JP6238722B2 - Monomer, polymer compound and photoresist composition containing carbamoyl group and lactone skeleton - Google Patents

Description

  The present invention relates to a monomer for a photoresist, a polymer compound, a photoresist composition, and a semiconductor manufacturing method using the photoresist composition, which are used when fine processing of a semiconductor is performed.

  In the manufacture of semiconductors, lithographic techniques for pattern formation have recently been made extremely fine in line width due to dramatic innovation. Initially, i-line and g-line were used for exposure for lithography, and the line width was wide. Therefore, the capacity of the manufactured semiconductor was low. However, recent technological developments have made it possible to use a KrF excimer laser, and the line width has become extremely fine. Since then, development has progressed with the aim of applying an ArF excimer laser having a shorter wavelength, and its practical application has been made in recent years. In the exposure with a KrF excimer laser, a conventional novolac or styrene resin was used, but the wavelength of the ArF excimer laser is 193 nm, which is even shorter, and aromatic such as a novolac or styrene resin. In order to absorb the wavelength, the structure of the resin was replaced with an alicyclic one that does not contain aromatics. The resin used is mainly acrylic, and applies a mechanism in which acrylic acid is protected with a protecting group, and the protecting group is eliminated by an acid generated by exposure to form a carboxylic acid, which becomes alkali-soluble. Many of the protective groups currently used are alicyclic and do not have a polar group, which alone lacks adhesion to the substrate or lacks affinity with an alkali developer, and so on. Many acrylic monomers having an alicyclic skeleton as an ester group have been proposed. Among them, an alicyclic skeleton having a lactone ring as a polar group is highly evaluated for its functionality and is used in large numbers. There exists patent document 1 as the part. There is also a proposal of a monocyclic ester group of a lactone ring in Patent Document 2 and the like, but the single ring lacks the most required function of a resist, ie, etching resistance, and does not seem to be used so much. Currently, a method called immersion exposure, in which the space between the substrate and the exposure machine is filled with a high-density liquid, has been studied. Further, the resist pattern has become finer and the film thickness tends to be reduced accordingly. There is a strong demand for monomers containing Further, a resin having a large amount of an alicyclic acrylic ester having a lactone ring has difficulty in solubility in an organic solvent such as a resist solvent, and there is a strong demand for a resin used in a resist for improving solubility.

  Patent Document 3 proposes to use, as a photoresist resin, a polymer obtained by polymerizing a vinyl monomer having a ring containing a cyano group and a lactone skeleton in its molecule. This polymer is advantageous in that it is easily dissolved in a resist solvent and has excellent hydrolyzability. However, it is not always sufficient in terms of affinity for water.

Japanese Patent Laid-Open No. 2000-026446 JP-A-10-274852 WO2009 / 107327

  The object of the present invention is to maintain stability such as chemical resistance when applied to a resist resin and the like, while having excellent solubility in organic solvents and high affinity for water, and therefore water after hydrolysis. Monomer containing a novel lactone skeleton useful as a monomer component such as a high-functional polymer excellent in solubility in water, its production method, a resin obtained by polymerizing the monomer, and a composition for photoresist Another object is to provide a semiconductor manufacturing method. A further object of the present invention is to provide a photoresist resin and a composition thereof excellent in the balance of performance such as etching resistance, affinity for an alkaline developer, solvent solubility when used as a resin for a photoresist. is there.

  As a result of various studies on monomers having a lactone skeleton used in photoresist resins, the present inventors have good solvent solubility when used as resins, high affinity for water, and after alkaline hydrolysis. The present inventors have completed the present invention by finding a monomer having excellent solubility in water and high resist performance.

［式中、Ｒ^aは水素原子、ハロゲン原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を示し、Ｒ¹は環に結合している置換基であって、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、ヒドロキシル基部分が保護基で保護されていてもよく且つハロゲン原子を有していてもよい炭素数１〜６のヒドロキシアルキル基、塩を形成していてもよいカルボキシル基、又は置換オキシカルボニル基を示す。Ａは炭素数１〜６のアルキレン基、酸素原子、硫黄原子又は非結合を示す。ｍはＲ¹の個数であって０〜８の整数を示す。Ｘは下記式（２）

（式中、Ｒ^b、Ｒ^cはそれぞれ独立に、水素原子、又は置換基を有していてもよいアルキル基を示す。Ｒ^b、Ｒ^cは互いに結合して、式中に示される窒素原子とともに環を形成していてもよい）
で表されるカルバモイル基を示す。ｎは環に結合しているＸの個数であって１〜９の整数を示す。Ｙは炭素数１〜６の２価の有機基を示す。ｋは０又は１を示す。ＣＨ₂＝Ｃ（Ｒ^a）ＣＯ−（Ｏ−Ｙ−ＣＯ）_k−Ｏ−基の立体的な位置はエンド、エキソの何れであってもよい］
で表されるカルバモイル基及びラクトン骨格を含む単量体を提供する。 That is, the present invention provides the following formula (1):

[Wherein, R ^a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ represents a substituent bonded to the ring, An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms in which a hydroxyl group portion may be protected with a protecting group and may have a halogen atom An alkyl group, a carboxyl group that may form a salt, or a substituted oxycarbonyl group is shown. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represent a hydrogen atom or an optionally substituted alkyl group. R ^b and R ^c are bonded to each other to form a nitrogen atom represented by the formula And may form a ring together)
The carbamoyl group represented by these is shown. n is the number of X bonded to the ring and represents an integer of 1 to 9. Y represents a divalent organic group having 1 to 6 carbon atoms. k represents 0 or 1. The steric position of the CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k —O— group may be either endo or exo.
The monomer containing the carbamoyl group represented by these and the lactone skeleton is provided.

［式中、Ｒ^aは水素原子、ハロゲン原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を示し、Ｒ¹は環に結合している置換基であって、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、ヒドロキシル基部分が保護基で保護されていてもよく且つハロゲン原子を有していてもよい炭素数１〜６のヒドロキシアルキル基、塩を形成していてもよいカルボキシル基、又は置換オキシカルボニル基を示す。Ａは炭素数１〜６のアルキレン基、酸素原子、硫黄原子又は非結合を示す。ｍはＲ¹の個数であって０〜８の整数を示す。Ｘは下記式（２）

（式中、Ｒ^b、Ｒ^cはそれぞれ独立に、水素原子、又は置換基を有していてもよいアルキル基を示す。Ｒ^b、Ｒ^cは互いに結合して、式中に示される窒素原子とともに環を形成していてもよい）
で表されるカルバモイル基を示す。Ｙは炭素数１〜６の２価の有機基を示す。ｋは０又は１を示す。ＣＨ₂＝Ｃ（Ｒ^a）ＣＯ−（Ｏ−Ｙ−ＣＯ）_k−Ｏ−基の立体的な位置はエンド、エキソの何れであってもよい］
で表される化合物が含まれる。 The monomer includes the following formula (1a)

[Wherein, R ^a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ represents a substituent bonded to the ring, An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms in which a hydroxyl group portion may be protected with a protecting group and may have a halogen atom An alkyl group, a carboxyl group that may form a salt, or a substituted oxycarbonyl group is shown. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represent a hydrogen atom or an optionally substituted alkyl group. R ^b and R ^c are bonded to each other to form a nitrogen atom represented by the formula And may form a ring together)
The carbamoyl group represented by these is shown. Y represents a divalent organic group having 1 to 6 carbon atoms. k represents 0 or 1. The steric position of the CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k —O— group may be either endo or exo.
The compound represented by these is included.

［式中、Ｒ^aは水素原子、ハロゲン原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を示し、Ｒ¹は環に結合している置換基であって、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、ヒドロキシル基部分が保護基で保護されていてもよく且つハロゲン原子を有していてもよい炭素数１〜６のヒドロキシアルキル基、塩を形成していてもよいカルボキシル基、又は置換オキシカルボニル基を示す。Ａは炭素数１〜６のアルキレン基、酸素原子、硫黄原子又は非結合を示す。ｍはＲ¹の個数であって０〜８の整数を示す。Ｘは下記式（２）

（式中、Ｒ^b、Ｒ^cはそれぞれ独立に、水素原子、又は置換基を有していてもよいアルキル基を示す。Ｒ^b、Ｒ^cは互いに結合して、式中に示される窒素原子とともに環を形成していてもよい）
で表されるカルバモイル基を示す。ｎは環に結合しているＸの個数であって１〜９の整数を示す。Ｙは炭素数１〜６の２価の有機基を示す。ｋは０又は１を示す。ＣＨ₂＝Ｃ（Ｒ^a）ＣＯ−（Ｏ−Ｙ−ＣＯ）_k−Ｏ−基の立体的な位置はエンド、エキソの何れであってもよい］
で表されるモノマー単位を少なくとも有する高分子化合物を提供する。 The present invention also provides the following formula (I)

[Wherein, R ^a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ represents a substituent bonded to the ring, An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms in which a hydroxyl group portion may be protected with a protecting group and may have a halogen atom An alkyl group, a carboxyl group that may form a salt, or a substituted oxycarbonyl group is shown. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represent a hydrogen atom or an optionally substituted alkyl group. R ^b and R ^c are bonded to each other to form a nitrogen atom represented by the formula And may form a ring together)
The carbamoyl group represented by these is shown. n is the number of X bonded to the ring and represents an integer of 1 to 9. Y represents a divalent organic group having 1 to 6 carbon atoms. k represents 0 or 1. The steric position of the CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k —O— group may be either endo or exo.
The polymer compound which has at least the monomer unit represented by these is provided.

［式中、Ｒ^aは水素原子、ハロゲン原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を示し、Ｒ¹は環に結合している置換基であって、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、ヒドロキシル基部分が保護基で保護されていてもよく且つハロゲン原子を有していてもよい炭素数１〜６のヒドロキシアルキル基、塩を形成していてもよいカルボキシル基、又は置換オキシカルボニル基を示す。Ａは炭素数１〜６のアルキレン基、酸素原子、硫黄原子又は非結合を示す。ｍはＲ¹の個数であって０〜８の整数を示す。Ｘは下記式（２）

（式中、Ｒ^b、Ｒ^cはそれぞれ独立に、水素原子、又は置換基を有していてもよいアルキル基を示す。Ｒ^b、Ｒ^cは互いに結合して、式中に示される窒素原子とともに環を形成していてもよい）
で表されるカルバモイル基を示す。Ｙは炭素数１〜６の２価の有機基を示す。ｋは０又は１を示す。ＣＨ₂＝Ｃ（Ｒ^a）ＣＯ−（Ｏ−Ｙ−ＣＯ）_k−Ｏ−基の立体的な位置はエンド、エキソの何れであってもよい］
で表されるモノマー単位が含まれる。 The monomer unit represented by the formula (I) includes the following formula (Ia):

[Wherein, R ^a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ represents a substituent bonded to the ring, An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms in which a hydroxyl group portion may be protected with a protecting group and may have a halogen atom An alkyl group, a carboxyl group that may form a salt, or a substituted oxycarbonyl group is shown. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represent a hydrogen atom or an optionally substituted alkyl group. R ^b and R ^c are bonded to each other to form a nitrogen atom represented by the formula And may form a ring together)
The carbamoyl group represented by these is shown. Y represents a divalent organic group having 1 to 6 carbon atoms. k represents 0 or 1. The steric position of the CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k —O— group may be either endo or exo.
The monomer unit represented by these is included.

  In addition to the monomer unit represented by the formula (I), the polymer compound may further include at least a monomer unit that is eliminated by the action of an acid and becomes alkali-soluble.

（式中、環Ｚ¹は置換基を有していてもよい炭素数３〜２０の脂環式炭化水素環を示す。Ｒ^aは水素原子、ハロゲン原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ²〜Ｒ⁴は、同一又は異なって、置換基を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ⁵は環Ｚ¹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、ｐ個のＲ⁵のうち少なくとも１つは、−ＣＯＯＲ^d基を示す。前記Ｒ^d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。ｐは１〜３の整数を示す。Ｒ⁶、Ｒ⁷は、同一又は異なって、水素原子又は置換基を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ⁸は水素原子又は有機基を示す。Ｒ⁶、Ｒ⁷、Ｒ⁸のうち少なくとも２つが互いに結合して隣接する原子とともに環を形成していてもよい）
から選ばれるモノマー単位であってもよい。 Monomer units that are eliminated by the action of the acid and become alkali soluble are represented by the following formulas (Va) to (Vd).

(In the formula, ring Z ¹ represents an alicyclic hydrocarbon ring having 3 to 20 carbon atoms which may have a substituent. R ^a may have a hydrogen atom, a halogen atom or a substituent. R ^{1 to} R ⁴ are the same or different and each represents an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ⁵ is a ring Z ^1. The same or different substituents bonded to the oxo group, alkyl group, hydroxyl group optionally protected with a protecting group, hydroxyalkyl group optionally protected with a protecting group, or protecting group And represents a carboxyl group which may be protected with at least one of p R ^{5 s} representing a —COOR ^d group, wherein R ^d is a tertiary carbon which may have a substituent. Represents a hydrogen group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group; Be .p is .R ^6, R ⁷ represents an integer of 1 to 3, same or different, .R ⁸ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms A hydrogen atom or an organic group, at least two of R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring with adjacent atoms)
It may be a monomer unit selected from

  In addition to the monomer unit represented by the formula (I), the polymer compound may further have at least a monomer unit containing an alicyclic skeleton having at least one substituent.

（式中、環Ｚ²は炭素数６〜２０の脂環式炭化水素環を示す。Ｒ^aは水素原子、ハロゲン原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ⁹は環Ｚ²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、ハロアルキル基、ハロゲン原子、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メルカプト基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいアミノ基、又は保護基で保護されていてもよいスルホン酸基を示す。ｑはＲ⁹の個数であって１〜５の整数を示す）
から選ばれるモノマー単位が含まれる。 The monomer unit containing an alicyclic skeleton having at least one substituent has the following formula (VI):

(In the formula, ring Z ² represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms. ^Ra represents ^a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms. R ⁹ is a substituent bonded to ring Z ² and is the same or different and is an oxo group, an alkyl group, a haloalkyl group, a halogen atom, a hydroxyl group optionally protected by a protecting group, a protected group A hydroxyalkyl group optionally protected with a group, a mercapto group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, an amino group optionally protected with a protecting group, or a protection A sulfonic acid group which may be protected by a group, q is the number of R ⁹ and represents an integer of 1 to 5)
A monomer unit selected from is included.

  The polymer compound includes at least one monomer unit represented by the formula (I), a monomer unit that is eliminated by the action of an acid and becomes alkali-soluble, and a substituent selected from a hydroxyl group and a hydroxymethyl group. And at least a monomer unit containing an alicyclic skeleton.

  In addition to the monomer unit represented by the formula (I), the polymer compound may further have at least a monomer unit having a lactone skeleton other than the monomer unit represented by the formula (I).

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

  The present invention further provides a method for producing a semiconductor, wherein a pattern is formed using the photoresist composition.

［式中、Ｒ^aは水素原子、ハロゲン原子、又は置換基を有していてもよい炭素数１〜６のアルキル基を示し、Ｒ¹は環に結合している置換基であって、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、ヒドロキシル基部分が保護基で保護されていてもよく且つハロゲン原子を有していてもよい炭素数１〜６のヒドロキシアルキル基、塩を形成していてもよいカルボキシル基、又は置換オキシカルボニル基を示す。Ａは炭素数１〜６のアルキレン基、酸素原子、硫黄原子又は非結合を示す。ｍはＲ¹の個数であって０〜８の整数を示す。Ｘは下記式（２）

（式中、Ｒ^b、Ｒ^cはそれぞれ独立に、水素原子、又は置換基を有していてもよいアルキル基を示す。Ｒ^b、Ｒ^cは互いに結合して、式中に示される窒素原子とともに環を形成していてもよい）
で表されるカルバモイル基を示す。ｎは環に結合しているＸの個数であって１〜９の整数を示す。Ｙは炭素数１〜６の２価の有機基を示す。ｋは０又は１を示す。ＣＨ₂＝Ｃ（Ｒ^a）ＣＯ−（Ｏ−Ｙ−ＣＯ）_k−Ｏ−基の立体的な位置はエンド、エキソの何れであってもよい］
で表されるカルバモイル基及びラクトン骨格を含む単量体の製造方法であって、下記式（３）

［式中、Ｒ¹は環に結合している置換基であって、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、ヒドロキシル基部分が保護基で保護されていてもよく且つハロゲン原子を有していてもよい炭素数１〜６のヒドロキシアルキル基、塩を形成していてもよいカルボキシル基、又は置換オキシカルボニル基を示す。Ａは炭素数１〜６のアルキレン基、酸素原子、硫黄原子又は非結合を示す。ｍはＲ¹の個数であって０〜８の整数を示す。ｎは環に結合しているシアノ基の個数であって１〜９の整数を示す。Ｒ^eは水素原子又は有機基を示す。Ｒ^eＯ−基の立体的な位置はエンド、エキソの何れであってもよい］
で表されるシアノ基含有ラクトン化合物を、下記式（４）

［式中、Ｒ¹は環に結合している置換基であって、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、ヒドロキシル基部分が保護基で保護されていてもよく且つハロゲン原子を有していてもよい炭素数１〜６のヒドロキシアルキル基、塩を形成していてもよいカルボキシル基、又は置換オキシカルボニル基を示す。Ａは炭素数１〜６のアルキレン基、酸素原子、硫黄原子又は非結合を示す。ｍはＲ¹の個数であって０〜８の整数を示す。Ｘは下記式（２）

（式中、Ｒ^b、Ｒ^cはそれぞれ独立に、水素原子、又は置換基を有していてもよいアルキル基を示す。Ｒ^b、Ｒ^cは互いに結合して、式中に示される窒素原子とともに環を形成していてもよい）
で表されるカルバモイル基を示す。ｎは環に結合しているＸの個数であって１〜９の整数を示す。Ｒ^eは水素原子又は有機基を示す。Ｒ^eＯ−基の立体的な位置はエンド、エキソの何れであってもよい］
で表されるカルバモイル基含有ラクトン化合物に転化する工程を少なくとも含むことを特徴とするカルバモイル基及びラクトン骨格を含む単量体の製造方法を提供する。 The present invention also provides the following formula (1):

[Wherein, R ^a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ represents a substituent bonded to the ring, An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms in which a hydroxyl group portion may be protected with a protecting group and may have a halogen atom An alkyl group, a carboxyl group that may form a salt, or a substituted oxycarbonyl group is shown. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represent a hydrogen atom or an optionally substituted alkyl group. R ^b and R ^c are bonded to each other to form a nitrogen atom represented by the formula And may form a ring together)
The carbamoyl group represented by these is shown. n is the number of X bonded to the ring and represents an integer of 1 to 9. Y represents a divalent organic group having 1 to 6 carbon atoms. k represents 0 or 1. The steric position of the CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k —O— group may be either endo or exo.
A monomer having a carbamoyl group and a lactone skeleton represented by the following formula (3):

[Wherein R ¹ is a substituent bonded to the ring, and a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxyl group moiety is protected with a protecting group. And a hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom, a carboxyl group which may form a salt, or a substituted oxycarbonyl group. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. n is the number of cyano groups bonded to the ring and represents an integer of 1 to 9. R ^e represents a hydrogen atom or an organic group. The steric position of the R ^e O- group may be either endo or exo]
A cyano group-containing lactone compound represented by the following formula (4)

[Wherein R ¹ is a substituent bonded to the ring, and a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxyl group moiety is protected with a protecting group. And a hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom, a carboxyl group which may form a salt, or a substituted oxycarbonyl group. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represent a hydrogen atom or an optionally substituted alkyl group. R ^b and R ^c are bonded to each other to form a nitrogen atom represented by the formula And may form a ring together)
The carbamoyl group represented by these is shown. n is the number of X bonded to the ring and represents an integer of 1 to 9. R ^e represents a hydrogen atom or an organic group. The steric position of the R ^e O- group may be either endo or exo]
A method for producing a monomer containing a carbamoyl group and a lactone skeleton, comprising at least a step of converting into a carbamoyl group-containing lactone compound represented by the formula:

The position numbers in the 6-oxabicyclo [3.2.1 ^1,5 ] octane ring and the position numbers in the 3-oxatricyclo [4.2.1.0 ^4,8 ] nonane ring are shown below ( The former is left and the latter is right).

  According to the present invention, a monomer of a high-performance polymer compound that has excellent solubility in organic solvents while maintaining stability such as chemical resistance when derived into a polymer compound, and also has excellent affinity for water. Monomer having a polycyclic ester group containing a novel lactone skeleton useful as a component, a method for producing the monomer, a polymer compound obtained by polymerizing the monomer, a composition for photoresist, and a method for producing a semiconductor Is provided. In particular, the monomer containing a lactone skeleton of the present invention has a greatly improved solubility in an alkali developer by introducing a carbamoyl group into a polycyclic skeleton containing a lactone skeleton, and the monomer unit derived from the monomer When a polymer containing is used as a resin for photoresist, performance such as etching resistance, affinity for alkaline developer, solvent solubility, etc. is well-balanced, and it is possible to draw clearer patterns in semiconductor manufacturing did. This is because the SP value of the compound having a carbamoyl group (amide group) is very high. However, since the carbamoyl group is more polar than the CN group and has a hydrogen bonding ability, a highly polar portion is gathered in the resist film. A phenomenon that a route through which the developing solution penetrates easily occurs. For this reason, even if the SP value, which is the average polarity of the whole molecule, is equal to or slightly lower than that of a compound having a CN group, the resin using a compound having a carbamoyl group as a monomer component is clearer. Pattern is formed.

[Monomer containing carbamoyl group and lactone skeleton]
Monomers containing a carbamoyl group and a lactone skeleton of the present invention (6-oxabicyclo [3.2.1 ^1,5 ] octane-7-one derivatives and 3-oxatricyclo [4.2.1.0 ^{4, 8} ] nonan-2-one derivatives and the like are represented by the formula (1). In the formula (1), R ^a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ represents a ring [6-oxabicyclo [3.2. 1 ^1,5 ] octane ring (when A is non-bonded), 3-oxatricyclo [4.2.1.0 ^4,8 ] nonane ring (when A is a methylene group), etc.] Substituent, which may have a halogen atom, a C1-C6 alkyl group which may have a halogen atom, or a hydroxyl group part may be protected with a protecting group and may have a halogen atom A hydroxyalkyl group having 1 to 6 carbon atoms, a carboxyl group which may form a salt, or a substituted oxycarbonyl group is shown. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X represents a substituted or unsubstituted carbamoyl group represented by the formula (2). n is a ring [6-oxabicyclo [3.2.1 ^1,5 ] octane ring (when A is non-bonded), 3-oxatricyclo [4.2.1.0 ^4,8 ] nonane ring (A Is an methylene group), etc.], and represents an integer of 1 to 9. Y represents a divalent organic group having 1 to 6 carbon atoms. k represents 0 or 1. The steric position of the CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k —O— group may be either endo or exo.

In the formula, X represents a substituted or unsubstituted carbamoyl group represented by the formula (2). In formula (2), R ^b and R ^c each independently represent a hydrogen atom or an alkyl group which may have a substituent. R ^b and R ^c may be bonded to each other to form a ring together with the nitrogen atom shown in the formula. Examples of the “alkyl group” of the “optionally substituted alkyl group” for R ^b and R ^c include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl , Hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl group and other alkyl groups having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 6). Examples of the “substituent” of the “optionally substituted alkyl group” include a halogen atom such as a fluorine atom, an alkoxy group such as a hydroxyl group and a methoxy group (C _1-6 alkoxy group etc.), Alkoxycarbonyl groups such as carboxyl groups and methoxycarbonyl groups (C _1-6 alkoxy-carbonyl groups etc.), acyl groups such as acetyl groups (C _1-6 acyl groups etc.), aryl groups such as cyano groups and phenyl groups (C _6-14 aryl groups), alkenyl groups such as vinyl groups (C _2-6 alkenyl groups, etc.), cycloalkyl groups such as cyclohexyl groups (C _3-12 cycloalkyl groups, etc.), nitro groups and the like.

Examples of the ring that R ^b and R ^c may be bonded to each other to form together with the nitrogen atom shown in the formula include 3 to 12 members (preferably a pyrrolidine ring, a piperidine ring, a morpholine ring, a piperazine ring, etc. 5-6 membered) non-aromatic nitrogen-containing heterocycle. A substituent may be bonded to the atoms constituting the ring. Examples of such a substituent include the same groups as the “substituent” of the “alkyl group optionally having substituent (s)” in R ^b and R ^c , methyl, ethyl, propyl, isopropyl, butyl, C1-C20 (preferably 1-10, more preferably 1-6) alkyl groups such as isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl group Etc. Among these substituents, an alkyl group having 1 to 6 carbon atoms such as a methyl group is preferable.

R ^b and R ^c are each preferably a hydrogen atom or an alkyl group having 1 to 6 (particularly 1 to 4) carbon atoms. R ^b and R ^c are preferably bonded to each other to form a 5- to 6-membered non-aromatic nitrogen-containing heterocycle together with the nitrogen atom shown in the formula. Further, R ^b and R ^c are particularly preferably a combination in which both are hydrogen atoms, and a combination in which one is a hydrogen atom and the other is an alkyl group having 1 to 6 (particularly 1 to 4) carbon atoms.

The halogen atoms as R ^a and R ¹ described in the formula (1) include, for example, fluorine, chlorine, bromine atoms and the like. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups. Among these, a C _1-4 alkyl group, particularly a methyl group is preferable. Examples of the alkyl group having 1 to 6 carbon atoms having a halogen atom include chloroalkyl groups such as chloromethyl group; fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl groups ( Preferably, a _C1-3 fluoroalkyl group) etc. are mentioned. As ^a C1-C6 alkyl group which has ^a substituent in ^Ra, the C1-C6 alkyl group which has the said halogen atom, etc. are mentioned.

Examples of the hydroxyalkyl group having 1 to 6 carbon atoms in R ¹ include, for example, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, and 6-hydroxyhexyl group. Etc. Examples of the C1-C6 hydroxyalkyl group having a halogen atom include difluorohydroxymethyl, 1,1-difluoro-2-hydroxyethyl, 2,2-difluoro-2-hydroxyethyl, 1,1,2, Examples include 2-tetrafluoro-2-hydroxyethyl group. Among the hydroxyalkyl groups having 1 to 6 carbon atoms which may have a halogen atom, a hydroxyalkyl group or hydroxyhaloalkyl group having 1 or 2 carbon atoms (particularly 1 carbon atom) is preferable. Examples of the protective group for the hydroxyl group of a hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom include a protective group usually used as a protective group for a hydroxyl group in the field of organic synthesis, such as a methyl group, a methoxy group, and the like. Examples include groups that form an ether or acetal bond with an oxygen atom that constitutes a hydroxyl group such as a methyl group; groups that form an ester bond with an oxygen atom that constitutes a hydroxyl group such as an acetyl group or a benzoyl group. Examples of the carboxyl group salt include alkali metal salts, alkaline earth metal salts, and transition metal salts.

Examples of the substituted oxycarbonyl group include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, propoxycarbonyl group (C _1-4 alkoxy-carbonyl group, etc.); vinyloxycarbonyl, allyloxycarbonyl group, etc. Examples thereof include alkenyloxycarbonyl groups (C _2-4 alkoxy-carbonyl groups and the like); cycloalkyloxycarbonyl groups such as cyclohexyloxycarbonyl groups; aryloxycarbonyl groups such as phenyloxycarbonyl groups and the like.

R ^a is preferably a hydrogen atom, a C _1-3 alkyl group such as a methyl group, or a C _1-3 haloalkyl group such as a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group. In addition, as R ¹ , an alkyl group having 1 to 3 carbon atoms such as a methyl group or a trifluoromethyl group or a haloalkyl group, a hydroxyalkyl group having 1 to 3 carbon atoms in which a hydroxy moiety may be protected with a protecting group, or A hydroxyhaloalkyl group (particularly a hydroxymethyl group which may be protected with a protective group such as a hydroxymethyl group or an acetoxymethyl group), a substituted oxycarbonyl group or the like is preferred.

m is 0-8, preferably 0-6, more preferably 0-3. When there are a plurality of R ^{1 s} , they may be the same or different. n is 1 to 9, preferably 1 to 5, and more preferably 1 or 2. When X is plural, they may be the same or different. When A is non-bonded, the substituent X is located at any position of the 1-position, 2-position, 3-position, 4-position, 5-position and 8-position of the 6-oxabicyclo [3.2.1 ^1,5 ] octane ring. Although they may be bonded, the 1-position (α position of the lactone) or the 2-position is preferable, and the 1-position (α position of the lactone) is particularly preferable. When A is an alkylene group having 1 to 6 carbon atoms, an oxygen atom, or a sulfur atom, the substituent X is the 1-position of a 3-oxatricyclo [4.2.1.0 ^4,8 ] nonane ring or the like. The 3-oxatricyclo [4.2.1.0 ^4,8 ] nonane ring may be bonded to any position such as 4-position, 5-position, 6-position, 7-position, 8-position, and 9-position. 1-position or 9-position (or a position corresponding thereto) is preferable, and the 1-position (or a position corresponding thereto; α-position of lactone) is particularly preferable.

  A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a non-bond, and examples of the alkylene group having 1 to 6 carbon atoms include a methylene group and an alkyl group which may be substituted with an alkyl group. And an ethylene group which may be substituted with and a propylene group which may be substituted with an alkyl group. Among these, as A, an alkylene group having 1 to 6 carbon atoms or a non-bond is preferable.

Y represents a divalent organic group having 1 to 6 carbon atoms. Examples of the divalent organic group include alkylene groups such as methylene, ethylene, propylene and butylene (particularly C _1-6 alkylene group); alkenylene groups such as vinylene (particularly C _2-6 alkenylene group); cyclopentylene, A cycloalkenylene group such as a cyclohexylene group; two or more of these are bonded via a linking group such as an ether bond (—O—), a thioether bond (—S—), or an ester bond (—COO—; —OCO—) And divalent organic groups. In particular, methylene, ethylene, propylene and the like are preferable. Of these exemplified groups, those substituted with a halogen atom, particularly a fluorine atom are also useful.

As a typical example of a monomer having a carbamoyl group and a lactone skeleton represented by the formula (1), a 1-substituted (X) -6-oxabicyclo [3.2.1 ^1, represented by the following formula: ⁵ ] octane-7-one compound (including each stereoisomer), 2-substituted (X) -6-oxabicyclo [3.2.1 ^1,5 ] octane-7-one compound (each stereoisomer is 1) -substituted (X) -5- (meth) acryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one compound (including each stereoisomer), 9-substituted (X) -5- (meth) acryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one compounds (including each stereoisomer), and A compound in which A in the corresponding formula (1) is an alkylene group other than a methylene group, an oxygen atom or a sulfur atom Thing, and the like. In the formula, R represents a CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k — group, and Ac represents an acetyl group. X as a substituent represents a substituted or unsubstituted carbamoyl group represented by the formula (2).

  Moreover, the compound represented by the said Formula (1a) is mentioned as a preferable example of the monomer which has a carbamoyl group represented by Formula (1), and a lactone skeleton. The compound represented by the formula (1a) is a compound in which the carbamoyl group X is bonded to the α-position of the lactone in the monomer having the carbamoyl group and the lactone skeleton represented by the formula (1).

  The monomer having a carbamoyl group and a lactone skeleton represented by the formula (1) is a cyano group-containing lactone compound represented by the formula (3), and a carbamoyl group-containing lactone compound represented by the formula (4). It can manufacture by passing through the process of converting into at least.

In formula (3), R ¹ , A and m are the same as described above. n is the number of cyano groups bonded to the ring and represents an integer of 1 to 9. R ^e represents a hydrogen atom or an organic group. The steric position of the R ^e O— group may be either endo or exo. In the formula (4), R ¹ , A, m, and X are the same as described above. n is the number of X bonded to the ring and represents an integer of 1 to 9. R ^e represents a hydrogen atom or an organic group. The steric position of the R ^e O— group may be either endo or exo.

As an organic group in R ^e , CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k — group or CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k by reaction. A group derivable to the group (R ^a , Y, k are the same as above); Examples of the group that can be derived to CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k — group by reaction include a Z ^a —Y—CO— group (Z ^a represents a halogen atom). It is done.

  As a typical compound represented by Formula (3), the compound represented by following formula (3a)-(3c) is mentioned.

In the above formula, R ^a , R ¹ , A, m, n, Y, and k are the same as in the above formula (3). Z ^a represents a halogen atom. Examples of the halogen atom include chlorine, bromine and iodine atoms.

  The compounds represented by the formulas (3a) to (3c) can be synthesized by a known production method (see, for example, WO2009 / 107327).

As a method for converting (converting) the cyano group-containing lactone compound represented by the formula (3) into the carbamoyl group-containing lactone compound represented by the formula (4), a known method for synthesizing an acid amide from a nitrile can be used. . For example, (i) a method in which a cyano group-containing lactone compound represented by formula (3) is hydrolyzed in the presence of an acid; (ii) a cyano group-containing lactone compound represented by formula (3) is present in the presence of manganese dioxide. Hydrolysis under the following method [A compound in which X is —CONH ₂ in the formula (4) is obtained] (Japanese Patent Laid-Open No. 9-24275, Japanese Translation of PCT International Publication No. 2009-512124, Japanese Patent Publication No. 2010-510276, etc. (Iii) A method in which a cyano group-containing lactone compound represented by formula (3) is reacted with an alcohol (R ^b OH) in the presence of sulfuric acid [a compound in which X is —CONHR ^b in formula (4) And (iv) a method of hydrolyzing a cyano group-containing lactone compound represented by formula (3) in the presence of an alkali [in formula (4), X is − CON _2, compound is obtained, in the method of the cyano group-containing lactone compound exerts a alkaline hydrogen peroxide [Equation (4), compounds wherein X is -CONH ₂ is represented by (v) (3) (Vi) a method of reacting a cyano group-containing lactone compound represented by formula (3) with an amine (HNR ^b R ^c ) in the presence of water [in formula (4), X is —CONR ^b R ^c is obtained as a compound].

In the method (i), examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and polyphosphoric acid; and sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid. In the method (iv), examples of the alkali include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide. In the method (v), examples of the alkaline hydrogen peroxide include a combination of potassium carbonate and hydrogen peroxide. The method (vi) is performed, for example, in the presence of a ruthenium catalyst [RuH ₂ (PPh ₃ ) ₄ etc.].

When the compound represented by the formula (3a) is used as the compound represented by the formula (3), the cyano group in the formula (3a) is converted into a carbamoyl group represented by the formula (2), The acid halide represented by CH ₂ ═C (R ^a ) CO—Z ^b , preferably in the presence of a base (such as a tertiary amine such as triethylamine) after the corresponding compound represented by formula (4) (Z ^b is a halogen atom) by reaction with, in the formula (1) can be prepared a compound that is k = 0. Examples of the halogen atom for Z ^b include chlorine, bromine and iodine atoms.

When the compound represented by the formula (3b) is used as the compound represented by the formula (3), the cyano group in the formula (3b) is converted into a carbamoyl group represented by the formula (2), After the corresponding compound represented by the formula (4), it is preferably reacted with a carboxylic acid represented by CH ₂ ═C (R ^a ) COOH in the presence of a base (a tertiary amine such as triethylamine). Thus, a compound in which k = 1 in the formula (1) can be produced.

  When the compound represented by formula (3c) is used as the compound represented by formula (3), the cyano group in formula (3c) is converted to a carbamoyl group represented by formula (2). Thus, the corresponding compound represented by the formula (4), that is, the compound represented by the formula (1) can be produced.

  The compound represented by the formula (4) and the compound represented by the formula (1) generated by the reaction are separated by means of separation such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc. Alternatively, they can be separated and purified by combining them.

[Polymer compound]
The polymer compound of the present invention includes a monomer unit (repeating unit) corresponding to a monomer containing a carbamoyl group and a lactone skeleton represented by the above formula (1), that is, a monomer unit represented by the above formula (I). It is out. The monomer unit may contain one kind or two or more kinds. Such a polymer compound can be obtained by subjecting a monomer containing a carbamoyl group represented by the above formula (1) and a lactone skeleton to polymerization.

The monomer unit represented by the formula (I) includes a 6-oxabicyclo [3.2.1 ^1,5 ] octane-7-one skeleton to which the carbamoyl group represented by the formula (2) is bonded, or the formula (2 ), A 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one skeleton to which, for example, a 6-oxabicyclo having a cyano group is bonded. Compared with units having [3.2.1 ^1,5 ] octane-7-one skeleton and 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one skeleton having a cyano group And it has a high affinity for water. Therefore, the polymer compound of the present invention is useful as a highly functional polymer used in a field where affinity for water is required, particularly as a resin for photoresist.

 The polymer compound of the present invention may have other monomer units in addition to the monomer unit represented by the formula (I) according to the use and required function. Such another monomer unit is obtained by copolymerizing a polymerizable unsaturated monomer corresponding to the other monomer unit with a monomer containing a carbamoyl group represented by the formula (1) and a lactone skeleton. Can be formed.

  Examples of the other monomer units include monomer units that are eliminated by the action of an acid and become alkali-soluble, for example, monomer units represented by the formulas (Va), (Vb), (Vc), and (Vd). . The polymerizable unsaturated monomers corresponding to the monomer units represented by the formulas (Va), (Vb), (Vc), and (Vd) are represented by the following formulas (5a), (5b), (5c), (5d).

In the above formula, ring Z ¹ represents an alicyclic hydrocarbon ring having 3 to 20 carbon atoms which may have a substituent. R ^a is the same as above. R < ² > -R < ⁴ > is the same or different and shows the C1-C6 alkyl group which may have a substituent. R ⁵ is a substituent bonded to ring Z ¹ and is the same or different and is an oxo group, an alkyl group, a hydroxyl group which may be protected with a protecting group, or a hydroxy group which is protected with a protecting group. An alkyl group or a carboxyl group which may be protected with a protecting group is shown. However, at least one of p R ⁵ 's represents a —COOR ^d group. R ^d represents a tertiary hydrocarbon group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group which may have a substituent. p shows the integer of 1-3. R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. R ⁸ represents a hydrogen atom or an organic group. At least two of R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring with adjacent atoms.

In formulas (5a) to (5c), the alicyclic hydrocarbon ring having 3 to 20 carbon atoms in ring Z ¹ 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, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclooctane ring, cyclodecane ring, adamantane ring, norbornane ring, norbornene ring, bornane ring, isobornane ring, perborn ring, Hydroindene 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 ¹ is preferably a polycyclic alicyclic hydrocarbon ring (bridged hydrocarbon ring) such as an adamantane ring.

As a C1-C6 alkyl group which may have a substituent in R < ² > -R < ⁴ >, R < ⁶ >, R < ⁷ > in Formula (5a), (5b), (5d), for example, methyl, Linear or branched alkyl groups having 1 to 6 carbon atoms such as ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl and hexyl groups; haloalkyl having 1 to 6 carbon atoms such as trifluoromethyl group Group and the like. In formula (5c), examples of the alkyl group represented by R ⁵ 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 ⁵ include a hydroxyl group and a substituted oxy group (for example, a C _1-4 alkoxy group such as 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 ^f group. R ^f 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 ⁵ , the tertiary hydrocarbon group in R ^d of the —COOR ^d group includes, for example, t-butyl, t-amyl, 2-methyl-2-adamantyl, (1-methyl-1-adamantyl) ethyl group Etc. The tetrahydrofuranyl group 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 organic group for R ⁸ include a group containing a hydrocarbon group and / or a heterocyclic group. The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded. Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, and octyl groups (C _{1- 8} alkyl groups); linear or branched alkenyl groups such as allyl groups (C _2-8 alkenyl groups, etc.); linear or branched alkynyl groups such as propynyl groups (C _2-8 alkynyl) Group, etc.). Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl groups (3 to 8 membered cycloalkyl groups); cycloalkenyl groups such as cyclopentenyl and cyclohexenyl groups (3 to 8 members). Cycloalkenyl groups and the like); bridged carbocyclic groups such as adamantyl and norbornyl groups (C _4-20 bridged carbocyclic groups and the like) and the like. Examples of the aromatic hydrocarbon group include C _6-14 aromatic hydrocarbon groups such as phenyl and naphthyl groups. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include benzyl and 2-phenylethyl groups. These hydrocarbon groups are protected with alkyl groups (C _1-4 alkyl groups, etc.), haloalkyl groups (C _1-4 haloalkyl groups, etc.), halogen atoms, hydroxyl groups that may be protected with protecting groups, and protecting groups. It may have a substituent such as a hydroxymethyl group which may be protected, a carboxyl group which may be protected with a protecting group, or an oxo group. As the protecting group, a protecting group conventionally used in the field of organic synthesis can be used.

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

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

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

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

The ring constituting the cyclic skeleton may be directly bonded to an oxygen atom (an oxygen atom adjacent to R ⁸ ) shown in the formula (5d) or may be bonded via a linking group. . Examples of the linking group include a linear or branched alkylene group such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene group; a carbonyl group; an oxygen atom (ether bond; —O—); an oxycarbonyl group ( An ester bond; —COO—); an aminocarbonyl group (amide bond; —CONH—); and a group in which a plurality of these are bonded.

At least two of R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring with adjacent atoms. Examples of the ring include cycloalkane rings such as cyclopropane ring, cyclopentane ring and cyclohexane ring; oxygen-containing rings such as tetrahydrofuran ring, tetrahydropyran ring and oxepane ring; bridged ring and the like.

  In the compounds represented by formulas (5a) to (5d), stereoisomers may exist, but they can be used alone or as a mixture of two or more.

  Although the following compound is mentioned as a typical example of a compound represented by Formula (5a), It is not limited to these. 2- (meth) acryloyloxy-2-methyladamantane, 1-hydroxy-2- (meth) acryloyloxy-2-methyladamantane, 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane, 2- ( (Meth) acryloyloxy-2-ethyladamantane.

  Although the following compound is mentioned as a typical example of a compound represented by Formula (5b), It is not limited to these. 1- (1- (meth) acryloyloxy-1-methylethyl) adamantane, 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane, 1- (1-ethyl-1- ( (Meth) acryloyloxypropyl) adamantane, 1- (1- (meth) acryloyloxy-1-methylpropyl) adamantane.

  Although the following compound is mentioned as a typical example of a compound represented by Formula (5c), It is not limited to these. 1-t-butoxycarbonyl-3- (meth) acryloyloxyadamantane, 1- (2-tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxyadamantane.

  Although the following compound is mentioned as a typical example of a compound represented by Formula (5d), It is not limited to these. 1-adamantyloxy-1-ethyl (meth) acrylate, 1-adamantylmethyloxy-1-ethyl (meth) acrylate, 2- (1-adamantylethyl) oxy-1-ethyl (meth) acrylate, 1-bornyloxy-1 -Ethyl (meth) acrylate, 2-norbornyloxy-1-ethyl (meth) acrylate, 2-tetrahydropyranyl (meth) acrylate, 2-tetrahydrofuranyl (meth) acrylate.

  The compound represented by the above formula (5d) can be obtained, for example, by reacting the corresponding vinyl ether compound and (meth) acrylic acid by a conventional method using an acid catalyst. For example, 1-adamantyloxy-1-ethyl (meth) acrylate can be produced by reacting 1-adamantyl-vinyl-ether with (meth) acrylic acid in the presence of an acid catalyst.

  In addition to the above, examples of the other monomer units include monomer units that can impart or improve hydrophilicity, water solubility, or other characteristics. Examples of the monomer corresponding to such a monomer unit include, for example, a hydroxyl group-containing monomer (including a compound in which the hydroxyl group is protected), a mercapto group-containing monomer (a compound in which the mercapto group is protected). ), Carboxyl group-containing monomers (including compounds in which carboxyl groups are protected), amino group-containing monomers (including compounds in which amino groups are protected), sulfonic acid group-containing monomers (including Sulfonate skeleton-containing monomers, cyclic ketone skeleton-containing monomers, acid anhydride group-containing monomers, imide group-containing monomers, etc. Examples include polar group-containing monomers.

  Examples of such other monomer units include monomer units containing an alicyclic skeleton having at least one substituent, for example, monomer units represented by the formula (VI). The polymerizable unsaturated monomer corresponding to the monomer unit represented by the formula (VI) is represented by the following formula (6).

In the above formula, ring Z ² represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms. R ^a is the same as above. R ⁹ is a substituent bonded to ring Z ² and is the same or different and protected with an oxo group, an alkyl group, a haloalkyl group, a halogen atom, a hydroxyl group which may be protected with a protecting group, or a protecting group Protected with a hydroxyalkyl group which may be protected, a mercapto group which may be protected with a protecting group, a carboxyl group which may be protected with a protecting group, an amino group which may be protected with a protecting group, or a protecting group The sulfonic acid group which may be made is shown. q is the number of R ⁹ and represents an integer of 1 to 5.

Among the monomers represented by the formula (6), at least one of q R ⁹ is an oxo group, a hydroxyl group which may be protected with a protecting group, or a hydroxy group which may be protected with a protecting group. An alkyl group, a mercapto group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, an amino group optionally protected with a protecting group, or a sulfone optionally protected with a protecting group The monomer that is an acid group corresponds to a polar group-containing monomer that can impart or improve hydrophilicity or water solubility to a polymer.

The alicyclic hydrocarbon ring having 6 to 20 carbon atoms in the ring Z ² may be a single ring or a polycyclic ring such as 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. Among the alicyclic hydrocarbon rings, a bridged alicyclic hydrocarbon ring such as an adamantane ring is particularly preferable.

In formula (6), the alkyl group for R ⁹ is a linear or branched chain such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl, dodecyl group, etc. And an alkyl group having about 1 to 20 carbon atoms (particularly, a C _1-4 alkyl group). Examples of the haloalkyl group include a haloalkyl group having about 1 to 20 carbon atoms such as a trifluoromethyl group (particularly, a C _1-4 haloalkyl group). Examples of the halogen atom include a fluorine atom and a chlorine atom. Examples of the amino group that may be protected with a protecting group include an amino group and a substituted amino group (for example, C _1-4 alkylamino groups such as methylamino, ethylamino, propylamino group, etc.). Examples of the sulfonic acid group that may be protected with a protecting group include a —SO ₃ R ^g group. R ^g 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. R ⁹ may be protected with a protecting group, a hydroxyl group which may be protected with a protecting group, a hydroxyalkyl group which may be protected with a protecting group, a mercapto group which may be protected with a protecting group, or a carboxyl which may be protected with a protecting group The groups are the same as described above.

  Although the following compound is mentioned as a typical example of a compound represented by Formula (6), It is not limited to these. 1-hydroxy-3- (meth) acryloyloxyadamantane, 1,3-dihydroxy-5- (meth) acryloyloxyadamantane, 1-carboxy-3- (meth) acryloyloxyadamantane, 1,3-dicarboxy-5 (Meth) acryloyloxyadamantane, 1-carboxy-3-hydroxy-5- (meth) acryloyloxyadamantane, 1-t-butoxycarbonyl-3- (meth) acryloyloxyadamantane, 1,3-bis (t-butoxycarbonyl) ) -5- (meth) acryloyloxyadamantane, 1-t-butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxyadamantane, 1- (2-tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxy Adamantane, , 3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane, 1-hydroxy-3- (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane, 1- (Meth) acryloyloxy-4-oxoadamantane.

  The monomer corresponding to the monomer unit containing an alicyclic skeleton having at least one substituent includes an alicyclic skeleton having at least one substituent selected from a hydroxyl group and a hydroxymethyl group (for example, adamantane). Monomers containing a skeleton etc. are preferred.

  Another example of the other monomer unit is a monomer unit having a lactone skeleton [excluding the monomer unit represented by the formula (I)]. Polymerizable unsaturated monomer corresponding to a monomer unit having a lactone skeleton [excluding the monomer unit represented by formula (I)] [lactone ring-containing monomer (excluding the compound represented by formula (1)) ] Specific examples of the compound include the following compounds.

1- (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-5-one, 1- (meth) acryloyloxy-4,7-dioxatricyclo [4. 4.1.1 ^3,9 ] dodecane-5,8-dione, 1- (meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-5,7 -Dione, 1- (meth) acryloyloxy-5,7-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-4,8-dione, 2- (meth) acryloyloxy-4-oxa Tricyclo [4.2.1.0 ^3,7 ] nonane-5-one, 2- (meth) acryloyloxy-2-methyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonane -5-one, 2- (meth) acryloyloxy-6-methyl-4-oxatrici B [4.2.1.0 ^{3, 7]} nonane-5-one, 2- (meth) acryloyloxy-9-methyl-4-oxatricyclo [4.2.1.0 ^3,7] nonane - 5-one, 2- (meth) acryloyloxy-9-carboxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, 2- (meth) acryloyloxy-9-methoxy Carbonyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, 2- (meth) acryloyloxy-9-ethoxycarbonyl-4-oxatricyclo [4.2.1. 0 ^3,7 ] nonan-5-one, 2- (meth) acryloyloxy-9-t-butoxycarbonyl-4-oxatricyclo [4.2.1.0 ^3,7 ] nonane-5-one, 8 -(Meth) acryloyloxy-4-oxatricyclo [5.2. .0 ^2,6] decan-5-one, 9- (meth) acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6] decan-5-one, 4- (meth) acryloyloxy -6-oxabicyclo [3.2.1] octane-7-one, 4- (meth) acryloyloxy-4-methyl-6-oxabicyclo [3.2.1] octane-7-one, 4- ( (Meth) acryloyloxy-5-methyl-6-oxabicyclo [3.2.1] octane-7-one, 4- (meth) acryloyloxy-4,5-dimethyl-6-oxabicyclo [3.2.1] ] Octane-7-one, 6- (meth) acryloyloxy-2-oxabicyclo [2.2.2] octane-3-one, 6- (meth) acryloyloxy-6-methyl-2-oxabicyclo [2] 2.2] Octane 3-one, 6- (meth) acryloyloxy-1-methyl-2-oxabicyclo [2.2.2] octane-3-one, 6- (meth) acryloyloxy-1,6-dimethyl-2-oxa Bicyclo [2.2.2] octane-3-one, β- (meth) acryloyloxy-γ-butyrolactone, β- (meth) acryloyloxy-α, α-dimethyl-γ-butyrolactone, β- (meth) acryloyl Oxy-γ, γ-dimethyl-γ-butyrolactone, β- (meth) acryloyloxy-α, α, β-trimethyl-γ-butyrolactone, β- (meth) acryloyloxy-β, γ, γ-trimethyl-γ- Butyrolactone, β- (meth) acryloyloxy-α, α, β, γ, γ-pentamethyl-γ-butyrolactone, α- (meth) acryloyloxy-γ-butyrolac , Α- (meth) acryloyloxy-α-methyl-γ-butyrolactone, α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone, α- (meth) acryloyloxy-α, β, β- Trimethyl-γ-butyrolactone, α- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone, α- (meth) acryloyloxy-α, γ, γ-trimethyl-γ-butyrolactone, α- (meth) acryloyl Oxy-β, β, γ, γ-tetramethyl-γ-butyrolactone, α- (meth) acryloyloxy-α, β, β, γ, γ-pentamethyl-γ-butyrolactone, γ- (meth) acryloyloxy-γ , Γ-dimethyl-γ-butyrolactone.

In the polymer compound of the present invention, the proportion of the monomer unit represented by the formula (I) is not particularly limited, but is generally 1 to 90 mol%, preferably 5 to 80, based on all monomer units constituting the polymer. It is about mol%, More preferably, it is about 10-60 mol%. The proportion of monomer units that are eliminated by the action of an acid and become alkali-soluble is, for example, about 10 to 95 mol%, preferably about 15 to 90 mol%, and more preferably about 20 to 60 mol%. A monomer unit corresponding to at least one monomer selected from a hydroxyl group-containing monomer, a mercapto group-containing monomer, and a carboxyl group-containing monomer [for example, in the monomer unit represented by the formula (VI) , At least one of q R ⁹ is a hydroxyl group which may be protected with a protecting group, a hydroxyalkyl group which may be protected with a protecting group, a mercapto group which may be protected with a protecting group, or The ratio of the monomer unit that is a carboxyl group that may be protected with a protecting group] is, for example, about 0 to 60 mol%, preferably about 5 to 50 mol%, and more preferably about 10 to 40 mol%.

  In obtaining the polymer compound of the present invention, the polymerization of the monomer mixture is carried out by a conventional method used for producing an acrylic polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. Although it can be performed, solution polymerization is particularly preferred. Furthermore, drop polymerization is preferable among solution polymerization. Specifically, for example, (i) a monomer solution previously dissolved in an organic solvent and a polymerization initiator solution dissolved in an organic solvent are prepared in an organic solvent kept at a constant temperature. A method in which the monomer solution and the polymerization initiator solution are respectively dropped, and (ii) a method in which a mixed solution in which the monomer and the polymerization initiator are dissolved in an organic solvent is dropped into an organic solvent maintained at a constant temperature. (Iii) A monomer solution previously dissolved in an organic solvent and a polymerization initiator solution dissolved in the organic solvent are respectively prepared, and the polymerization initiator solution is dropped into the monomer solution maintained at a constant temperature. It is performed by a method or the like.

  As the polymerization solvent, a known solvent can be used. For example, ether (chain ether such as diethyl ether, propylene glycol monomethyl ether, etc., chain ether such as tetrahydrofuran, dioxane, etc.), ester (methyl acetate, ethyl acetate, Glycol ether esters such as butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.) ), Sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, etc.), hydrocarbon (aromatic hydrocarbons such as benzene, toluene, xylene, etc.) Aliphatic hydrocarbons such as hexane, and alicyclic hydrocarbons such as cyclohexane), and mixtures of these solvents. Moreover, a well-known polymerization initiator can be used as a polymerization initiator. The polymerization temperature can be appropriately selected within a range of about 30 to 150 ° C., for example.

  The polymer obtained by polymerization can be purified by precipitation or 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.), esters (aliphatic carboxylic acid esters such as ethyl acetate and butyl acetate), carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohols (methanol, ethanol, propanol, isopropyl alcohol, butanol) Etc.), carboxylic acids (such as acetic acid), mixed solvents containing these solvents, and the like.

Especially, as an organic solvent used as said precipitation or reprecipitation solvent, the solvent containing at least hydrocarbon (especially aliphatic hydrocarbons, such as hexane), and the mixed solvent of methanol and water are preferable. In such a solvent containing at least hydrocarbon, the ratio of hydrocarbon (for example, aliphatic hydrocarbon such as hexane) and other solvent (for example, aliphatic carboxylic acid ester such as ethyl acetate) is, for example, the former / the latter (Volume ratio; 25 ° C.) = 10/90 to 99/1, preferably the former / the latter (volume ratio; 25 ° C.) = 30/70 to 98/2, more preferably the former / the latter (volume ratio; 25 ° C.) = About 50/50 to 97/3.
The weight average molecular weight (Mw) of the polymer compound is, for example, about 1000 to 500000, preferably about 3000 to 50000, and the molecular weight distribution (Mw / Mn) is, for example, about 1.5 to 2.5. In addition, said Mn shows a number average molecular weight, and both Mn and Mw are values of polystyrene conversion.

  The polymer compound of the present invention has high stability such as chemical resistance, is excellent in solubility in an organic solvent, and is excellent in affinity for water. Further, it has excellent water solubility after hydrolysis of the lactone ring by alkali development or the like. Therefore, it can be used as a highly functional polymer in various fields.

  The photoresist composition of the present invention contains at least the polymer compound of the present invention and a photoacid generator, and usually contains a resist solvent. The photoresist composition can be prepared, for example, by adding a photoacid generator to the above-described polymer compound solution of the present invention (resist solvent solution).

  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.

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

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

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

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

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

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

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of a polymer show the standard polystyrene conversion value calculated | required by GPC measurement using a tetrahydrofuran solvent using the refractometer (RI). GPC was performed using three columns “KF-806L” connected in series by Showa Denko KK in a column temperature of 40 ° C., an RI temperature of 40 ° C., and a tetrahydrofuran flow rate of 0.8 ml / min.

Example 1
1-carbamoyl-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one was prepared according to the following reaction formula.

To a three-necked flask equipped with a stirrer substituted with nitrogen was added 5 g (20.2 mmol) of 1-cyano-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one. ), 10.5 g of concentrated hydrochloric acid was added and stirred and mixed. The mixture was stirred for 46 hours while maintaining the liquid temperature at 15 to 25 ° C. in a water bath. While cooling in an ice bath, 90 g of water was added dropwise over 30 minutes while maintaining the internal temperature at 0 to 5 ° C. The precipitated crystals were filtered and rinsed twice with 5 g of water to obtain crude crystals. By subjecting the crude crystals to silica gel column chromatography, 1.7 g of 1-carbamoyl-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (6. 4 mmol, yield 32%). The NMR spectrum data is shown below.
¹ H-NMR (DMSO-d6) δ: 7.58 (1H, brs), 7.37 (1H, brs), 6.07 (1H, s), 5.72 (1H, s), 4.65 (1H, d), 4.56 (1H, s), 3.48 (1H, d), 2.51-2.54 (1H, m), 2.44 (1H, dd), 1.92 ( 1H, d), 1.89 (3H, s), 1.76 (1H, dd), 1.59 (1H, d)

Example 2
1-carbamoyl-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one was prepared according to the following reaction formula.

Into a 200 ml three-neck flask equipped with a stirrer substituted with nitrogen, 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 2 0.5 g (8.2 mmol), p-methoxyphenol 0.05 g, toluene 50 g and manganese dioxide 28.5 g (328 mmol) were added and stirred and mixed. The mixture was stirred for 48 hours while maintaining the liquid temperature at 80 ° C. in an oil bath. The reaction solution was filtered, 50 g of acetonitrile was added to manganese dioxide remaining on the filter paper, and the mixture was stirred for 30 minutes to extract the target product, filtered, and rinsed with 25 g of acetonitrile. The reaction solution filtrate, acetonitrile extraction filtrate, and rinse solution were mixed and concentrated under reduced pressure. The concentrated residue was subjected to silica gel column chromatography to give 1-carbamoyl-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one. 50 g (1.6 mmol, yield 20%) was obtained. The NMR spectrum data is shown below.
¹ H-NMR (DMSO-d6) δ: 7.56 (1H, brs), 7.37 (1H, brs), 6.13 (1H, s), 5.80 (1H, s), 4.77 (1H, s), 4.59 (1H, s), 3.48 (1H, s), 2.49 (1H, m), 2.42 (1H, dd), 1.92 (3H, s) , 1.83 (1H, d), 1.77 (1H, d), 1.57 (1H, d)

Example 3
1- (Nt-butylcarbamoyl) -5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one was prepared according to the following reaction formula.

To a three-necked flask equipped with a stirrer substituted with nitrogen was added 5 g (20.2 mmol) of 1-cyano-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one. ), 50 g of acetic acid, and 3.0 g (40.4 mmol) of t-butyl alcohol were added and stirred and mixed. While maintaining the internal temperature at 15 to 20 ° C. in a water bath, 1.98 g (20.2 mmol) of sulfuric acid was added dropwise over 30 minutes. After dropping, the mixture was stirred for 45 hours while maintaining the liquid temperature at 15 to 25 ° C. Water was placed in a nitrogen-substituted 200 ml three-necked flask equipped with a stirrer and cooled to 2 ° C. with an ice bath. The adjusted reaction solution was added dropwise over 30 minutes while maintaining the internal temperature at 0 to 5 ° C. in an ice bath. The mixture was stirred for 1 hour while maintaining the temperature at 0 to 5 ° C. The precipitated crystals were filtered and rinsed twice with 5 g of water to obtain 5.5 g of crude crystals. After 33 g of toluene was added to the crude crystals and dissolved at a liquid temperature of 40 ° C., 50 g of cyclohexane was added dropwise over 1 hour while maintaining the liquid temperature at 40 ° C. After completion of the dropwise addition, the liquid temperature was further lowered to 0-5 ° C. and cooled for 1 hour. The precipitated crystals were filtered and rinsed with 5.5 g of cyclohexane. The obtained crystals were dried under reduced pressure, and 1- (Nt-butylcarbamoyl) -5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 represented by the formula (2c). Nonane-2-one 4.1 g (13 mmol, yield 63%) was obtained. The NMR spectrum data is shown below.
¹ H-NMR (DMSO-d6) δ: 7.58 (1H, brs), 6.07 (1H, s), 5.72 (1H, s), 4.61 (1H, d), 4.54 (1H, s), 3.46 (1H, d), 2.51 (1H, m), 2.45 (1H, dd), 1.92 (1H, s), 1.89 (3H, s) , 1.73 (1H, d), 1.60 (1H, d)

Example 4
Synthesis of polymer compounds (copolymers) with the following structure

In a round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 59.5 g of cyclohexanone was placed in a nitrogen atmosphere to maintain the temperature at 80 ° C., and 1-carbamoyl-5-methacryloyloxy-3 was stirred. -Oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 12.33 g (46.5 mmol), 1-hydroxy-3-methacryloyloxyadamantane 5.49 g (23.3 mmol), 1- (1-Methacryloyloxy-1-methylethyl) adamantane 12.19 g (46.5 mmol) dimethyl 2,2′-azobisisobutyrate [made by Wako Pure Chemical Industries, Ltd., trade name “V-601 ]] A monomer solution mixed with 1.80 g and cyclohexanone 110.5 g was added dropwise at a constant rate over 6 hours. After completion of the dropwise addition, stirring was further continued for 2 hours. After completion of the polymerization reaction, the mixture was added dropwise with stirring to a 9: 1 (weight ratio) mixture of hexane and ethyl acetate in 7 times the amount of the reaction solution. The resulting precipitate was filtered and dried under reduced pressure to obtain 28.2 g of the desired resin. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 8400, and molecular weight distribution (Mw / Mn) was 1.86.

Example 5
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 1-carbamoyl-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 12.88 g (48.6 mmol) as a monomer component, 1 The same operation as in Example 4 was performed except that 5.74 g (24.3 mmol) of 2-hydroxy-3-methacryloyloxyadamantane and 11.38 g (48.6 mmol) of 2-methacryloyloxy-2-methyladamantane were used. As a result, 25.5 g of the desired resin was obtained. When the recovered polymer was analyzed by GPC, it was found that Mw (weight average molecular weight) was 8800 and molecular weight distribution (Mw / Mn) was 1.90.

Example 6
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 1-carbamoyl-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 13.41 g (50.6 mmol) as a monomer component, 1 Example 4 except that 5.97 g (25.3 mmol) of 1-hydroxy-3-methacryloyloxyadamantane and 10.62 g (50.6 mmol) of 1- (1-methacryloyloxy-1-methylethyl) cyclohexane were used. The same operation was performed to obtain 28.0 g of the desired resin. When the recovered polymer was analyzed by GPC, Mw (weight average molecular weight) was 8800 and molecular weight distribution (Mw / Mn) was 1.88.

Example 7
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 1-carbamoyl-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 12.25 g (46.2 mmol) as a monomer component, 1 The same operation as in Example 4 was carried out except that 5.45 g (23.1 mmol) of 1-hydroxy-3-methacryloyloxyadamantane and 12.30 g (46.2 mmol) of 1- (bornyloxy) ethyl methacrylate were used. As a result, 27.1 g of the desired resin was obtained. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 8300, and molecular weight distribution (Mw / Mn) was 1.85.

Example 8
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 1-carbamoyl-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 14.07 g (53.1 mmol) as a monomer component, 1 The same operation as in Example 4 except that 6.27 g (26.5 mmol) of 1-hydroxy-5-methacryloyloxyadamantane and 9.66 g (53.1 mmol) of 1-methacryloyloxy-1-ethylcyclopentane were used. As a result, 26.9 g of the desired resin was obtained. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 9000 and molecular weight distribution (Mw / Mn) was 1.91.

Example 9
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 1-carbamoyl-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 13.78 g (42. 7 mmol), 5.04 g (21.3 mmol) of 1-hydroxy-3-methacryloyloxyadamantane, and 11.18 g (42.7 mmol) of 1- (1-methacryloyloxy-1-methylethyl) adamantane were used. Were the same operations as in Example 4 to obtain 27.4 g of the desired resin. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 8200 and molecular weight distribution (Mw / Mn) was 1.85.

Example 10
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, as monomer component, 1- (Nt-butylcarbamoyl) -5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 13.74 g ( 42.8 mmol), 1-hydroxy-3-methacryloyloxyadamantane 5.05 g (21.4 mmol), 1- (1-methacryloyloxy-1-methylethyl) adamantane 11.21 g (42.8 mmol) Except for the above, the same operation as in Example 4 was performed to obtain 28.0 g of the desired resin. When the recovered polymer was analyzed by GPC, the Mw (weight average molecular weight) was 8400, the molecular weight distribution (Mw / Mn) was 1. 87.

Example 11
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 9.60 g (36.2 mmol) of 1-carbamoyl-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one as a monomer component, 1 -Hydroxy-3-methacryloyloxyadamantane 5.70 g (24.1 mmol), 1- (1-methacryloyloxy-1-methylethyl) adamantane 12.65 g (48.3 mmol), α-methacryloyloxy-γ-butyrolactone The same operation as in Example 4 was carried out except that 2.05 g (12.1 mmol) was used, and 28.4 g of the desired resin was obtained. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 8500, and molecular weight distribution (Mw / Mn) was 1.86.

Example 12
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 13.71 g (51.7 mmol) of 1-carbamoyl-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one as a monomer component, 1 The same operation as in Example 4 was performed except that 16.29 g (77.6 mmol) of-(1-methacryloyloxy-1-methylethyl) cyclohexane was used, and 25.6 g of a desired resin was obtained. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 8700 and molecular weight distribution (Mw / Mn) was 1.88.

Example 13
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, as a monomer component, 1-carbamoyl-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 12.79 g (48.3 mmol), 1-hydroxy-3-methacryloyloxyadamantane 5.70 g (24.1 mmol), 1- (1-methacryloyloxy-1-methylethyl) adamantane 9.49 g (36.2 mmol), 1- (1-methacryloyloxy) The same operation as in Example 4 was carried out except that 2.03 g (12.1 mmol) of (-1-methylethyl) cyclopropane was used, and 28.3 g of the desired resin was obtained. The recovered polymer was analyzed by GPC. As a result, Mw (weight average molecular weight) was 8600, and molecular weight distribution (Mw / Mn) was 1.88.

Comparative Example 1
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 11.06 g (49.8 mmol), 1-hydroxy-3 as a monomer component -Operations similar to Example 4 except that 5.88 g (24.9 mmol) of methacryloyloxyadamantane and 13.06 g (49.8 mmol) of 1- (1-methacryloyloxy-1-methylethyl) adamantane were used. As a result, 28.0 g of the desired resin was obtained. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 8500, and molecular weight distribution (Mw / Mn) was 1.86.

Comparative Example 2
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 11.60 g (52.3 mmol) of 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one as monomer component, 1-hydroxy-3 -The same operation as in Example 4 was performed except that 6.17 g (26.1 mmol) of methacryloyloxyadamantane and 12.23 g (52.3 mmol) of 2-methacryloyloxy-2-methyladamantane were used. 25.9 g of the desired resin was obtained. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 9000 and molecular weight distribution (Mw / Mn) was 1.90.

Comparative Example 3
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, as the monomer component, 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 12.11 g (54.5 mmol), 1-hydroxy-3 -The same operation as in Example 4 was performed except that 6.44 g (27.3 mmol) of methacryloyloxyadamantane and 11.45 g (54.5 mmol) of 2-methacryloyloxy-2-methyladamantane were used. 28.1 g of the desired resin was obtained. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 8700, and molecular weight distribution (Mw / Mn) was 1.87.

Comparative Example 4
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 10.99 g (49.5 mmol) as a monomer component, 1-hydroxy-3 -The same operation as in Example 4 was carried out except that 5.84 g (24.8 mmol) of methacryloyloxyadamantane and 13.70 g (49.5 mmol) of 1- (bornyloxy) ethyl methacrylate were used. 26.9 g of the desired resin was obtained. When the recovered polymer was analyzed by GPC, it was found that Mw (weight average molecular weight) was 8500 and molecular weight distribution (Mw / Mn) was 1.85.

Comparative Example 5
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, as a monomer component, 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 12.76 g (57.5 mmol), 1-hydroxy-3 -The same operation as in Example 4 was performed except that 6.78 g (28.7 mmol) of methacryloyloxyadamantane and 10.46 g (57.5 mmol) of 1-methacryloyloxy-1-ethylcyclopentane were used. To give 26.7 g of the desired resin. GPC analysis of the recovered polymer revealed that Mw (weight average molecular weight) was 9100 and molecular weight distribution (Mw / Mn) was 1.90.

Comparative Example 6
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, 11.82 g (47.8 mmol) of 1-cyano-5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one as a monomer component, 1 Example 4 except that 5.65 g (23.9 mmol) of 1-hydroxy-3-methacryloyloxyadamantane and 12.54 g (47.8 mmol) of 1- (1-methacryloyloxy-1-methylethyl) adamantane were used. As a result of the same operation as described above, 28.2 g of the desired resin was obtained. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 8400, and molecular weight distribution (Mw / Mn) was 1.85.

Comparative Example 7
Synthesis of polymer compounds (copolymers) with the following structure

In Example 4, as monomer component, 1-cyano-5- (2-methacryloyloxyacetoxy) -3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one 13.36 g (43. 8 mmol), 5.17 g (26.9 mmol) of 1-hydroxy-3-methacryloyloxyadamantane, and 11.47 g (43.8 mmol) of 1- (1-methacryloyloxy-1-methylethyl) adamantane were used. Were the same operations as in Example 4 to obtain 28.5 g of the desired resin. As a result of GPC analysis of the recovered polymer, Mw (weight average molecular weight) was 8200, and molecular weight distribution (Mw / Mn) was 1.84.

Evaluation test 1
The solubility parameter (SP value) of the carbamoyl group and lactone skeleton-containing monomer synthesized in Examples 1 to 3 and the monomer to be compared was calculated by the Fedors method. The results are shown in Table 1. The unit of SP value is (cal / cm ³ ) ^1/2 . “TBu” in the formula represents a t-butyl group.
No. 1 (monomer of Example 1) and No. 1 2, No. 3 (monomer of Example 2) and No. 2 From the numerical value of each compound of 4, it was found that the compound having a carbamoyl group had a higher solubility parameter and higher affinity for water than the corresponding compound having a cyano group.
Similarly, no. 5 (monomer of Example 3) and From the numerical value of 6, it was found that the compound having an Nt-butylcarbamoyl group had a larger solubility parameter and higher affinity for water than the corresponding compound having a t-butoxycarbonyl group.

Evaluation test 2
Cyclohexanone was added to each photoresist polymer resin obtained in Examples 4 to 13 and Comparative Examples 1 to 7, and the resin was dissolved so that a cyclohexanone solution having a polymer concentration of 20% by weight was obtained. To each obtained polymer solution for photoresist, 10 parts by weight of triphenylsulfonium hexafluoroantimonate is added to 100 parts by weight of polymer, and cyclohexanone is further added to adjust the polymer concentration to 15% by weight. A photoresist composition was prepared by filtering with a filter.
This photoresist composition was applied to a silicon wafer by spin coating to form a photosensitive layer having a thickness of 0.7 μm. After pre-baking on a hot plate at a temperature of 100 ° C. for 150 seconds, using an ArF excimer laser with a wavelength of 193 nm, the film was exposed through a mask at an irradiation dose of 30 mJ / cm ² and then post-baked at a temperature of 100 ° C. for 60 seconds. Subsequently, it developed for 60 second with the 2.38M tetramethylammonium hydroxide aqueous solution, and rinsed with the ultrapure water. When any of the photoresist polymer solutions of Examples and Comparative Examples was used, a 0.25 μm line and space pattern was obtained, but Examples 4 to 13 were clearly clearer than the Comparative Examples. And there were few defects.

Claims (13)

The following formula (1a)

[Wherein, R ^a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ represents a substituent bonded to the ring, An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms in which a hydroxyl group portion may be protected with a protecting group and may have a halogen atom An alkyl group, a carboxyl group that may form a salt, or a substituted oxycarbonyl group is shown. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^b and R ^c are bonded to each other, and together with the nitrogen atom shown in the formula, 5- a non-aromatic nitrogen-containing heterocyclic 6-membered may form)
The carbamoyl group represented by these is shown . Y represents a divalent organic group having 1 to 6 carbon atoms. k represents 0 or 1. The steric position of the CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k —O— group may be either endo or exo.
The monomer containing the carbamoyl group represented by these, and a lactone skeleton. 2. The monomer containing a carbamoyl group and a lactone skeleton according to claim 1 , wherein R ^b and R ^c are both hydrogen atoms, or one is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms . The following formula (Ia)

[Wherein, R ^a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ represents a substituent bonded to the ring, An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms in which a hydroxyl group portion may be protected with a protecting group and may have a halogen atom An alkyl group, a carboxyl group that may form a salt, or a substituted oxycarbonyl group is shown. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^b and R ^c are bonded to each other, and together with the nitrogen atom shown in the formula, 5- a non-aromatic nitrogen-containing heterocyclic 6-membered may form)
The carbamoyl group represented by these is shown . Y represents a divalent organic group having 1 to 6 carbon atoms. k represents 0 or 1. The steric position of the CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k —O— group may be either endo or exo.
The high molecular compound which has at least the monomer unit represented by these. 4. The polymer compound according to claim 3 , wherein R ^b and R ^c are both hydrogen atoms, or one is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms . 5. The polymer compound according to claim 3, further comprising at least a monomer unit that becomes alkali-soluble by the action of an acid in addition to the monomer unit represented by formula (Ia) . Monomer units which are eliminated by the action of an acid and become alkali-soluble are represented by the following formulas (Va) to (Vd)

(In the formula, ring Z ¹ represents an alicyclic hydrocarbon ring having 3 to 20 carbon atoms which may have a substituent. R ^a may have a hydrogen atom, a halogen atom or a substituent. R ^{1 to} R ⁴ are the same or different and each represents an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ⁵ is a ring Z ^1. The same or different substituents bonded to the oxo group, alkyl group, hydroxyl group optionally protected with a protecting group, hydroxyalkyl group optionally protected with a protecting group, or protecting group And represents a carboxyl group which may be protected with at least one of p R ^{5 s} representing a —COOR ^d group, wherein R ^d is a tertiary carbon which may have a substituent. Represents a hydrogen group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group; Be .p is .R ^6, R ⁷ represents an integer of 1 to 3, same or different, .R ⁸ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms A hydrogen atom or an organic group, at least two of R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring with adjacent atoms)
The polymer compound according to claim 5, which is a monomer unit selected from the group consisting of: The polymer according to any one of claims 3 to 6, further comprising at least a monomer unit containing an alicyclic skeleton having at least one substituent in addition to the monomer unit represented by the formula (Ia). Compound. A monomer unit containing an alicyclic skeleton having at least one substituent is represented by the following formula (VI):

(In the formula, ring Z ² represents an alicyclic hydrocarbon ring having 6 to 20 carbon atoms. ^Ra represents ^a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms. R ⁹ is a substituent bonded to ring Z ² and is the same or different and is an oxo group, an alkyl group, a haloalkyl group, a halogen atom, a hydroxyl group optionally protected by a protecting group, a protected group A hydroxyalkyl group optionally protected with a group, a mercapto group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, an amino group optionally protected with a protecting group, or a protection A sulfonic acid group which may be protected by a group, q is the number of R ⁹ and represents an integer of 1 to 5)
The polymer compound according to claim 7, which is a monomer unit selected from: An alicyclic skeleton having a monomer unit represented by the formula (Ia) , a monomer unit that becomes alkali-soluble by the action of an acid, and at least one substituent selected from a hydroxyl group and a hydroxymethyl group The polymer compound according to claim 5 or 6, which has at least a monomer unit to be contained. The monomer unit according to any one of claims 3 to 9, further comprising at least a monomer unit having a lactone skeleton other than the monomer unit represented by the formula (Ia) in addition to the monomer unit represented by the formula (Ia). High molecular compound.   A photoresist composition comprising at least the polymer compound according to claim 3 and a photoacid generator.   A pattern is formed using the photoresist composition of Claim 11, The manufacturing method of the semiconductor characterized by the above-mentioned. The following formula (1a)

[Wherein, R ^a represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, and R ¹ represents a substituent bonded to the ring, An alkyl group having 1 to 6 carbon atoms which may have an atom or a halogen atom, or a hydroxy group having 1 to 6 carbon atoms in which a hydroxyl group portion may be protected with a protecting group and may have a halogen atom An alkyl group, a carboxyl group that may form a salt, or a substituted oxycarbonyl group is shown. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^b and R ^c are bonded to each other, and together with the nitrogen atom shown in the formula, 5- a non-aromatic nitrogen-containing heterocyclic 6-membered may form)
The carbamoyl group represented by these is shown . Y represents a divalent organic group having 1 to 6 carbon atoms. k represents 0 or 1. The steric position of the CH ₂ ═C (R ^a ) CO— (O—Y—CO) _k —O— group may be either endo or exo.
A monomer having a carbamoyl group and a lactone skeleton represented by the following formula (3 ′):

[Wherein R ¹ is a substituent bonded to the ring, and a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxyl group moiety is protected with a protecting group. And a hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom, a carboxyl group which may form a salt, or a substituted oxycarbonyl group. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8 . R ^e represents a hydrogen atom or an organic group. The steric position of the R ^e O- group may be either endo or exo]
A cyano group-containing lactone compound represented by the following formula (4 ′)

[Wherein R ¹ is a substituent bonded to the ring, and a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxyl group moiety is protected with a protecting group. And a hydroxyalkyl group having 1 to 6 carbon atoms which may have a halogen atom, a carboxyl group which may form a salt, or a substituted oxycarbonyl group. A represents an alkylene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom or a non-bond. m is the number of R ¹ and represents an integer of 0-8. X is the following formula (2)

(In the formula, R ^b and R ^c each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^b and R ^c are bonded to each other, and together with the nitrogen atom shown in the formula, 5- a non-aromatic nitrogen-containing heterocyclic 6-membered may form)
The carbamoyl group represented by these is shown . R ^e represents a hydrogen atom or an organic group. The steric position of the R ^e O- group may be either endo or exo]
A process for producing a monomer containing a carbamoyl group and a lactone skeleton, comprising at least a step of converting to a carbamoyl group-containing lactone compound represented by the formula: