripping, you may age | cure | ripen for appropriate time (for example, about 0.1 to 10 hours, Preferably about 1 to 6 hours) and appropriate temperature (for example, 60-130 degreeC), and you may complete superposition | polymerization.

  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.

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 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.

  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 1 to 10% by weight, preferably 1.5 to 8% by weight, particularly preferably about 2 to 6% 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 1% 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.

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

As the solvent used for the repulping treatment (solvent for repulping) and the solvent used for the rinsing treatment (solvent for rinsing), a poor solvent for the polymer used for precipitation or reprecipitation is preferred. Of these, hydrocarbon solvents are particularly preferred. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene. You may use these in mixture of 2 or more types. Among these, aliphatic hydrocarbons, particularly hexane or heptane, or a mixed solvent containing hexane or heptane is preferable.
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 a low-boiling organic solvent such as hexane. 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, for example, ultraviolet rays, X-rays, etc. can be used. For semiconductor resist, g-line, i-line, excimer laser (for example, XeCl, KrF, KrCl, ArF, ArCl, etc.) 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 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.
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３５ｋｇ導入し、７５℃に昇温後、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）５ｋｇ（２２モル）、２−メタクリロイルオキシ−２−メチルアダマンタン（２ＭＭＡ）５ｋｇ（２１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）５ｋｇ（２１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」）９３０ｇ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）４０ｋｇ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）５５ｋｇを加えて混合し、さらに水２００ｋｇ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１０００ｋｇ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。スラリー濃度は３．６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、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２００Ｌ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１３０ｋｇ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０．５重量％、ヘプタンと酢酸エチルの合計が０．１重量％であった。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８２００で、分子量分布は１．９であった。
実施例２
遠心分離機での固液分離工程での遠心分離機の脱液における回転数、及び純水によるリンス後の脱液時の回転数を５００Ｇ相当にした以外は、実施例１と同様な操作を実施した。得られた湿結晶は含液率６６重量％であり、単蒸留による濃縮後、ポリマー濃度２０重量％に濃度調整した結果、フォトレジスト用樹脂溶液として、水分０．５重量％、ヘプタンと酢酸エチルの合計が０．１重量％の溶液が得られた。得られた高分子化合物の分子量及び分子量分布は実施例１と同等であった。
実施例３
遠心分離機での固液分離工程での遠心分離機の脱液における回転数、及び純水によるリンス後の脱液時の回転数を７００Ｇ相当にした以外は、実施例１と同様な操作を実施した。得られた湿結晶は含液率６５重量％であり、単蒸留による濃縮後、ポリマー濃度２０重量％に濃度調整した結果、フォトレジスト用樹脂溶液として、水分０．５重量％、ヘプタンと酢酸エチルの合計が０．１重量％の溶液が得られた。得られた高分子化合物の分子量及び分子量分布は実施例１と同等であった。
比較例１
遠心分離機での固液分離工程での遠心分離機の脱液における回転数、及び純水によるリンス後の脱液時の回転数を３００Ｇ相当にした以外は、実施例１と同様な操作を実施した。得られた湿結晶は含液率７３重量％であり、単蒸留による濃縮後、ポリマー濃度２０重量％に濃度調整した結果、フォトレジスト用樹脂溶液として、水分１．５重量％、ヘプタンと酢酸エチルの合計が０．４重量％の溶液が得られ、低沸点成分が多いので再処理が必要であった。得られた高分子化合物の分子量及び分子量分布は実施例１と同等であった。
比較例２
遠心分離機での固液分離工程での遠心分離機の脱液における回転数、及び純水によるリンス後の脱液時の回転数を８００Ｇ相当にした以外は、実施例１と同様な操作を実施した。湿結晶の含液率は６４重量％であったが、結晶が硬くて、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）に添加しても溶解しない。湿結晶は粉砕して、ＰＧＭＥに溶解させた。しかし、完全には溶解できず、濾過が必要であった。得られた高分子化合物の分子量及び分子量分布は実施例１と同等であった。

35 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 inlet, and after raising the temperature to 75 ° C., 5-methacryloyloxy-2, 6-norbornylcarbolactone (MNBL) 5 kg (22 mol), 2-methacryloyloxy-2-methyladamantane (2MMA) 5 kg (21 mol), 1-methacryloyloxy-3-hydroxyadamantane (HMA) 5 kg (21 mol) ), 930 g of dimethyl-2,2′-azobis (2-methylpropionate) (initiator: Wako Pure Chemical Industries, trade name “V-601”), and 40 kg of propylene glycol monomethyl ether acetate (PGMEA) The mixed solution 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), 55 kg of methyl isobutyl ketone (MIBK) was added thereto and mixed. Further, 200 kg of water was added, and after stirring well, the mixture was allowed to stand for 30 minutes for separation. I let you. After removing the lower layer (aqueous layer), the upper layer (organic layer) was added dropwise to 1000 kg 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 slurry concentration was 3.6% by weight. The deposited precipitate was centrifuged with a centrifuge (batch centrifuge). When supplying the polymer slurry solution of heptane / ethyl acetate, the centrifuge sets the rotation speed so as to be 300 G, and after the completion of the liquid supply, the rotation speed is increased to 600 G for 2 minutes. Draining was performed. Further, the rotational speed was lowered to 300 G, rinsed with 200 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 130 kg of propylene glycol monomethyl ether (PGME) to 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 0.5% by weight and the total of heptane and ethyl acetate was 0.1% by weight. A part of the wet crystals was sampled and dried, and the molecular weight and molecular weight distribution were measured. The molecular weight was 8,200 and the molecular weight distribution was 1.9.
Example 2
The same operation as in Example 1 was carried out except that the rotation speed at the time of liquid removal of the centrifuge in the solid-liquid separation process at the centrifuge and the rotation speed at the time of liquid removal after rinsing with pure water were equivalent to 500G. Carried out. The obtained wet crystals had a liquid content of 66% by weight. After concentration by simple distillation, the polymer concentration was adjusted to 20% by weight. As a result, the photoresist resin solution contained 0.5% by weight of water, heptane and ethyl acetate. A solution with a total of 0.1% by weight was obtained. The molecular weight and molecular weight distribution of the obtained polymer compound were the same as in Example 1.
Example 3
The same operation as in Example 1 was performed except that the number of rotations in the centrifuge dewatering in the solid-liquid separation process in the centrifuge and the number of rotations in the dewatering after rinsing with pure water were equivalent to 700G. Carried out. The obtained wet crystals had a liquid content of 65% by weight. After concentration by simple distillation, the concentration of the polymer was adjusted to 20% by weight. As a result, the photoresist resin solution contained 0.5% by weight of water, heptane and ethyl acetate. A solution with a total of 0.1% by weight was obtained. The molecular weight and molecular weight distribution of the obtained polymer compound were the same as in Example 1.
Comparative Example 1
The same operation as in Example 1 was carried out except that the rotation speed in the centrifuge drainage in the solid-liquid separation process in the centrifuge and the rotation speed in the drainage after rinsing with pure water were equivalent to 300G. Carried out. The obtained wet crystals had a liquid content of 73% by weight. After concentration by simple distillation, the polymer concentration was adjusted to 20% by weight. As a result, the resin solution for photoresist was 1.5% by weight water, heptane and ethyl acetate. As a result, a solution with a total of 0.4% by weight was obtained, and since there were many low-boiling components, reprocessing was necessary. The molecular weight and molecular weight distribution of the obtained polymer compound were the same as in Example 1.
Comparative Example 2
The same operation as in Example 1 was performed except that the rotation speed at the time of liquid removal of the centrifuge in the solid-liquid separation process at the centrifuge and the rotation speed at the time of liquid removal after rinsing with pure water were equivalent to 800G. Carried out. The liquid content of wet crystals was 64% by weight, but the crystals were hard and did not dissolve even when added to propylene glycol monomethyl ether (PGME). The wet crystals were crushed and dissolved in PGME. However, it could not be completely dissolved and filtration was necessary. The molecular weight and molecular weight distribution of the obtained polymer compound were the same as in Example 1.

Claims (9)

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. The polymer solution is added dropwise to a poor solvent (precipitation solvent), the polymer is precipitated, the precipitate is centrifuged by a centrifuge, the solvent is removed, and the wet crystal is dissolved in a glycol solvent. In the method of producing a solution of a photoresist polymer compound by dissolving in a vacuum and concentrating by vacuum distillation, the centrifugal force in centrifugation is 400 to 700 G (G: gravitational acceleration), and the liquid is removed. A method for producing a polymer compound for photoresist. 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. 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 solution of a photoresist polymer compound by concentrating by distillation under reduced pressure, characterized by rinsing with pure water after centrifugation and further removing the solution at a centrifugal force of 400 to 700 G in centrifugation. A method for producing a polymer compound for photoresists according to claim 1. 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 photoresist polymer compound according to claim 1, wherein the monomer is at least one selected monomer. 2. The method for producing a polymer compound for photoresist according to claim 1, wherein when the polymer slurry is supplied to the centrifuge in the centrifugation step, the centrifugal force of the centrifuge is 50 to 600G. . The mixture of a hydrocarbon solvent and a polar solvent is used as a poor solvent when the polymerized polymer compound solution is precipitated. 2. The high molecular weight compound for photoresist according to claim 1, wherein the slurry concentration of the slurry solution to be processed by the centrifuge is 1 to 10 wt% (wt% of the weight of wet crystals with respect to the total slurry solution). Manufacturing method. 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. 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 concentration by distillation under reduced pressure, wherein the photopolymer comprises at least a polymer compound for photoresist and a photoacid generator produced according to claim 1. Resin resin composition. A method for producing a semiconductor, comprising applying the resin composition for a photoresist according to claim 8 on a substrate and exposing the substrate to light with a wavelength of 193 nm.