JP2011001542A - Acid-cleavable ester monomer having spiro ring structure, polymer compound, resist material and pattern-forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acid-cleavable ester monomer having a spiro ring structure and useful for producing a base resin giving a resist material having high resolution and small PEB temperature dependency, a polymer compound produced by using the acid-cleavable ester monomer having the spiro ring structure, the resist material containing the polymer compound as the base resin, and a pattern-forming method to use the resist material.SOLUTION: The acid-cleavable ester monomer having the spiro ring structure is expressed by general formula (1) (wherein Z is univalent group having polymerizable double bond; X is bivalent group forming substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with carbon atom bonded thereto; Ris hydrogen atom or univalent hydrocarbon group; Rand Rare each hydrogen atom or univalent hydrocarbon group, or Rand Rare bonded together to form bivalent group forming substituted or unsubstituted cyclopentane ring or cyclohexane ring together with carbon atom bonded thereto; and n is 1 or 2).

Description

The present invention relates to an acid-eliminating ester-type monomer (monomer, that is, a polymerizable compound) having a spiro ring structure useful as a raw material for functional materials. This acid-eliminating ester monomer having a spiro ring structure has excellent transparency to radiation having a wavelength of 500 nm or less, particularly 300 nm or less, such as KrF laser light, ArF laser light, and F ₂ laser light. It is very useful as a raw material monomer for polymer to produce a base resin of radiation sensitive resist material that has excellent resolution and development properties due to elimination reaction in the presence of acid. It is.
Furthermore, the present invention relates to a polymer (polymer compound) having a repeating unit derived from the acid-eliminating ester-type monomer having a spiro ring structure, a photoresist material containing the polymer compound, and the photoresist The present invention relates to a pattern forming method using a material.

In recent years, along with the high integration and high speed of LSIs, far-ultraviolet lithography is considered promising as a next-generation microfabrication technique, while miniaturization of pattern rules is required. In particular, photolithography using KrF laser light, ArF laser light, or F ₂ laser light as a light source is highly desired to be realized as an indispensable technique for ultrafine processing of 0.3 μm or less. Various alkali-soluble resins are used as the base resin for these resist materials.

  As a base resin for the KrF resist material, a polyhydroxystyrene resin has become a de facto standard. As base resins for ArF resist materials, poly (meth) acrylate resins using carboxyl groups as alkali-soluble groups and resins using aliphatic cyclic olefins such as norbornene as polymerization units have been studied, and among these, poly (meth) acrylates Is practically used because of its ease of polymerization.

  As a poly (meth) acrylate, as a repeating unit having an acid labile group (acid labile unit) described in JP-A-9-90637, a repeat having an adamantyl (meth) acrylate and an adhesive group is mentioned. A combination with a (meth) acrylate having a lactone ring as a unit has been proposed. Patent Document 2: JP-A-9-73173 discloses an acid labile group having an alkylcycloalkyl type tertiary alkyl group. Patent Document 3: JP 2000-327633 A introduces an acid labile group having an exo isomer of an alkylbicyclo [2.2.1] heptanol type tertiary alkyl group. Since this has high acid detachability and low activation energy in acid detachment, high resolution and low post-exposure bake (PEB) dependency can be obtained. Furthermore, the adhesive group having enhanced etching resistance includes norbornane lactone and oxanorbornane lactone described in Patent Document 4: JP 2000-26446 A, Patent Document 5: JP 2000-159758 A (meth). Acrylate units have been proposed. These studies have greatly improved the resolution of ArF resist. Further, in Patent Document 6: Japanese Patent Application Laid-Open No. 2003-113213, in addition to an acid labile group unit and a lactone unit, 3 is used as a unit for controlling diffusion of an acid generated by exposure from a photoacid generator in a resist film. A ternary polymer to which a repeating unit having a hydroxyl group such as -hydroxy-1-adamantyl (meth) acrylate is added has also been put into practical use as a base resin of a resist material.

  In the acid-catalyzed desorption reaction in the resist film, if the desorption reactivity of the acid labile unit is high, the desorption reaction proceeds even at low temperatures, so the post-exposure bake (PEB) temperature can be lowered. Thus, the thermal diffusion of the acid during the PEB process can be suppressed. Further, by imparting appropriate fat solubility to the acid labile unit, the exposure dose-dependent contrast of the dissolution rate with respect to the developer can be increased. Low acid diffusivity and high contrast contribute to improvement of resolution, that is, expansion of various process margins such as exposure margin (EL), depth of focus (DOF) and mask fidelity in a fine pattern. It is also effective to minimize pattern roughness (Line Edge Roughness and Line Width Roughness in line and space patterns, Circularity in hole patterns, etc.). In addition, highly desorbable, acid-labile units reduce PEB temperature dependence of pattern dimensions and suppress dimensional variations due to slight thermal history differences between different locations on the wafer surface. I can expect that. In view of the above, there is a strong demand for highly desorbable, acid-labile units having appropriate fat solubility.

JP-A-9-90637 JP-A-9-73173 JP 2000-327633 A JP 2000-26446 A JP 2000-159758 A JP 2003-113213 A

  The present invention relates to an acid-eliminating ester-type monomer having a spiro ring structure and an acid-eliminating ester having a spiro ring structure, which are useful for obtaining a base resin that provides a resist material having high resolution and low PEB temperature dependency It is an object of the present invention to provide a polymer compound using a type monomer, a resist material containing the polymer compound as a base resin, and a pattern forming method using the resist material.

  As a result of various studies for realizing a resist material having high resolution and low PEB temperature dependency in photolithography using a high energy beam such as ArF excimer laser light as a light source, the present inventors It has been found that an acid-eliminating ester type monomer having a specific spiro ring structure is extremely useful as a monomer of the above.

  That is, the present inventors can easily produce an acid-eliminating ester type monomer having a spiro ring structure represented by the following general formula (1), and furthermore, an acid-eliminating ester having this spiro ring structure. It was found that a resist material using a polymer compound obtained from a type monomer as a base resin has a high contrast, and that this polymer compound is extremely effective as a resist material for precise microfabrication. It came to make.

（式中、Ｚは重合性二重結合を有する１価の基を表す。Ｘはこれが結合する炭素原子と共に置換又は非置換のシクロペンタン環、シクロヘキサン環、又はノルボルナン環を形成する２価の基を表す。Ｒ²は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表す。Ｒ³、Ｒ⁴はそれぞれ独立に水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表し、又は、Ｒ³とＲ⁴は互いに結合してこれらが結合する炭素原子と共に置換又は非置換のシクロペンタン環、又はシクロヘキサン環を形成する２価の基を表す。ｎは１又は２を表す。）

（式中、Ｘはこれが結合する炭素原子と共に置換又は非置換のシクロペンタン環、シクロヘキサン環、又はノルボルナン環を形成する２価の基を表す。Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表す。Ｒ³、Ｒ⁴はそれぞれ独立に水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表し、又は、Ｒ³とＲ⁴は互いに結合してこれらが結合する炭素原子と共に置換又は非置換のシクロペンタン環、又はシクロヘキサン環を形成する２価の基を表す。Ｒ⁵は水素原子、又はメチル基を表す。ｎは１又は２を表す。ｐは０又は１を表す。） Accordingly, the present invention provides an acid-eliminating ester-type monomer having a spiro ring structure represented by the following general formula (1), or the following general formula (2) or (3).

(In the formula, Z represents a monovalent group having a polymerizable double bond. X represents a divalent group which forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ² represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom or 1 to 1 carbon atom. 10 linear, branched or cyclic monovalent hydrocarbon groups, or R ³ and R ⁴ are bonded to each other and substituted or unsubstituted cyclopentane ring or cyclohexane ring together with the carbon atom to which they are bonded Represents a divalent group forming n. N represents 1 or 2.)

(In the formula, X represents a divalent group which forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trivalent group. Represents a fluoromethyl group, R ² represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ and R ⁴ each independently represents a hydrogen atom or carbon Represents a linear, branched or cyclic monovalent hydrocarbon group of 1 to 10, or R ³ and R ⁴ are bonded to each other and substituted or unsubstituted cyclopentane ring together with the carbon atom to which they are bonded; Or a divalent group that forms a cyclohexane ring, R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, and p represents 0 or 1.)

（式中、Ｚａは重合性二重結合を有する１価の基Ｚに由来し、重合によって生じる３価の基を表す。Ｘはこれが結合する炭素原子と共に置換又は非置換のシクロペンタン環、シクロヘキサン環、又はノルボルナン環を形成する２価の基を表す。Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表す。Ｒ³、Ｒ⁴はそれぞれ独立に水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表し、又は、Ｒ³とＲ⁴は互いに結合してこれらが結合する炭素原子と共に置換又は非置換のシクロペンタン環、又はシクロヘキサン環を形成する２価の基を表す。Ｒ⁵は水素原子、又はメチル基を表す。ｎは１又は２を表す。ｐは０又は１を表す。） The present invention also includes a repeating unit obtained from the acid-eliminating ester-type monomer having the spiro ring structure represented by the following general formulas (1a) to (3a). A molecular compound is provided.

(In the formula, Za is derived from a monovalent group Z having a polymerizable double bond, and represents a trivalent group generated by polymerization. X represents a substituted or unsubstituted cyclopentane ring, cyclohexane together with the carbon atom to which it is bonded. R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R ² represents a hydrogen atom, or a straight chain having 1 to 10 carbon atoms. Represents a branched or cyclic monovalent hydrocarbon group, each of R ³ and R ⁴ independently represents a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, Or R ³ and R ⁴ represent a divalent group which forms a substituted or unsubstituted cyclopentane ring or cyclohexane ring together with the carbon atom to which they are bonded, and R ⁵ represents a hydrogen atom or a methyl group N represents 1 or 2. p It represents 0 or 1.)

（式中、Ｒ⁶、Ｒ⁷、Ｒ⁸はそれぞれ独立に水素原子、又はそれぞれヘテロ原子を含んでもよい炭素数１〜２０の直鎖状、分岐状又は環状の１価の炭化水素基、炭素数１〜１０のアルコキシ基、又は、ハロゲン原子を示す。Ｒ⁹はヘテロ原子を含んでもよい炭素数１〜３０の直鎖状、分岐状又は環状の１価の炭化水素基を示す。Ｒ¹⁰は水素原子又はトリフルオロメチル基を示す。） Furthermore, the present invention provides a resist material characterized in that it contains the above polymer compound as a base resin and a compound that generates an acid in response to actinic rays or radiation.
In this case, the compound that generates an acid in response to the actinic ray or radiation is preferably a sulfonium salt compound represented by the following general formula (4).

(Wherein R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, each of which may contain a hetero atom, carbon C 1 -C 10 alkoxy group, or, .R ¹⁰ indicating a halogen atom .R ⁹ is carbon atoms which may contain a heteroatom 1-30 linear, monovalent hydrocarbon group branched or cyclic Represents a hydrogen atom or a trifluoromethyl group.)

  The present invention also includes a step of applying the resist material on the substrate, a step of exposing with a high energy beam or an electron beam through a photomask after the heat treatment, a heat treatment if necessary, and then a developer. And a developing process using the pattern forming method.

  The acid-eliminating ester type monomer having a spiro ring structure of the present invention is useful as a raw material for functional materials and has excellent transparency to radiation having a wavelength of 500 nm or less, particularly 300 nm or less. The polymer compound of the present invention is extremely useful as a monomer for producing a base resin of a radiation-sensitive resist material having extremely high reactivity in an acid elimination reaction and good resolution. It is useful as a base resin for radiation resist materials. In addition, the resist material of the present invention has a high resolving power, an excellent performance in exposure margin, depth of focus, mask fidelity, and low roughness. Furthermore, the PEB temperature dependency of the pattern dimension is small, which is effective for improving the yield in actual production.

Hereinafter, the present invention will be described in detail.
In the present invention, in the following chemical formulas, there may be enantiomers or diastereomers in terms of chemical structure, but in any case, unless otherwise specified, Is representative of all of these stereoisomers. In addition, these stereoisomers may be used alone or as a mixture.

（式中、Ｚは重合性二重結合を有する１価の基を表す。Ｘはこれが結合する炭素原子と共に置換又は非置換のシクロペンタン環、シクロヘキサン環、又はノルボルナン環を形成する２価の基を表す。Ｒ²は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表す。Ｒ³、Ｒ⁴はそれぞれ独立に水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表し、又は、Ｒ³とＲ⁴は互いに結合してこれらが結合する炭素原子と共に置換又は非置換のシクロペンタン環、又はシクロヘキサン環を形成する２価の基を表す。ｎは１又は２を表す。） The acid-eliminating ester monomer having a spiro ring structure of the present invention is represented by the following general formula (1).

(In the formula, Z represents a monovalent group having a polymerizable double bond. X represents a divalent group which forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ² represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom or 1 to 1 carbon atom. 10 linear, branched or cyclic monovalent hydrocarbon groups, or R ³ and R ⁴ are bonded to each other and substituted or unsubstituted cyclopentane ring or cyclohexane ring together with the carbon atom to which they are bonded Represents a divalent group forming n. N represents 1 or 2.)

Z represents a monovalent group having a polymerizable double bond. Specific examples of Z include vinyl group, ethynyl group, 1-propenyl group, isopropenyl group, 3,3,3-trifluoro-2-propenyl group, allyl group, 1,3-butadienyl group, 2-methyl- 1-propenyl group, 5-norbornen-2-yl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] a group containing multiple bonds such as dodec-8-en-3-yl group, or acrylic acid ester, methacrylic acid ester, α-trifluoromethyl acrylic acid ester, vinyl ether, allyl ether, Norbornene, tricyclo [5.2.1.0 ^2,6 ] decene, tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] groups containing a partial structure such as dodecene, such as acryloyloxymethyl group, methacryloyloxymethyl group, α-trifluoromethylacryloylmethyl group, 1- (acryloyloxy) ethyl group, 1- (methacryloyloxy) ethyl Group, 1- (α-trifluoromethylacryloyloxy) ethyl group, 2- (acryloyloxy) ethyl group, 2- (methacryloyloxy) ethyl group, 2- (α-trifluoromethylacryloyloxy) ethyl group, 3- (Acryloyloxy) propyl group, 3- (methacryloyloxy) propyl group, 3- (α-trifluoromethylacryloyloxy) propyl group, 4- (acryloyloxy) butyl group, 4- (methacryloyloxy) butyl group, 3- (Α-trifluoromethylacryloylio Xyl) butyl, 2-vinyloxyethyl, 2-vinyloxypropyl, 3-vinyloxypropyl, 2-allyloxyethyl, 2-allyloxypropyl, 3-allyloxypropyl, 5-norbornene 2-carbonyloxymethyl group, 2- (5-norbornene-2-carbonyloxy) ethyl group, 5-norbornen-2-ylmethyl group, 2- (5-norbornen-2-yl) ethyl group, 5-acryloyloxy Norbornane-2-carbonyloxymethyl group, 2- (5-acryloyloxynorbornane-2-carbonyloxy) ethyl group, 5-acryloyloxynorbornan-2-ylmethyl group, 2- (5-acryloyloxynorbornan-2-yl) Ethyl group, 5-methacryloyloxynorbornane-2-cal Nyloxymethyl group, 2- (5-methacryloyloxynorbornane-2-carbonyloxy) ethyl group, 5-methacryloyloxynorbornane-2-ylmethyl group, 2- (5-methacryloyloxynorbornan-2-yl) ethyl group, 5 -(Α-trifluoromethylacryloyloxy) norbornane-2-carbonyloxymethyl group, 2- (5- (α-trifluoromethylacryloyloxy) norbornane-2-carbonyloxy) ethyl group, 5- (α-trifluorooxy) Methylacryloyloxy) norbornan-2-ylmethyl group, 2- (5- (α-trifluoromethylacryloyloxy) norbornan-2-yl) ethyl group, (tricyclo [5.2.1.0 ^2,6 ] deca- 8-ene-4-carbonyloxy) methyl group, 2- (tri Black [5.2.1.0 ^{2, 6]} dec-8-ene-4-carbonyloxy) ethyl group, (tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-8-ene-3-carbonyloxy) methyl group, 2- (tetracyclo [4.4.0.1 ^2,5 7.1 ^7,10 ] dodec-8-ene-3-carbonyloxy ) An ethyl group or the like.

（式中、Ｘはこれが結合する炭素原子と共に置換又は非置換のシクロペンタン環、シクロヘキサン環、又はノルボルナン環を形成する２価の基を表す。Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表す。Ｒ³、Ｒ⁴はそれぞれ独立に水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表し、又は、Ｒ³とＲ⁴は互いに結合してこれらが結合する炭素原子と共に置換又は非置換のシクロペンタン環、又はシクロヘキサン環を形成する２価の基を表す。Ｒ⁵は水素原子、又はメチル基を表す。ｎは１又は２を表す。ｐは０又は１を表す。） Among these, vinyl group, isopropenyl group, 3,3,3-trifluoro-2-propenyl group or 5-norbornen-2-yl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-en-3-yl group, and in these cases, the acid-eliminating ester type monomer having a spiro ring structure is represented by the following general formulas (2) and (3). The

(In the formula, X represents a divalent group which forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trivalent group. Represents a fluoromethyl group, R ² represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ and R ⁴ each independently represents a hydrogen atom or carbon Represents a linear, branched or cyclic monovalent hydrocarbon group of 1 to 10, or R ³ and R ⁴ are bonded to each other and substituted or unsubstituted cyclopentane ring together with the carbon atom to which they are bonded; Or a divalent group that forms a cyclohexane ring, R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, and p represents 0 or 1.)

（式中、点線は結合手を表す。）
は、置換又は非置換のシクロペンタン環、シクロヘキサン環、又はノルボルナン環、即ち、下記部分構造

（式中、点線は結合手を表す。）
で表される環構造を表し、又は、これらを含む縮合環でもよい。これらの構造中の単数又は複数の水素原子が炭素数１〜３のアルキル基、水酸基（−ＯＨ）又はハロゲン原子に置換されていてもよく、これらの構造中の単数又は複数のメチレン基（−ＣＨ₂−）がカルボニル基［−（Ｃ＝Ｏ）−］又は酸素原子（−Ｏ−）等のヘテロ原子に置換されていてもよい。 X represents a divalent group that forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring, or norbornane ring together with the carbon atom to which it is bonded. That is, the following partial structure

(In the formula, the dotted line represents a bond.)
Is a substituted or unsubstituted cyclopentane ring, cyclohexane ring, or norbornane ring, that is, the following partial structure:

(In the formula, the dotted line represents a bond.)
Or a condensed ring containing these may be used. One or more hydrogen atoms in these structures may be substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxyl group (—OH) or a halogen atom, and one or more methylene groups (— CH ₂ —) may be substituted with a heteroatom such as a carbonyl group [— (C═O) —] or an oxygen atom (—O—).

R ² represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples of a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group Tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group , Cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, methylcyclohexylmethyl group, ethylcyclohexylmethyl group, ethylcyclohexylethyl group, bicyclo [2.2.1 ] Heptyl group, bicyclo [2.2.1] heptylmethyl Group, bicyclo [2.2.1] heptylethyl group, bicyclo [2.2.1] heptylbutyl group, methylbicyclo [2.2.1] heptylmethyl group, ethylbicyclo [2.2.1] heptylmethyl Group, ethylbicyclo [2.2.1] heptylethyl group, bicyclo [2.2.2] octyl group, bicyclo [2.2.2] octylmethyl group, bicyclo [2.2.2] octylethyl group, Bicyclo [2.2.2] octylbutyl group, methylbicyclo [2.2.2] octylmethyl group, ethylbicyclo [2.2.2] octylmethyl group, ethylbicyclo [2.2.2] octylethyl group , Tricyclo [5.2.1.0 ^2,6 ] decyl group, tricyclo [5.2.1.0 ^2,6 ] decylmethyl group, tricyclo [5.2.1.0 ^2,6 ] decylethyl group, tricyclo [5 2.1.0 ^2,6] Deshirubuchiru group, methyltricyclo [5.2.1.0 ^2,6] Deshirumechiru group, ethyl tricyclo [5.2.1.0 ^2,6] Deshirumechiru group, ethyltri Cyclo [5.2.1.0 ^2,6 ] decylethyl group, adamantyl group, adamantylmethyl group, adamantylethyl group, adamantylbutyl group, methyladamantylmethyl group, ethyladamantylmethyl group, ethyladamantylethyl group, tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] dodecyl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecylmethyl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecylethyl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecylbutyl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecylmethyl group, ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecylmethyl group, ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] linear, branched or cyclic monovalent hydrocarbon groups such as ^dodecylethyl group, phenyl group, tolyl group and naphthyl group. These groups may contain an unsaturated bond. Among these, R ² is particularly preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or an n-butyl group.

R ³ and R ⁴ each independently represent a hydrogen atom, a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. As a specific example when R ³ and R ⁴ are linear, branched or cyclic monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ² is linear or branched having 1 to 10 carbon atoms. Or the thing similar to the specific example in the case of being a cyclic | annular monovalent hydrocarbon group can be illustrated. Of these, a hydrogen atom and a methyl group are particularly preferred. Alternatively, R ³ and R ⁴ may be bonded to each other to form a substituted or unsubstituted cyclopentane ring or cyclohexane ring together with the carbon atom to which they are bonded, or may be a condensed ring containing these. One or more hydrogen atoms in these structures may be substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxyl group (—OH) or a halogen atom, and one or more methylene groups (— CH ₂ —) may be substituted with a carbonyl group or a heteroatom such as an oxygen atom (—O—).

  Specific examples of the acid-eliminating ester-type monomer having a spiro ring structure of the present invention include the following, but are not limited to these.

（式中、Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を表す。）

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.)

（式中、Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を表す。）

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.)

（式中、Ｒ⁵は水素原子又はメチル基を表す。ｐは０又は１を表す。）

(In the formula, R ⁵ represents a hydrogen atom or a methyl group. P represents 0 or 1.)

（式中、Ｒ⁵は水素原子又はメチル基を表す。ｐは０又は１を表す。）

(In the formula, R ⁵ represents a hydrogen atom or a methyl group. P represents 0 or 1.)

The design concept of the acid-eliminating ester-type monomer having a spiro ring structure represented by the general formula (1) of the present invention will be described.
The acid-eliminating ester-type monomer having a spiro ring structure of the present invention is used as a repeating unit of a polymer compound, and this polymer compound is used as a base resin for a radiation-sensitive resist material described later. In the acid-catalyzed elimination reaction in the resist film, an olefin elimination reaction from the acid-eliminating ester occurs by the acid catalyst, and carboxylic acid is generated (this is the solubility in the developer that realizes the resist dissolution contrast). Cause changes). Patent Document 2: Japanese Patent Application Laid-Open No. 9-73173 discloses an acid labile group having an alkylcycloalkyl type tertiary alkyl group and exemplifies a spiro ring structure. There is no description. In the acid-eliminating ester type monomer having a spiro ring structure represented by the general formulas (1), (2), and (3) of the present invention, it is necessary for improving the performance at a specific position of the spiro ring structure. The high reactivity in the acid-catalyzed elimination reaction was realized by arranging various structural elements.

  During the acid-catalyzed elimination reaction in the resist film, a carbocation is generated on the carbon atom to which the polymerizable ester is bonded, and an olefin is generated from the generated carbocation by the elimination of a proton. It is considered that the more stable the carbocation produced in this reaction, the lower the activation energy of the acid catalyst elimination reaction and the higher the reactivity. In the acid-eliminating ester type monomer having a spiro ring structure of the present invention, the greatest feature is that the carbon atom to which the polymerizable ester is bonded and the quaternary carbon atom of the spiro ring are directly bonded. It is considered that high reactivity is realized from the following three points.

1) A carbon atom adjacent to a carbon atom to which a polymerizable ester is bonded (hereinafter referred to as the first carbon atom), that is, a quaternary carbon atom to which X is bonded (= spiro carbon atom; hereinafter, a carbon atom at the second position And an alkyl substitution such as a cyclopentane ring, a cyclohexane ring, or a norbornane ring, and the cation on the 1st carbon atom is stabilized due to the electron donating effect of the alkyl group. It is thought. Further, an alkyl group may be substituted on the carbon atom (hereinafter referred to as the 2′-position carbon atom) to which R ³ and R ⁴ adjacent to the 1-position carbon atom are bonded. Cation stabilization on the carbon atom at the position is expected.

2) Alkyl substitution of the carbon atom at the 2-position (including the carbon atom at the 2′-position when there is a substitution at the 2′-position) resulted in a sterically crowded area around the carbon atom at the 1-position (Sterically) It is thought that the steric hindrance is eliminated by cation formation and subsequent olefin formation, the energy of the production system becomes more stable, and the reaction is more likely to proceed. It is done. As a specific example showing the magnitude of steric hindrance, as will be described later in Examples, the equilibrium between conformations at room temperature is suppressed, and ¹³ C-NMR signal broadening is observed.

  3) In the carbocation intermediate formed on the carbon atom at the 1-position, the rearrangement reaction (1,2-alkyl shift) of the 2-position (or 2'-position) alkyl group occurs, and a more stable carbocation can be generated. In some cases, this equilibrium between carbocations contributes to cation stabilization and is thought to reduce the activation energy of the reaction. As specific examples, as will be described later in Examples, for example, in the case of 6-methylspiro [4.5] decyl ester compound, cation transfer and resultant olefin formation as observed in the following chemical reaction formula are observed. The

Among the acid-eliminating ester monomers having a spiro ring structure represented by the general formula (1) of the present invention, an appropriate structure can be selected for adjusting the elimination reactivity. For example, the number of alicyclic rings to which the polymerizable ester is bonded (whether n is 1 or 2) and the type of substituent R ² bonded to the carbon atom at the 1-position (a hydrogen atom or a monovalent hydrocarbon group) In the case of a monovalent hydrocarbon group, appropriate elimination reactivity adjustment in the resist film can be realized by selection of the type). In addition, an appropriate acid diffusion distance in the resist film can be adjusted by selecting the structure of the alicyclic ring bonded to the 2-position spiro carbon atom, the type of R ³ and R ⁴ , and the like.

A method for producing an acid-eliminating ester monomer having a spiro ring structure represented by the general formulas (1), (2) and (3) of the present invention will be described.
As a typical non-limiting example, an acid-eliminating ester-type monomer having a spiro ring structure represented by the general formulas (1), (2), and (3) of the present invention is an acyl of the corresponding alcohol compound. It can be synthesized by chemical reaction. The corresponding alcohol compound can be synthesized by alkylation of a ketone compound (or reduction when R ² is a hydrogen atom).

（式中、Ｚは重合性二重結合を有する１価の基を表す。Ｘはこれが結合する炭素原子と共に置換又は非置換のシクロペンタン環、シクロヘキサン環、又はノルボルナン環を形成する２価の基を表す。Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表す。Ｒ³、Ｒ⁴はそれぞれ独立に水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表し、又は、Ｒ³とＲ⁴は互いに結合してこれらが結合する炭素原子と共に置換又は非置換のシクロペンタン環、又はシクロヘキサン環を形成する２価の基を表す。Ｒ⁵は水素原子、又はメチル基を表す。ｎは１又は２を表す。ｐは０又は１を表す。）

(In the formula, Z represents a monovalent group having a polymerizable double bond. X represents a divalent group which forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring with the carbon atom to which it is bonded. R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and R ² represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ³ and R ⁴ each independently represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, or R ³ and R ⁴ are bonded to each other. R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, p represents a substituted or unsubstituted cyclopentane ring or a cyclohexane ring together with the carbon atom to which they are bonded. Represents 0 or 1.)

As the esterification reaction, a known ester production method, for example, a reaction with an acylating agent, a reaction with a carboxylic acid, or a transesterification reaction can be applied. In the reaction using an acylating agent, chlorinated solvents such as methylene chloride, chloroform and trichloroethylene, hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether , Ethers such as tetrahydrofuran and 1,4-dioxane, nitriles such as acetonitrile, ketones such as acetone and 2-butanone, esters such as ethyl acetate and n-butyl acetate, N, N-dimethylformamide, dimethylsulfate Select from aprotic polar solvents such as foxoxide, hexamethylphosphoric triamide, etc., in a solvent that is used alone or in a mixture of two or more, alcohol compound as raw material, acrylic acid chloride, methacrylic acid Chloride, acrylic acid bromide, methacrylic acid bromide, α-trifluoromethylacrylic acid chloride, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid chloride, bicyclo [2.2.1] hepta-5 -En-2-methyl-2-carboxylic acid chloride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid chloride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] acid halides such as dodeca-8-ene-3-methyl-3-carboxylic acid chloride, acrylic anhydride, methacrylic anhydride, α-trifluoromethylacrylic anhydride, bicyclo anhydride [2. 2.1] Hepta-5-ene-2-carboxylic acid, bicyclo [2.2.1] hept-5-ene-2-methyl-2-carboxylic acid anhydride, tetracyclo [4.4.0.1 ^{2 , 5} . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid, anhydrous tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodec-8-ene-3-methyl-3-carboxylic acid, acrylic acid trifluoroacetic acid mixed acid anhydride, methacrylic acid trifluoroacetic acid mixed acid anhydride, α-trifluoromethylacrylic acid trifluoroacetic acid Mixed acid anhydride, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid trifluoroacetic acid mixed acid anhydride, bicyclo [2.2.1] hept-5-en-2-methyl-2 -Carboxylic acid trifluoroacetic acid mixed acid anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid trifluoroacetic acid mixed acid anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-methyl-3-carboxylic acid trifluoroacetic acid mixed acid anhydride, acrylic acid pivalic acid mixed acid anhydride, methacrylic acid pivalic acid mixed acid anhydride, α-trifluoromethyl Acrylic acid pivalic acid mixed acid anhydride, bicyclo [2.2.1] hept-5-ene-2-carboxylic acidpivalic acid mixed acid anhydride, bicyclo [2.2.1] hept-5-en-2- Methyl-2-carboxylic acid pivalic acid mixed acid anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid pivalic acid mixed acid anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-methyl-3-carboxylic acid pivalic acid mixed acid anhydride, acrylic acid p-nitrobenzoic acid mixed acid anhydride, methacrylic acid p-nitrobenzoic acid mixed acid anhydride, Ethyl acrylate carbonate mixed acid anhydride, ethyl methacrylate carbonate mixed acid anhydride, p-nitrophenyl acrylate, p-nitrophenyl methacrylate, α-trifluoromethyl acrylate p-nitrophenyl, p-toluene sulfone acrylate Acid mixed acid anhydride, methacrylic acid p-toluenesulfonic acid mixed acid anhydride, α-trifluoromethylacrylic acid p-toluenesulfonic acid mixed acid anhydride, bicyclo [2.2.1] hept-5-ene-2 -Carboxylic acid p-toluenesulfonic acid mixed acid anhydride, bicyclo [2.2.1] hept-5-ene-2-methyl-2-carboxylic acid Acid p-toluenesulfonic acid mixed acid anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid p-toluenesulfonic acid mixed acid anhydride, tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodec-8-ene-3-methyl-3-carboxylic acid, acylating agents such as acid anhydrides such as p-toluenesulfonic acid mixed acid anhydride, triethylamine, diisopropylethylamine, N, N-dimethyl Bases such as aniline, pyridine and 4-dimethylaminopyridine are added sequentially or simultaneously to react. In reactions using acylating agents such as acid anhydrides, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfone instead of base The reaction can also be carried out under an acid catalyst selected from organic acids such as acids. The acylation reaction temperature can be selected appropriately depending on the type of acylating agent used and the reaction conditions, but generally it is preferably from -50 ° C to the boiling point of the solvent, more preferably from -20 ° C to room temperature. The amount of the acylating agent used depends on the structure, but is in the range of 1 to 40 mol, preferably 1 to 5 mol, per 1 mol of the starting alcohol compound.

The reaction with the carboxylic acid is carried out by the corresponding carboxylic acid, ie acrylic acid, methacrylic acid, α-trifluoromethylacrylic acid, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid, bicyclo [2 2.1] hepta-5-ene-2-methyl-2-carboxylic acid, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid, tetracyclo [4.4.0.1 ^2,5 . [1 ^7,10 ] is a dehydration reaction from any of dodeca-8-ene-3-methyl-3-carboxylic acid and a starting alcohol compound, and is generally carried out in the presence of an acid catalyst. Although the usage-amount of carboxylic acid is dependent on a structure, it is 1-40 mol with respect to 1 mol of alcohol compounds of a raw material, Preferably it is the range of 1-5 mol. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and nitric acid, and organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid. Are used alone or in combination. The usage-amount of an acid catalyst is 0.001-1 mol with respect to 1 mol of alcohol compounds of a raw material, Preferably it is a catalyst amount of 0.01-0.05 mol. Examples of the solvent include the same solvents as those mentioned above for the reaction with the esterifying agent, but generally the temperature is preferably from -50 ° C to the boiling point of the solvent. Using a solvent containing hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene, the reaction may be allowed to proceed while removing the generated water out of the system by azeotropic distillation. In this case, water may be distilled off while refluxing at the boiling point of the solvent at normal pressure, but water may be distilled off at a temperature lower than the boiling point under reduced pressure.

In the transesterification reaction, the corresponding ester of carboxylic acid, ie acrylic acid ester, methacrylic acid ester, α-trifluoromethyl acrylic acid ester, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid ester Bicyclo [2.2.1] hept-5-ene-2-methyl-2-carboxylic acid ester, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid ester, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] any of dodec-8-ene-3-methyl-3-carboxylic acid ester is reacted with the starting alcohol compound in the presence of a catalyst, and the resulting alcohol is removed. As the carboxylic acid ester to be used, a primary alkyl ester is preferable, and methyl ester, ethyl ester, and n-propyl ester are particularly preferable from the viewpoints of price, easiness of progress of reaction, and the like. The amount of the carboxylic acid ester used depends on the structure, but is in the range of 1 to 40 mol, preferably 1 to 5 mol, per 1 mol of the starting alcohol compound. Catalysts include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and nitric acid, organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, sodium methoxide, sodium ethoxy , Bases such as potassium t-butoxide, 4-dimethylaminopyridine, sodium cyanate, potassium cyanate, sodium acetate, potassium acetate, calcium acetate, tin acetate, aluminum acetate, aluminum acetoacetate, alumina, and other salts, aluminum trichloride , Aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, Titanium tetrabromide, titanium (IV) methoxide Titanium (IV) ethoxide, titanium (IV) isopropoxide, Lewis acids such as titanium (IV) oxide can be mentioned, which may be used alone or in combination. The catalyst is used in an amount of 0.001 to 20 mol, preferably 0.01 to 0.05 mol, per mol of the starting alcohol compound. The reaction can be carried out without a solvent (the carboxylic acid ester itself as a reaction reagent may be used as a solvent), and it is preferable because it does not require extra operations such as concentration and solvent recovery. It is also possible to use a solvent supplementarily for the purpose of preventing polymerization. In this case, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene, and ethers such as dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane are used alone or in combination. Is preferred. An appropriate reaction temperature can be selected as the reaction temperature depending on the type of carboxylic acid ester used and the reaction conditions, but it is usually carried out under heating, and a low-boiling point alcohol produced by the transesterification reaction, that is, methanol, ethanol, 1-propanol, etc. It is good to carry out the reaction in the vicinity of the boiling point of the solvent while distilling off the resulting alcohol. The alcohol may be distilled off at a temperature lower than the boiling point under reduced pressure.

  The starting alcohol compound as the acylation starting material can be synthesized by the addition reaction of the organometallic reagent to the corresponding ketone compound or the reduction reaction of the corresponding ketone compound. Examples of the organometallic reagent used in the addition reaction include an organolithium reagent, an organosodium reagent, an organopotassium reagent, an organomagnesium reagent (for example, Grignard reagent), an organozinc reagent, an organotin reagent, an organoboron reagent, and an organosilicon reagent. Can be mentioned. Of these, organolithium reagents and Grignard reagents are particularly preferred. As a solvent for the reaction, ethers such as dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, and hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene can be used alone or in combination. preferable. The reducing reagent used in the reduction reaction includes metal hydrides such as sodium hydride, potassium hydride, calcium hydride, aluminum hydride, borane, diisobutylaluminum hydride, metals such as sodium borohydride, lithium aluminum hydride, etc. Examples thereof include hydrogen complex compounds or alkyl and alkoxy derivatives thereof. As the reaction solvent, in addition to those exemplified in the addition reaction of the organometallic reagent, alcohols such as water, methanol, ethanol and isopropyl alcohol are preferably used alone or in combination.

  The monomer and synthetic intermediate of the present invention can be purified and used according to conventional methods such as distillation, crystallization, recrystallization, chromatography and the like, if necessary.

（式中、Ｚａは重合性二重結合を有する１価の基Ｚに由来し、重合によって生じる３価の基を表す。Ｘはこれが結合する炭素原子と共に置換又は非置換のシクロペンタン環、シクロヘキサン環、又はノルボルナン環を形成する２価の基を表す。Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表す。Ｒ³、Ｒ⁴はそれぞれ独立に水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を表し、又は、Ｒ³とＲ⁴は互いに結合してこれらが結合する炭素原子と共に置換又は非置換のシクロペンタン環、又はシクロヘキサン環を形成する２価の基を表す。Ｒ⁵は水素原子、又はメチル基を表す。ｎは１又は２を表す。ｐは０又は１を表す。なお、Ｘ、Ｒ²〜Ｒ⁴の具体例は上述した通りである。） The polymer compound of the present invention contains a repeating unit obtained from an acid-eliminating ester-type monomer having a spiro ring structure represented by the following general formulas (1a) to (3a). It is a molecular compound.

(In the formula, Za is derived from a monovalent group Z having a polymerizable double bond, and represents a trivalent group generated by polymerization. X represents a substituted or unsubstituted cyclopentane ring, cyclohexane together with the carbon atom to which it is bonded. R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R ² represents a hydrogen atom, or a straight chain having 1 to 10 carbon atoms. Represents a branched or cyclic monovalent hydrocarbon group, R ³ and R ⁴ each independently represent a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, Or R ³ and R ⁴ represent a divalent group which forms a substituted or unsubstituted cyclopentane ring or cyclohexane ring together with the carbon atom to which they are bonded, and R ⁵ represents a hydrogen atom or a methyl group N represents 1 or 2. p 0 or represents 1. Incidentally, X, specific examples of R ² to R ⁴ are as defined above.)

（式中、Ｚａは上記と同様である。Ｒ¹¹及びＲ¹²はそれぞれ独立に水素原子又は水酸基を示す。Ｒｘは酸不安定基を示す。Ｒｙはラクトン構造を有する置換基を示す。Ｒｚは水素原子、炭素数１〜１５のフルオロアルキル基又は炭素数１〜１５のフルオロアルコール含有置換基を示す。） In addition to the above repeating units, the polymer compound of the present invention may contain any one or more of the repeating units represented by the following general formulas (5a) to (8a).

(In the formula, Za is the same as above. R ¹¹ and R ¹² each independently represents a hydrogen atom or a hydroxyl group. Rx represents an acid labile group. Ry represents a substituent having a lactone structure. Rz represents A hydrogen atom, a C1-C15 fluoroalkyl group, or a C1-C15 fluoroalcohol-containing substituent is shown.)

としては、下記式で表すことができる。

（式中、Ｒ¹、Ｒ⁵、ｐは上述した通りである。） Here, Za is derived from the monovalent group Z having a polymerizable double bond as described above, and Z is as described above, and the specific examples thereof are also as described above. Vinyl group, isopropenyl group, 3,3,3-trifluoro-2-propenyl group or 5-norbornen-2-yl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-en-3-yl group. So for example

Can be represented by the following formula.

(Wherein R ¹ , R ⁵ and p are as described above.)

  The polymer containing the repeating unit represented by the general formula (5a) is decomposed by the action of an acid to generate a carboxylic acid, thereby giving a polymer that becomes alkali-soluble. The acid labile group Rx can be variously used, and specifically, groups represented by the following general formulas (L1) to (L4), a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms. , Each alkyl group may be a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the like.

Here, a broken line shows a bond (hereinafter the same). In the formula, R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group, an ethyl group or a propyl group. , Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, norbornyl group, tricyclodecanyl group, tetracyclododecanyl group, Examples thereof include an adamantyl group. R ^L03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group, Examples include those in which a part of hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 may be bonded to each other to form a ring together with the carbon atom or oxygen atom to which they are bonded. R ^L01 , R ^L02 and R ^L03 involved in the formation each represent a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.

R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above general formula ( L1) represents a group represented by a tertiary alkyl group, specifically, a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, a 2-cyclopentylpropan-2-yl group, 2 -Cyclohexylpropan-2-yl group, 2- (bicyclo [2.2.1] heptan-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propan-2-yl group, -Ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexyl Examples include xenyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group and the like. Specific examples of trialkylsilyl group include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group and the like. Specific examples of the oxoalkyl group include 3-oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-2-oxooxolan-5-yl group. it can. y is an integer of 0-6.

R ^L05 represents an ^optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group having 6 to 20 carbon atoms, and may be substituted. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, and n-hexyl group. A linear, branched or cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group, and a part of these hydrogen atoms are a hydroxyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, an oxo group, an amino group, an alkylamino group, Examples include those substituted with a cyano group, a mercapto group, an alkylthio group, a sulfo group, and the like. Specific examples of the aryl group that may be substituted include phenyl Illustrative examples include a sulfur group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. In the formula (L3), m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.

R ^L06 represents an ^optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group having 6 to 20 carbon atoms, specifically, R ^L05 And the like. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, n-butyl, sec- Butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl Group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group and other linear, branched or cyclic alkyl groups, and some of these hydrogen atoms are hydroxyl groups, alkoxy groups, carboxy groups, alkoxycarbonyl groups Oxo group, amino group, alkylamino group, cyano group, mercapto group, alkylthio group, Or the like can be exemplified those substituted in sulfo group. R ^{L07 to} R ^L16 may be bonded to each other to form a ring with the carbon atom to which they are bonded (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12 , R ^L13 and R ^L14, etc.), in which case the group involved in ring formation represents a divalent hydrocarbon group having 1 to 15 carbon atoms, specifically the monovalent The thing etc. which remove | excluded one hydrogen atom from what was illustrated by the hydrocarbon group of this can be illustrated. R ^{L07 to} R ^L16 may be bonded to each other adjacent to each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 etc.).

Of the acid labile groups represented by the above formula (L1), specific examples of the linear or branched ones include the following groups.

  Among the acid labile groups represented by the above formula (L1), specific examples of cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, Examples thereof include a 2-methyltetrahydropyran-2-yl group.

  Specific examples of the acid labile group of the above formula (L2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethyl. Propyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2 Examples include -cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  Specific examples of the acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec- Butylcyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxy-n-butyl) cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopentene Examples include -3-yl, 3-methyl-1-cyclohexen-3-yl, and 3-ethyl-1-cyclohexen-3-yl.

As the acid labile group of the above formula (L4), groups represented by the following formulas (L4-1) to (L4-4) are particularly preferable.

In the general formulas (L4-1) to (L4-4), a broken line indicates a coupling position and a coupling direction. R ^L41 each independently represents a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, n Examples include -butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.

  In the general formulas (L4-1) to (L4-4), enantiomers and diastereomers may exist, but the general formulas (L4-1) to (L4-4) may exist. Represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

（式中、Ｒ^L41は前述と同様である。） For example, the general formula (L4-3) represents one or a mixture of two selected from the groups represented by the following general formulas (L4-3-1) and (L4-3-2). And

(In the formula, R ^L41 is the same as described above.)

（式中、Ｒ^L41は前述と同様である。） The general formula (L4-4) represents one or a mixture of two or more selected from groups represented by the following general formulas (L4-4-1) to (L4-4-4). Shall.

(In the formula, R ^L41 is the same as described above.)

  The above general formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) Enantioisomers and enantioisomer mixtures are also shown representatively.

  The bonding directions of (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) are respectively By being on the exo side with respect to the bicyclo [2.2.1] heptane ring, high reactivity in the acid-catalyzed elimination reaction is realized (see JP-A-12-336121). In the production of a monomer having a tertiary exo-alkyl group having a bicyclo [2.2.1] heptane skeleton as a substituent, the following general formulas (L4-1-endo) to (L4-4-endo) are used. In some cases, the exo ratio is preferably 50% or more, and the exo ratio is 80% or more in order to achieve good reactivity. More preferably it is.

（式中、Ｒ^L41は前述と同様である。）

(In the formula, R ^L41 is the same as described above.)

Specific examples of the acid labile group of the above formula (L4) include the following groups.

Further, tertiary alkyl groups having 4 to 20 carbon atoms, trialkylsilyl groups each having 1 to 6 carbon atoms, and oxoalkyl groups having 4 to 20 carbon atoms are specifically exemplified as R ^L04 . The thing similar to a thing etc. can be illustrated.

  Specific examples of the partial structure O-Rx of the repeating unit represented by the general formula (5a) include the following, but are not limited thereto.

（式中、Ｍｅはメチル基を示す。） Specific examples of the partial structure O-Ry of the repeating unit represented by the general formula (7a) include the following, but are not limited thereto.

(In the formula, Me represents a methyl group.)

Specific examples of the partial structure O-Rz of the repeating unit represented by the general formula (8a) include the following, but are not limited thereto.

In addition to the above, the polymer compound of the present invention is a repeating unit obtained from a monomer containing a carbon-carbon double bond, for example, substitution of methyl methacrylate, methyl crotonic acid, dimethyl maleate, dimethyl itaconate, etc. Acrylic acid esters, unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid, norbornene, norbornene derivatives, tetracyclo [4.4.0.1 ^2,5 . 17 ^7,10 ] may contain a repeating unit obtained from cyclic olefins such as dodecene derivatives, unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, imides, and other monomers.

  In addition, the weight average molecular weight of the polymer compound of the present invention is 1,000 to 500,000, preferably 3,000 to 100,000, when measured using gel permeation chromatography (GPC) in terms of polystyrene. is there. If it is out of this range, the etching resistance may be extremely lowered, or the difference in dissolution rate before and after the exposure cannot be ensured and the resolution may be lowered.

In the polymer compound of the present invention, a preferable content ratio of each repeating unit obtained from each monomer can be set, for example, in the following range (mol%), but is not limited thereto.
(I) a structural unit represented by the formula (1a) based on the monomer of the above formula (1) (or the formula (2a) or (3a) based on the monomer of the formula (2) or (3)) More than 0 mol% and not more than 100 mol%, preferably 2 to 70 mol%, more preferably 5 to 50 mol%, and (II) one of the structural units represented by the above formulas (5a) to (8a) Or 2 mol% or more and less than 100 mol%, preferably 1 to 95 mol%, more preferably 20 to 80 mol%, and if necessary, (III) a structural unit based on other monomer One or two or more of these can be contained in an amount of 0 to 80 mol%, preferably 0 to 70 mol%, more preferably 0 to 50 mol%.

  In this case, the sum of the repeating units of formula (1a) (or formula (2a) or (3a)) and formula (5a) is 1 to 95 mol%, particularly 20 to 80 mol%, and the repeating unit of formula (6a) is 0 to 95 mol%, especially 0 to 50 mol%, 0 to 95 mol%, especially 20 to 80 mol% of repeating units of the formula (7a), 0 to 95 mol% of repeating units of the formula (8a), especially 0 It is preferable to contain -50 mol%.

  In the production of the polymer compound of the present invention, the compound represented by the general formula (1), (2) or (3) is used as a first monomer, and a compound containing a polymerizable double bond is used as a second compound. It is carried out by the copolymerization reaction used for the subsequent monomers. The monomer (1), (2) or (3) of the present invention, which is the first monomer used for copolymerization, and the second and subsequent monomers have an oligomer or high molecular weight content of 10 mol. % Or less, preferably 3 mol% or less, more preferably 1 mol% or less is preferably used.

  Various copolymerization reactions for producing the polymer compound of the present invention can be exemplified, and radical polymerization, anionic polymerization or coordination polymerization is preferred.

  The reaction conditions for the radical polymerization reaction are as follows: (a) As a solvent, hydrocarbons such as benzene, ethers such as tetrahydrofuran, alcohols such as ethanol, or ketones such as methyl isobutyl ketone, and (b) as a polymerization initiator Using an azo compound such as 2,2′-azobisisobutyronitrile or a peroxide such as benzoyl peroxide or lauroyl peroxide, (c) maintaining the reaction temperature at about 0 to 100 ° C., and (d) reaction The time is preferably about 0.5 to 48 hours, but this does not exclude the case where the time is out of this range.

  The reaction conditions for the anionic polymerization reaction are as follows: (a) hydrocarbons such as benzene, ethers such as tetrahydrofuran, or liquid ammonia as the solvent; (a) metals such as sodium and potassium as the polymerization initiator, n-butyllithium , Using an alkyl metal such as sec-butyllithium, ketyl, or Grignard reactant, (c) maintaining the reaction temperature at about -78 ° C to 0 ° C, and (d) setting the reaction time to about 0.5 to 48 hours, (E) It is preferable to use a proton-donating compound such as methanol, a halide such as methyl iodide, and other electrophilic substances as the terminator, but this does not exclude the case where it is outside this range.

  The reaction conditions for the coordination polymerization are as follows: (a) a hydrocarbon such as n-heptane or toluene as the solvent; and (a) a Ziegler-Natta catalyst comprising a transition metal such as titanium and an alkylaluminum as the catalyst, chromium and nickel compounds. (C) the reaction temperature is kept at about 0 to 100 ° C., and (d) the reaction time is set at 0. 0 ° C. using a Phillips catalyst in which a metal oxide is supported, an olefin-metathesis mixed catalyst represented by a mixed catalyst of tungsten and rhenium, and the like. Although it is preferable to set it as about 5-48 hours, the case where it remove | deviates from this range is not excluded.

The polymer compound of the present invention is suitably used as a base polymer for resist materials, particularly chemically amplified positive resist materials, and the present invention provides resist materials containing the above polymer compounds, particularly chemically amplified positive resist materials. . In this case, as a resist material,
(A) The polymer compound as a base resin,
(B) an acid generator,
(C) If an organic solvent is required,
(D) a nitrogen-containing organic compound,
(E) What contains surfactant is preferable.

  As the base resin of the component (A), in addition to the polymer compound of the present invention, other resins that increase the dissolution rate in an alkaline developer by the action of an acid may be added as necessary. Examples include i) poly (meth) acrylic acid derivatives, ii) copolymers of norbornene derivatives-maleic anhydride, iii) hydrogenated ring-opening metathesis polymers, iv) vinyl ether-maleic anhydride- (meth). Examples include, but are not limited to, copolymers of acrylic acid derivatives.

  Among these, a method for synthesizing a hydrogenated product of a ring-opening metathesis polymer is specifically described in Examples of JP-A No. 2003-66612. Specific examples include those having the following repeating units, but are not limited thereto.

The blending ratio of the polymer compound of the present invention to another polymer compound is preferably in the range of mass ratio of 100: 0 to 10:90, particularly 100: 0 to 20:80. When the compounding ratio of the polymer compound of the present invention is less than this, a preferable performance as a resist material may not be obtained. The performance of the resist material can be adjusted by appropriately changing the blending ratio.
The polymer compound is not limited to one type, and two or more types can be added. The performance of the resist material can be adjusted by using a plurality of types of polymer compounds.

  When a photoacid generator is added as the acid generator of the component (B) used in the present invention, any compound can be used as long as it generates an acid by irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, N-sulfonyloxyimide, oxime-O-sulfonate acid generators, and the like. Although described in detail below, these may be used alone or in combination of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate or bis (substituted alkylsulfonyl) imide or tris (substituted alkylsulfonyl) methide. As the sulfonium cation, triphenylsulfonium, 4-tert-butoxyphenyldiphenylsulfonium, bis (4-tert -Butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, 3-tert-butoxyphenyldiphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, 3,4-di-tert-butoxyphenyldiphenylsulfonium, bis (3,4-di-tert-butoxyphenyl) phenylsulfonium, Lis (3,4-di-tert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, 4-tert-butoxycarbonylmethyloxyphenyldiphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium , (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 4-methylphenyldiphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium, bis (4-methyl Phenyl) phenylsulfonium, bis (4-tert-butylphenyl) phenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-tert-butyl) Ruphenyl) sulfonium, tris (phenylmethyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl (2-naphthyl) sulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, Trinaphthylsulfonium, tribenzylsulfonium, diphenylmethylsulfonium, dimethylphenylsulfonium, 2-oxopropylthiacyclopentanium, 2-oxobutylthiacyclopentanium, 2-oxo-3,3-dimethylbutylthiacyclopentanium, 2 -Oxo-2-phenylethylthiacyclopentanium, 4-n-butoxynaphthyl-1-thiacyclopentanium, 2-n-butoxynaphthyl-1-thiacyclopentanium and the like. Examples of the sulfonate include trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, tridecafluorohexanesulfonate, perfluoro ( 4-ethylcyclohexane) sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4- (trifluoromethyl) benzene sulfonate, 4-fluorobenzene sulfonate, mesitylene sulfonate, 2, 4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (p-toluenesulfonyloxy) ) Benzenesulfonate, 6- (p-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (p-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (p-toluenesulfonyloxy) naphthalene-1-sulfonate, 8 -(P-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 1,1-difluoro-2-naphthylethanesulfonate, 1,1,2 , 2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-3-en-8-yl) ethanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro -2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3 Pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2- (1-a Nanthanecarbonyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3 -Pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-tosyloxyethane sulfonate, adamantane methoxycarbonyl difluoromethane sulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-6-yloxycarbonyl) Examples include difluoromethanesulfonate, 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate, and bis (substituted alkylsulfonyl) imide includes bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, bis ( Heptafluoropropylsulfonyl) imide, perfluoro (1,3-propylenebissulfonyl) imide and the like, and tris (substituted alkylsulfonyl) methide includes tris (trifluoromethylsulfonyl) methide, and sulfonium of these combinations Salt.

The iodonium salt is a salt of an iodonium cation and a sulfonate, bis (substituted alkylsulfonyl) imide, or tris (substituted alkylsulfonyl) methide. Examples of the iodonium cation include diphenyliodonium, bis (4-tert-butylphenyl) iodonium, 4-tert. -Butoxyphenyl phenyl iodonium, 4-methoxyphenyl phenyl iodonium, etc., and sulfonates include trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, tridecafluorohexane sulfonate, perfluoro (4- Ethylcyclohexane) sulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoro Tan sulfonate, pentafluorobenzene sulfonate, 4- (trifluoromethyl) benzene sulfonate, 4-fluorobenzene sulfonate, mesitylene sulfonate, 2,4,6-triisopropylbenzene sulfonate, toluene sulfonate, benzene sulfonate, 4- (p-toluene) Sulfonyloxy) benzenesulfonate, 6- (p-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (p-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (p-toluenesulfonyloxy) naphthalene-1-sulfonate 8- (p-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenes Phonate, butanesulfonate, methanesulfonate, 1,1-difluoro-2-naphthylethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2 - tetrafluoro-2- (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodeca-3-en-8-yl) ethanesulfonate, 2-benzoyloxy -1,1,3,3 , 3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivalo Yloxypropanesulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3 , 3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy) -1,1 , 3,3,3-pentafluoropropanesulfonate, 2- (1-adamantanecarbonylcarbonyl) -1,1,3,3,3-pentafluoropropanesulfonate, 2-acetyloxy-1,1,3,3 , 3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1 -Difluoro-2-tosyloxyethane sulfonate, adamantane methoxycarbonyl difluoromethane Sulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-6-yloxy Carbonyl) difluoromethanesulfonate, 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate, and the like. Examples of bis (substituted alkylsulfonyl) imide include bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, Examples thereof include bis (heptafluoropropylsulfonyl) imide, perfluoro (1,3-propylenebissulfonyl) imide, and the like as tris (substituted alkylsulfonyl) methide. Tris (trifluoromethylsulfonyl) methide and the like, iodonium salts and combinations thereof.

Examples of the N-sulfonyloxydicarboximide photoacid generator include succinimide, naphthalene dicarboximide, phthalic imide, cyclohexyl dicarboximide, 5-norbornene-2,3-dicarboximide, 7-oxabicyclo [ 2.2.1] Imido skeletons such as -5-heptene-2,3-dicarboximide and trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, tridecafluorohexanesulfonate, perfluoro (4-ethylcyclohexane) sulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4- (trifluoromethyl) benzene Zensulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (p-toluenesulfonyloxy) benzenesulfonate, 6- (p-toluenesulfonyloxy) Naphthalene-2-sulfonate, 4- (p-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (p-toluenesulfonyloxy) naphthalene-1-sulfonate, 8- (p-toluenesulfonyloxy) naphthalene-1-sulfonate , Naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 1,1-difluoro-2-naphthyl Tan sulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [6.2.1.1 ^{3 , 6,0,2,7} ] dodec-3-en-8-yl) ethanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3 -Pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3 3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy 1,1,3,3,3-pentafluoropropane sulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2- (1-adamantanecarbonyl Oxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro 2-hydroxypropanesulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate, 1,1-difluoro-2-tosyloxyethanesulfonate, adamantanemethoxycarbonyldifluoromethanesulfonate, 1- ( 3-hydroxymethyladamantane) methoxycarbonyldifluorome Tansulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-6-yloxycarbonyl) difluoromethanesulfonate, 4-oxo-1-adamantyloxy Combination compounds such as carbonyldifluoromethanesulfonate are exemplified.

（上記式中、Ｒ⁴⁰¹は置換又は非置換の炭素数１〜１０のハロアルキルスルホニル又はハロベンゼンスルホニル基を表す。Ｒ⁴⁰²は炭素数１〜１１のハロアルキル基を表す。Ａｒ⁴⁰¹は置換又は非置換の芳香族基又はヘテロ芳香族基を表す。） The O-arylsulfonyl oxime compound or O-alkyl sulfonyl oxime compound (oxime sulfonate) type photoacid generator is represented by the following formula (Ox-1) in which the stability of the compound is increased by an electron withdrawing group such as a trifluoromethyl group. And the oxime sulfonates indicated.

(In the above formula, R ⁴⁰¹ represents a substituted or unsubstituted haloalkylsulfonyl group having 1 to 10 carbon atoms or a halobenzenesulfonyl group. R ⁴⁰² represents a haloalkyl group having 1 to 11 carbon atoms. Ar ⁴⁰¹ is substituted or unsubstituted. Represents an aromatic group or a heteroaromatic group.)

  Specifically, 2- (2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) pentyl) fluorene, 2- (2,2,3, 3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) butyl) fluorene, 2- (2,2,3,3,4,4,5,5,6,6-decafluoro-1 -(Nonafluorobutylsulfonyloxyimino) hexyl) fluorene, 2- (2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) pentyl) -4- Biphenyl, 2- (2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) butyl) -4-biphenyl, 2- (2,2,3,3,4, 4, 5, 5 6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) hexyl) -4-biphenyl and the like, and 2-benzoyloxy-1,1,3,3,3-pentafluoropropane in the above skeleton Sulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2 Cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1 , 3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy) 1,1,3,3,3-pentafluoropropanesulfonate, 2- (1-adamantanecarbonylcarbonyl) -1,1,3,3,3-pentafluoropropanesulfonate, 2-acetyloxy-1,1, 3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-tosyloxyethane sulfonate, adamantane methoxycarbonyl difluoromethane sulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyl difluoromethane sulfonate, methoxycarbonyl difluoromethane sulfonate, 1- (hexahydro-2-oxo- 3, 5-methano-2H-cyclopenta [b] furan-6-yloxycarbonyl) difluoromethanesulfonate, compounds substituted with 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

（式中、Ｒ⁶、Ｒ⁷、Ｒ⁸はそれぞれ独立に水素原子、又はそれぞれヘテロ原子を含んでもよい炭素数１〜２０の直鎖状、分岐状又は環状の１価の炭化水素基、炭素数１〜１０のアルコキシ基、又は、ハロゲン原子を示す。Ｒ⁹はヘテロ原子を含んでもよい炭素数１〜３０の直鎖状、分岐状又は環状の１価の炭化水素基を示す。Ｒ¹⁰は水素原子又はトリフルオロメチル基を示す。） Among them, an acid generator represented by the following general formula (4) is more preferably used.

(Wherein R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, each of which may contain a hetero atom, carbon C 1 -C 10 alkoxy group, or, .R ¹⁰ indicating a halogen atom .R ⁹ is carbon atoms which may contain a heteroatom 1-30 linear, monovalent hydrocarbon group branched or cyclic Represents a hydrogen atom or a trifluoromethyl group.)

Here, in formula, R < ⁶ >, R <^7> , R < ⁸ > is a hydrogen atom or a C1-C20 linear, branched or cyclic monovalent hydrocarbon group which may each contain a hetero atom respectively. , An alkoxy group having 1 to 10 carbon atoms, or a halogen atom which may contain a hetero atom, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec- Butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyladamantyl group A group, a butyladamantyl group, and between any carbon-carbon bonds of these groups -O-, -S-, -SO-, _{SO 2 -, - NH -,} - C (= O) -, - C (= O) O -, - C (= O) or a group hetero atom group is inserted in NH- such that any hydrogen atom Examples include groups substituted with functional groups such as —OH, —NH ₂ , —CHO, and —CO ₂ H. R ⁹ represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, and specific examples thereof include, but are not limited to, It is not a thing.

（式中、Ｒ¹⁰は水素原子又はトリフルオロメチル基を示す。） More specifically, the following can be illustrated.

(In the formula, R ¹⁰ represents a hydrogen atom or a trifluoromethyl group.)

（式中、Ｒ¹⁰は水素原子又はトリフルオロメチル基を示す。）

(In the formula, R ¹⁰ represents a hydrogen atom or a trifluoromethyl group.)

  Since the anion portion of the acid generator represented by the general formula (4) has an ester moiety, it is easy to introduce a bulky acyl group, a benzoyl group, a naphthoyl group, an anthracenecarbonyl group, etc. from a bulky acyl group. Therefore, it can have a wide range of molecular design, and it is easy to adjust solvent solubility and transmittance and to control the diffusion of the generated acid. In addition, the sulfonic acid generated from the acid generator represented by the general formula (4) has a strong acidity similar to that of perfluoroalkanesulfonic acid, but has a low fluorine content, and therefore has compatibility with the base resin. High dispersibility and low roughness can be expected. In particular, the roughness is extremely small by combining the acid generator represented by the general formula (4) with a resist base resin having an acid-eliminating ester monomer having a specific spiro ring structure of the present invention as a constituent component. I found out that Further, the acid generator represented by the general formula (4) can be used without any problem in the steps of coating, baking before exposure, exposure, baking after exposure, and development in the device production process. Furthermore, not only elution into water during ArF immersion exposure can be suppressed, but also the influence of water remaining on the wafer is small, and defects can be suppressed. When the resist waste solution is processed after device fabrication, the ester moiety is hydrolyzed by alkali, so it can be converted to a compound with a lower molecular weight and a low accumulation, and the fluorine substitution rate is low even when discarded by combustion. Therefore, it can be expected that the combustibility is high and the environmental load is small.

  The amount of the photoacid generator added as the component (B) in the chemically amplified resist material of the present invention may be any as long as it does not interfere with the effects of the present invention, but 100 parts of the base resin in the resist material ( 0.1 to 40 parts, preferably 2 to 30 parts relative to parts by mass. When the proportion of the photoacid generator of the component (B) is too large, there is a possibility that the resolution is deteriorated and a foreign matter problem occurs during development / resist peeling. The (B) component photoacid generators can be used alone or in admixture of two or more. Furthermore, a photoacid generator having a low transmittance at the exposure wavelength can be used, and the transmittance in the resist film can be controlled by the amount of the photoacid generator added.

When two or more photoacid generators are used in combination, and one of the photoacid generators is an onium salt that generates a so-called weak acid, a function of acid diffusion control can be provided. That is, when a photoacid generator that generates a strong acid (for example, fluorine-substituted sulfonic acid) and an onium salt that generates a weak acid (for example, a sulfonic acid or carboxylic acid that is not fluorine-substituted) are mixed and used, When a strong acid generated from a photoacid generator upon irradiation collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, since the strong acid is exchanged with a weak acid having a lower catalytic ability, the acid is apparently deactivated and the acid diffusion can be controlled.
Here, when the photoacid generator for generating a strong acid is an onium salt, the strong acid generated by the high energy beam irradiation can be exchanged for the weak acid as described above, but the weak acid generated by the high energy beam irradiation is not yet. The salt exchange cannot be performed by colliding with an onium salt that generates a strong acid of reaction. These are due to the phenomenon that the onium cation is more likely to form an ion pair with the anion of the strong acid.

  In addition, a compound capable of decomposing with an acid to generate an acid (acid-growing compound) may be added to the resist material of the present invention. For these compounds, see J. et al. Photopolym. Sci. and Tech. , 8. 43-44, 45-46 (1995), J. MoI. Photopolym. Sci. and Tech. , 9. 29-30 (1996).

  Examples of the acid-proliferating compound include tert-butyl-2-methyl-2-tosyloxymethyl acetoacetate and 2-phenyl-2- (2-tosyloxyethyl) -1,3-dioxolane. It is not limited to. Of the known photoacid generators, compounds that are inferior in stability, particularly thermal stability, often exhibit the properties of acid-proliferating compounds.

  The addition amount of the acid multiplication compound in the resist material of the present invention is preferably 2 parts or less (0 to 2 parts), more preferably 1 part or less (0 to 1 part) with respect to 100 parts of the base resin in the resist material. is there. When the addition amount is too large, it is difficult to control diffusion, and resolution and pattern shape may be deteriorated.

  The organic solvent of component (C) used in the present invention may be any organic solvent that can dissolve the base resin, acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and methyl amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and the like. Alcohols, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxypropio Examples include esters such as ethyl acid, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyrolactone. These are used alone or in combination of two or more. However, it is not limited to these. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, and mixed solvents thereof, which have the highest solubility of the acid generator in the resist component, are preferably used. .

  The amount of the organic solvent used is preferably 200 to 5,000 parts, particularly 400 to 3,000 parts, based on 100 parts of the base resin.

  Furthermore, 1 type, or 2 or more types of nitrogen-containing organic compounds can be mix | blended with the resist material of this invention as (D) component.

  As the nitrogen-containing organic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By compounding nitrogen-containing organic compounds, the acid diffusion rate in the resist film is suppressed and resolution is improved, sensitivity change after exposure is suppressed, substrate and environment dependency is reduced, and exposure margins and patterns are reduced. Profiles and the like can be improved.

  Such nitrogen-containing organic compounds include primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, sulfonyl Nitrogen-containing compounds having a group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, carbamates and the like.

  Specifically, as primary aliphatic amines, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, Examples include cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. Secondary aliphatic amines include dimethylamine , Diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentyl Min, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, etc. As the tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tripentylamine, Cyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine, etc. Is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dim Lupyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4 -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4-pyrrolidinopyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H- Indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoli Derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives And uridine derivatives.

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) Ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated. Examples of amides include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, 1-cyclohexylpyrrolidone and the like. Examples of imides include phthalimide, succinimide, maleimide and the like. Examples of carbamates include Nt-butoxycarbonyl-N, N-dicyclohexylamine, Nt-butoxycarbonylbenzimidazole, oxazolidinone, and the like.

Furthermore, the nitrogen-containing organic compound represented by the following general formula (B) -1 is illustrated.
N (X) _n (Y) _3-n (B) -1
(In the above formula, n is 1, 2 or 3. The side chains X may be the same or different and are represented by the following general formula (X) -1, (X) -2 or (X) -3. The side chain Y represents the same or different hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group. They may combine to form a ring.)

（上記式中、Ｒ³⁰⁰、Ｒ³⁰²、Ｒ³⁰⁵は炭素数１〜４の直鎖状又は分岐状のアルキレン基であり、Ｒ³⁰¹、Ｒ³⁰⁴は水素原子、又は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、ヒドロキシ基、エーテル基、エステル基、ラクトン環を１個あるいは複数個含んでいてもよい。Ｒ³⁰³は単結合、又は炭素数１〜４の直鎖状又は分岐状のアルキレン基であり、Ｒ³⁰⁶は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、ヒドロキシ基、エーテル基、エステル基、又はラクトン環を１個あるいは複数個含んでいてもよい。）

(In the above formula, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are hydrogen atoms or linear chains having 1 to 20 carbon atoms. R ³⁰³ is a single bond or a straight chain having 1 to 4 carbon atoms, which may contain one or more hydroxy groups, ether groups, ester groups and lactone rings. A branched or branched alkylene group, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and includes one or more hydroxy groups, ether groups, ester groups, or lactone rings May be included.)

  Specific examples of the compound represented by the general formula (B) -1 include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, and tris {2- (2- Methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7 , 13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 1,4,10,13-tetraoxa-7,16-di Zabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) ) Amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2 -Pivaloyloxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) Amine, tris [2- (2-oxopropoxy) ethyl] amine, tris 2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) Amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(2-methoxyethoxycarboni ) Ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2 -Acetoxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2 -(2-oxopropoxycarbonyl) ethylamine, N, N- (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) ) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis ( 2-formyloxyethyl) 2- (2-formyloxy) Ethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxy) Ethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) Ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbi [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine N-methylbis (2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxy Examples include carbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone.

（上記式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状又は分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基又はスルフィドを１個あるいは複数個含んでいてもよい。） Furthermore, the nitrogen-containing organic compound which has a cyclic structure represented by the following general formula (B) -2 is illustrated.

(In the above formula, X is as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, and contains one or more carbonyl groups, ether groups, ester groups or sulfides. May be.)

  Specific examples of the general formula (B) -2 include 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl. ] Morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) ) Methoxy] ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate , 2- (1-pyrrolidinyl) ethyl methoxyacetate, 4- [2- (methoxycarbonyloxy) ethyl ] Morpholine, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-pi Methyl peridinopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3-piperidino Methoxycarbonylmethyl propionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3- Morpholinopropionic acid tetrahydrofur Furyl, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-pi Cyclohexyl peridinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, Methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate, 2-morpholinoethyl 2-methoxyacetate, 2-morpholinoethyl 2- (2-methoxyethoxy) acetate, 2- [2- (2-methoxy Ethoxy) ethoxy] acetic acid 2-mo Rumorpholinoethyl, 2-morpholinoethyl hexanoate, 2-morpholinoethyl octoate, 2-morpholinoethyl decanoate, 2-morpholinoethyl laurate, 2-morpholinoethyl myristic acid, 2-morpholinoethyl palmitate, 2-morpholinoethyl stearate Is exemplified.

（上記式中、Ｘ、Ｒ³⁰⁷、ｎは前述の通り、Ｒ³⁰⁸、Ｒ³⁰⁹は同一又は異種の炭素数１〜４の直鎖状又は分岐状のアルキレン基である。） Furthermore, the nitrogen-containing organic compound containing the cyano group represented by the following general formula (B) -3-(B) -6 is illustrated.

(In the above formula, X, R ³⁰⁷ and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different linear or branched alkylene groups having 1 to 4 carbon atoms.)

  Specific examples of the nitrogen-containing organic compound containing a cyano group represented by the general formulas (B) -3 to (B) -6 include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxy). Ethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N , N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- Methyl (2-methoxyethyl) -3-aminopropionate, methyl N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionate, N- (2-a Toxiethyl) -N- (2-cyanoethyl) -3-aminopropionate methyl, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2- Hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxy Ethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ) Ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropio Nitrile, N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl)- 3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N , N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2- Methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl] amino Acetonitrile, methyl N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate methyl, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N -(3-Hydroxy-1-propyl) amino Acetonitrile, N- (3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) amino Acetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis Cyanomethyl (2-hydroxyethyl) -3-aminopropionate, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-formyloxyethyl) -3-aminop Cyanomethyl pionate, cyanomethyl N, N-bis (2-methoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl) ), N, N-bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N , N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), 1-pyrrolidine Cyanomethyl propionate, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl) Is exemplified.

（上記式中、Ｒ³¹⁰は炭素数２〜２０の直鎖状、分岐状又は環状の極性官能基を有するアルキル基であり、極性官能基として水酸基、カルボニル基、エステル基、エーテル基、スルフィド基、カーボネート基、シアノ基、又はアセタール基を１個あるいは複数個含む。Ｒ³¹¹、Ｒ³¹²、Ｒ³¹³は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、アリール基又はアラルキル基である。） Furthermore, a nitrogen-containing organic compound having an imidazole skeleton and a polar functional group represented by the following general formula (B) -7 is exemplified.

(In the above formula, R ³¹⁰ is an alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms, and the polar functional group includes a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group. , Carbonate group, cyano group, or acetal group, wherein R ³¹¹ , R ³¹² and R ³¹³ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and an aryl group. Or an aralkyl group.)

（上記式中、Ｒ³¹⁴は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、アリール基又はアラルキル基である。Ｒ³¹⁵は炭素数１〜２０の直鎖状、分岐状又は環状の極性官能基を有するアルキル基であり、極性官能基としてエステル基、アセタール基、又はシアノ基を一つ以上含み、その他に水酸基、カルボニル基、エーテル基、スルフィド基、又はカーボネート基を一つ以上含んでいてもよい。） Furthermore, a nitrogen-containing organic compound having a benzimidazole skeleton and a polar functional group represented by the following general formula (B) -8 is exemplified.

(In the above formula, R ³¹⁴ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group. R ³¹⁵ is a straight chain having 1 to 20 carbon atoms, An alkyl group having a branched or cyclic polar functional group, which contains at least one ester group, acetal group, or cyano group as the polar functional group, and in addition, a hydroxyl group, a carbonyl group, an ether group, a sulfide group, or a carbonate group May contain one or more.)

（上記式中、Ａは窒素原子又は≡Ｃ−Ｒ³²²である。Ｂは窒素原子又は≡Ｃ−Ｒ³²³である。Ｒ³¹⁶は炭素数２〜２０の直鎖状、分岐状又は環状の極性官能基を有するアルキル基であり、極性官能基としては水酸基、カルボニル基、エステル基、エーテル基、スルフィド基、カーボネート基、シアノ基又はアセタール基を一つ以上含む。Ｒ³¹⁷、Ｒ³¹⁸、Ｒ³¹⁹、Ｒ³²⁰は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基又はアリール基であるか、又はＲ³¹⁷とＲ³¹⁸、Ｒ³¹⁹とＲ³²⁰はそれぞれ結合してこれらが結合する炭素原子と共にベンゼン環、ナフタレン環あるいはピリジン環を形成してもよい。Ｒ³²¹は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基又はアリール基である。Ｒ³²²、Ｒ³²³は水素原子、又は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基又はアリール基である。Ｒ³²¹とＲ³²³は結合してこれらが結合する炭素原子と共にベンゼン環又はナフタレン環を形成してもよい。） Furthermore, the nitrogen-containing heterocyclic compound which has a polar functional group represented with the following general formula (B) -9 and (B) -10 is illustrated.

(In the above formula, A is a nitrogen atom or ≡C—R ^322. B is a nitrogen atom or ≡C—R ^323. R ³¹⁶ is a linear, branched or cyclic polarity having 2 to 20 carbon atoms. An alkyl group having a functional group, and the polar functional group includes one or more of a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, a cyano group, or an acetal group R ³¹⁷ , R ³¹⁸ , R ³¹⁹ R ³²⁰ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group, or R ³¹⁷ and R ³¹⁸ , and R ³¹⁹ and R ³²⁰ are bonded to each other. A benzene ring, a naphthalene ring or a pyridine ring may be formed together with the carbon atoms to be bonded, and R ³²¹ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group. ³²² and R ³²³ are hydrogen atoms or charcoal It is a linear, branched or cyclic alkyl group or aryl group having a prime number of 1 to 10. R ³²¹ and R ³²³ may combine to form a benzene ring or a naphthalene ring together with the carbon atom to which they are bonded. )

（上記式中、Ｒ³²⁴は炭素数６〜２０のアリール基又は炭素数４〜２０のヘテロ芳香族基であって、水素原子の一部又は全部が、ハロゲン原子、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜１０のアシルオキシ基、又は、炭素数１〜１０のアルキルチオ基で置換されていてもよい。Ｒ³²⁵はＣＯ₂Ｒ³²⁶、ＯＲ³²⁷又はシアノ基である。Ｒ³²⁶は一部のメチレン基が酸素原子で置換されていてもよい炭素数１〜１０のアルキル基である。Ｒ³²⁷は一部のメチレン基が酸素原子で置換されていてもよい炭素数１〜１０のアルキル基又はアシル基である。Ｒ³²⁸は単結合、メチレン基、エチレン基、硫黄原子又はＯ（ＣＨ₂ＣＨ₂Ｏ）_n−基である。ｎ＝０，１，２，３又は４である。Ｒ³²⁹は水素原子、メチル基、エチル基又はフェニル基である。Ｘは窒素原子又はＣＲ³³⁰である。Ｙは窒素原子又はＣＲ³³¹である。Ｚは窒素原子又はＣＲ³³²である。Ｒ³³⁰、Ｒ³³¹、Ｒ³³²はそれぞれ独立に水素原子、メチル基又はフェニル基であるか、あるいはＲ³³⁰とＲ³³¹又はＲ³³¹とＲ³³²が結合してこれらが結合する炭素原子と共に炭素数６〜２０の芳香環又は炭素数２〜２０のヘテロ芳香環を形成してもよい。） Furthermore, the nitrogen-containing organic compound which has an aromatic carboxylic acid ester structure represented with the following general formula (B) -11- (B) -14 is illustrated.

(In the above formula, R ³²⁴ is an aryl group having 6 to 20 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms, and part or all of the hydrogen atoms are halogen atoms, A linear, branched or cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or carbon R ³²⁵ is CO ₂ R ³²⁶ , OR ³²⁷ or cyano group R ³²⁶ is a carbon in which some methylene groups may be substituted with oxygen atoms R ³²⁷ is an alkyl group or acyl group having 1 to 10 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom, R ³²⁸ is a single bond or a methylene group. , an ethylene group, a sulfur atom or a O (CH ₂ CH ₂ O _n - .R ³²⁹ is .n = 0, 1, 2, 3 or 4 is a radical is a hydrogen atom, a methyl group, an ethyl group or a phenyl group .X is a nitrogen atom or CR ³³⁰ .Y nitrogen An atom or CR ^331. Z is a nitrogen atom or CR ^332. R ³³⁰ , R ³³¹ and R ³³² are each independently a hydrogen atom, a methyl group or a phenyl group, or R ³³⁰ and R ³³¹ or R ^331. And R ³³² may be bonded together to form a C 6-20 aromatic ring or a C 2-20 heteroaromatic ring together with the carbon atom to which they are bonded.

（上記式中、Ｒ³³³は水素又は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基である。Ｒ³³⁴及びＲ³³⁵はそれぞれ独立に、エーテル、カルボニル、エステル、アルコール、スルフィド、ニトリル、アミン、イミン、アミドなどの極性官能基を一つ又は複数含んでいてもよい炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基であって水素原子の一部がハロゲン原子で置換されていてもよい。Ｒ³³⁴とＲ³³⁵は互いに結合してこれらが結合する窒素原子と共に炭素数２〜２０のヘテロ環又はヘテロ芳香環を形成してもよい。） Furthermore, a nitrogen-containing organic compound having a 7-oxanorbornane-2-carboxylic acid ester structure represented by the following general formula (B) -15 is exemplified.

(In the above formula, R ³³³ is hydrogen or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. R ³³⁴ and R ³³⁵ are each independently ether, carbonyl, ester, alcohol, sulfide, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, which may contain one or more polar functional groups such as nitrile, amine, imine and amide. A part of the hydrogen atoms may be substituted with a halogen atom, and R ³³⁴ and R ³³⁵ are bonded to each other to form a C 2-20 heterocycle or heteroaromatic ring together with the nitrogen atom to which they are bonded. May be good.)

  The compounding amount of the nitrogen-containing organic compound is preferably 0.001 to 20 parts, particularly 0.01 to 10 parts with respect to 100 parts of the base resin. When the blending amount is less than 0.001 part, there is no blending effect, and when it exceeds 20 parts, the sensitivity may be excessively lowered.

  To the resist material of the present invention, a surfactant (E) conventionally used for improving the coating property as an optional component can be added in addition to the above components. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  Here, the surfactant is preferably nonionic, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane compound, and the like. Can be mentioned. For example, Florard “FC-430”, “FC-431” (all manufactured by Sumitomo 3M Limited), Surflon “S-141”, “S-145”, “KH-10”, “KH-20”, “ KH-30 "," KH-40 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), Mega For example, “F-8151” (manufactured by Dainippon Ink Industries, Ltd.), “X-70-092”, “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.) can be used. Preferably, Florard “FC-430” (manufactured by Sumitomo 3M Limited), “KH-20”, “KH-30” (all manufactured by Asahi Glass Co., Ltd.), “X-70-093” (Shin-Etsu Chemical Co., Ltd.) Product).

  In the resist material of the present invention, as an optional component other than the above components, it is unevenly distributed on the upper part of the coating film, and the hydrophilic / hydrophobic balance of the surface is adjusted, the water repellency is increased, or the coating film is water or other You may add the high molecular compound which has a function which prevents the outflow and inflow of a low molecular component, when it touches a liquid. The amount of the polymer compound added may be a normal amount as long as the effects of the present invention are not impaired, but is preferably 15 parts or less, particularly 10 parts or less, based on 100 parts of the base resin. The lower limit is preferably set to 1 part or more from the viewpoint of exhibiting the effect.

  Here, the polymer compound unevenly distributed on the upper part of the coating film is preferably a polymer or copolymer composed of one or more fluorine-containing units, and a copolymer composed of fluorine-containing units and other units. Specific examples of the fluorine-containing unit and other units include, but are not limited to, the following.

  The weight average molecular weight of the polymer compound unevenly distributed on the upper part of the coating film is preferably 1,000 to 50,000, more preferably 2,000 to 20,000. If it is out of this range, the surface modification effect may not be sufficient or development defects may occur. In addition, the said weight average molecular weight shows the polystyrene conversion value by a gel permeation chromatography (GPC).

  The basic components of the resist material of the present invention are the above-mentioned polymer, acid generator, organic solvent and nitrogen-containing organic compound, but in addition to the above-mentioned components, if necessary, a dissolution inhibitor, acidic Other components such as compounds, stabilizers, pigments may be added. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  Pattern formation using the resist material of the present invention can be performed by using a known lithography technique, and passes through each step of coating, heat treatment (pre-baking), exposure, heat treatment (post-exposure baking, PEB), and development. Achieved. If necessary, some additional steps may be added.

When pattern formation is performed, first, the resist material of the present invention is applied to an integrated circuit manufacturing substrate (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, Cr, CrO, CrON, (MoSi, etc.) is applied on the hot plate by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. so that the coating film thickness is 0.01 to 2.0 μm. At 50 to 150 ° C. for 1 to 10 minutes, preferably 60 to 140 ° C. for 1 to 5 minutes. The processing is becoming more severe due to the etching selectivity ratio of the substrate to be processed along with the thinning of the resist, the silicon-containing intermediate film under the resist, the underlayer film with high carbon density and high etching resistance under it, and the processing underneath Three-layer processes for laminating substrates are being studied. The etching selectivity between the silicon-containing intermediate film using oxygen gas, hydrogen gas, ammonia gas, or the like and the lower layer film is high, and the silicon-containing intermediate film can be thinned. The etching selectivity between the single-layer resist and the silicon-containing intermediate layer is also relatively high, and the single-layer resist can be thinned. In this case, examples of the method for forming the lower layer film include a method using coating and baking, and a method using CVD. In the case of the coating type, a novolak resin or a resin obtained by polymerizing an olefin having a condensed ring is used, and a gas such as butane, ethane, propane, ethylene, or acetylene is used for forming a CVD film. Also in the case of a silicon-containing intermediate layer, there are a coating type and a CVD type. Examples of the coating type include silsesquioxane and cage oligosilsesquioxane, and various silane gases are used as a raw material for CVD. The silicon-containing intermediate layer may have an antireflection function having light absorption, and may be a light-absorbing group such as a phenyl group or a SiON film. An organic film may be formed between the silicon-containing intermediate film and the photoresist film, and the organic film in this case may be an organic antireflection film.
After formation of the photoresist film, pure water rinsing (post-soak) may be performed to extract the acid generator or the like from the film surface, or the particles may be washed away, or a protective film may be applied.

Next, using a light source selected from ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotron radiation, and the like, exposure is performed through a predetermined mask for forming a target pattern. Exposure is preferably about 1 to 200 mJ / cm ^2, particularly about 10 to 100 mJ / cm ² is more preferable. Next, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes. Further, 0.1 to 5% by weight, preferably 2 to 3% by weight, using an aqueous developer such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes. The target pattern is formed on the substrate by development using a conventional method such as a dip method, a paddle method, or a spray method. The resist material of the present invention is preferably a far ultraviolet ray having a wavelength of 254 to 193 nm, a vacuum ultraviolet ray having a wavelength of 157 nm, an electron beam, a soft X-ray, an X-ray, an excimer laser, a γ ray, a synchrotron radiation, and more preferably a wavelength of 180. It can be applied to fine patterning with high energy rays in the range of ˜200 nm.

  The resist material of the present invention can also be applied to immersion lithography. In ArF immersion lithography, a liquid that has a refractive index of 1 or more and is highly transparent at the exposure wavelength, such as pure water or alkane, is used as the immersion solvent. In immersion lithography, pure water or other liquid is inserted between a pre-baked resist film and a projection lens. As a result, a lens with an NA of 1.0 or more can be designed, and a finer pattern can be formed. Immersion lithography is an important technique for extending the life of ArF lithography to the 45 nm node, and its development has been accelerated. In the case of immersion exposure, pure water rinsing (post-soak) after exposure to remove the water droplet residue remaining on the resist film may be performed, and elution from the resist film is prevented, and the surface lubricity of the film is prevented. In order to increase the thickness, a protective film may be formed on the resist film after pre-baking. As a resist protective film used in immersion lithography, for example, a polymer compound having a 1,1,1,3,3,3-hexafluoro-2-propanol residue that is insoluble in water and dissolved in an alkaline developer is used. A base and a material dissolved in an alcohol solvent having 4 or more carbon atoms, an ether solvent having 8 to 12 carbon atoms, or a mixed solvent thereof is preferable.

The resolution that can be reached with the highest NA of water immersion lithography using an NA 1.35 lens is 40 to 38 nm and cannot reach 32 nm. Therefore, development of a high refractive index material for further increasing NA is being carried out. It is the minimum refractive index among the projection lens, liquid, and resist film that determines the limit of the NA of the lens. In the case of water immersion, the refractive index of water is the lowest compared with the projection lens (refractive index of 1.5 for synthetic quartz) and resist film (refractive index of 1.7 for conventional methacrylate system). The lens NA was fixed. Recently, highly transparent liquids having a refractive index of 1.65 have been developed. In this case, it is necessary to develop a projection lens material having the lowest refractive index and a high refractive index of the projection lens made of synthetic quartz. LUAG (Lu ₃ Al ₅ O ₁₂ ) has a refractive index of 2 or more and is the most expected material.
The resist of the present invention can also be applied to lithography with a high refractive index liquid.

  Further, as a technique for extending the life of ArF lithography, a double patterning process in which a pattern is formed by the first exposure and development and a pattern is formed between the first pattern by the second exposure (Proc SPIE Vol.5754 p1508 (2005)). Many processes have been proposed as a double patterning method. For example, the first exposure and development form a photoresist pattern with 1: 3 line and space spacing, the lower hard mask is processed by dry etching, and another hard mask is laid on the first hard mask. In this exposure method, a line pattern is formed by exposure and development of a photoresist film in a space portion of the exposure, and a hard mask is processed by dry etching to form a line-and-space pattern that is half the pitch of the initial pattern. Further, a photoresist pattern having a space and line spacing of 1: 3 is formed by the first exposure and development, the underlying hard mask is processed by dry etching, and a photoresist film is applied thereon. The second space pattern is exposed to the portion where the hard mask remains, and the hard mask is processed by dry etching. In either case, the hard mask is processed by two dry etchings.

In the above-described method, it is necessary to lay a hard mask twice. In the latter method, only one hard mask is required, but it is necessary to form a trench pattern that is difficult to resolve compared to a line pattern. In the latter method, there is a method using a negative resist material for forming a trench pattern. This can use the same high contrast light as forming a line with a positive pattern, but the negative resist material has a lower dissolution contrast than the positive resist material. Compared with the case of forming a line, the case of using a negative resist material to form a trench pattern having the same dimensions is compared. The latter method uses a positive resist material to form a wide trench pattern, then heats the substrate to shrink the trench pattern, or coats a water-soluble film on the developed trench pattern. It may be possible to apply the RELACS method in which the trench is shrunk by heating and then crosslinking the resist film surface. .
Even in the former method and the latter method, etching for substrate processing is required twice, so that there is a problem in that throughput is reduced and pattern deformation and displacement occur due to the two etchings.

In order to complete the etching once, there is a method in which a negative resist material is used in the first exposure and a positive resist material is used in the second exposure. There is also a method in which a positive resist material is used in the first exposure, and a negative resist material dissolved in a higher alcohol having 4 or more carbon atoms that does not dissolve in the second exposure. In these cases, resolution degradation using a negative resist material with low resolution occurs.
When the second exposure is performed at a position shifted by a half pitch next to the first exposure, the energy of the second time is canceled and the contrast becomes zero. When a contrast enhancement film (CEL) is applied on the resist film, the light incident on the resist film becomes non-linear, and the first and second light beams do not cancel each other and an image with a half pitch is formed (Jpn. Appl.Phy.Vol. 33 (1994) p6874-6877). In addition, it is expected that a similar effect can be produced by generating a non-linear contrast using a two-photon absorption acid generator as an acid generator of the resist.

  The most critical problem in double patterning is the alignment accuracy of the first and second patterns. Since the size of the positional deviation is a variation in the line dimensions, for example, when an attempt is made to form a 32 nm line with an accuracy of 10%, an alignment accuracy within 3.2 nm is required. Since the alignment accuracy of the current scanner is about 8 nm, a significant improvement in accuracy is necessary.

After the first resist pattern is formed, the pattern is insolubilized in a resist solvent and an alkali developer by some method, the second resist is applied, and the second resist pattern is formed in the space portion of the first resist pattern. Resist pattern freezing technology has been studied. If this method is used, the substrate is etched only once, so that the problem of misalignment due to improvement in throughput and stress relaxation of the etching hard mask is avoided. As a technique of freezing, a method of forming a film on a resist pattern for the first time and a method of insolubilizing a resist pattern by light or heat have been studied. The resist material of the present invention can also be applied to such a process. Is possible. The light for freezing is preferably a wavelength of 300 nm or less, more preferably an ArF excimer light having a wavelength of 193 nm, a Xe ₂ excimer light having a wavelength of 172 nm, an F ₂ excimer light having a wavelength of 157 nm, a Kr ₂ excimer light having a wavelength of 146 nm, Ar ₂ excimer light is preferable, and in the case of light, the exposure amount is in the range of 10 mJ / cm ^{2 to} 10 J / cm ² . Irradiation with an excimer laser or excimer lamp having a wavelength of 200 nm or less, particularly 193 nm, 172 nm, 157 nm, 146 nm, or 122 nm, not only generates acid from the photoacid generator, but also promotes a crosslinking reaction by light irradiation. Further, a thermal acid generator of ammonium salt is added as a photoresist material in an amount of 0.001 to 20 parts, preferably 0.01 to 10 parts with respect to 100 parts of the base resin of the photoresist material, and the acid is heated by heating. It can also be generated. In this case, the generation of acid and the crosslinking reaction proceed simultaneously. The heating conditions are preferably 100 to 300 ° C., particularly 130 to 250 ° C. and preferably 10 to 300 seconds. Thereby, a crosslinked resist film insoluble in the solvent and the alkaline developer is formed.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, Me represents a methyl group.

The monomer of this invention was synthesize | combined by the prescription shown below.
Synthesis Example 1 Synthesis of methacrylic acid (6-methyl-6-spiro [4.5] decyl) (Monomer 1)

  While stirring at room temperature under a nitrogen atmosphere, 1.28 mol of a methylmagnesium chloride-tetrahydrofuran solution (prepared from 31.1 g of magnesium metal, 400 ml of tetrahydrofuran and chloromethane) was added to spiro [4.5] decan-6-one (this was A mixture of 100 g of tetrahydrofuran and 200 ml of tetrahydrofuran was added dropwise at 60 ° C. or lower from a cyclohexanone document: A. P. Krapcho, Synthesis, 1974, p. After the reaction mixture was refluxed for 30 minutes, a saturated aqueous ammonium chloride solution was added to stop the reaction. After ordinary post-treatment operations such as extraction, washing and drying, distillation was performed under reduced pressure to obtain 93.3 g (yield 87%) of the desired product 6-methylspiro [4.5] decan-6-ol.

6-Methylspiro [4.5] decan-6-ol Colorless liquid Boiling point: 55 ° C./6.7 Pa
IR (film): ν = 3614, 3480, 2937, 2862, 1464, 1447, 1375, 1335, 1321, 1260, 1202, 1173, 1153, 1111, 1084, 1002, 925, 878 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.03 (3H, s), 1.09-1.21 (3H, m), 1.26 to 1.62 (12H, m), 1.85 (1H, dt-like, J = 7, 13 Hz), 3.83 (1H, OH, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 21.91, 22.24, 24.20, 25.55, 25.79, 32.39 [broad (hereinafter abbreviated as br)], 33 84, 35.20, 37.97, 49.62, 71.77 ppm.
GC-MS (EI): (m / z) ⁺ = 71, 108, 121, 135, 150, 168 (M ⁺ ).

  While stirring at 40 ° C. under a nitrogen atmosphere, 142.4 g of methacryloyl chloride was added to a mixture of 156.82 g of 6-methylspiro [4.5] decan-6-ol, 183.8 g of triethylamine, 11 g of 4-dimethylaminopyridine, and 500 ml of acetonitrile. A mixture of 300 ml of acetonitrile was added dropwise. After stirring at 40 ° C. for 4 hours, 50 ° C. for 20 hours, and further at 60 ° C. for 5 hours, the reaction was stopped by adding a saturated aqueous sodium hydrogen carbonate solution. After the usual post-treatment operations for extraction, washing and drying, 163 g (yield 74%) of the desired product methacrylic acid (6-methyl-6-spiro [4.5] decyl) was obtained by distillation under reduced pressure.

Methacrylic acid (6-methyl-6-spiro [4.5] decyl)
Colorless liquid Boiling point: 77 ° C / 10.6Pa
IR (film): ν = 2936, 2864, 1712, 1637, 1452, 1399, 1377, 1328, 1305, 1186, 1164, 1147, 1101, 1009, 935, 905, 813 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.3-1.30 (2H, m), 1.32-1.46 (5H, m), 1.43 (3H, s), 1.47-1.59 (6H, m), 1.74 (1H, br), 1.85 (3H, br. S), 1.91 (1H, dt-like, J = 7, 13 Hz), 2 .21 (1H, br), 5.58 (1H, quint-like, J = 2 Hz), 5.93 (1H, s-like) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 18.20, 19.34, 21.42, 21.48, 25.60, 25.80, 31.93, 33.11 (br), 34.15 (br), 34.96, 50.13, 86.57, 124.43, 137.67, 165.52 ppm.
A broad peak was observed in the signal of some carbon atoms in the ¹³ C-NMR spectrum. Normally, when the equilibrium between conformations is sufficiently fast, a sharp peak is given to the average position according to the probability of each conformation, so this balancing is due to steric hindrance between the conformations between multiple conformations. It is suggested that it is suppressed.
GC-MS (EI): (m / z) ⁺ = 41, 69, 108, 135, 149, 236 (M ⁺ ).

Using the NMR measurement sample, the structure of the olefin produced by adding a catalytic amount of trifluoromethanesulfonic acid and heating to 40 ° C. to advance the elimination reaction was analyzed by ¹ H- and ¹³ C-NMR. However, it was identified as follows (the molar ratio in parentheses is the production molar ratio). The production of decalin-type olefin with skeletal transition due to 1,2-alkyl shift was observed.

[Synthesis Example 2] Synthesis of 6- (6-ethylspiro [4.5] decyl) methacrylate (Monomer2)

  While stirring at −8 ° C. under a nitrogen atmosphere, a mixture of 13.16 g of metallic lithium and 270 g of tetrahydrofuran was mixed with 73.21 g of spiro [4.5] decan-6-one, 103.3 g of ethyl bromide, and 500 g of tetrahydrofuran. The solution was added dropwise while maintaining the temperature at 0 ° C. or lower. Saturated aqueous ammonium chloride solution was added under ice cooling to stop the reaction. After ordinary post-treatment operations such as extraction, washing and drying, distillation under reduced pressure gave 71.1 g (yield 81%) of the desired product 6-ethylspiro [4.5] decan-6-ol.

6-Ethylspiro [4.5] decan-6-ol Colorless liquid Boiling point: 68 ° C / 16Pa
IR (film): ν = 3613, 3481, 2938, 2863, 1456, 1370, 1335, 1270, 1152, 1135, 1111, 1027, 1000, 972, 957, 897, 854, 799, 776 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 0.78 (3H, t, J = 7.3 Hz), 1.60-1.12 (1H, m), 1.15-1.67 (16H, m), 1.85 (1H, dt-like, 7, 13 Hz), 3.64 (1H, OH, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 27.30, 21.69, 22.10, 25.12, 25.51, 25.78, 31.63 (br), 31.90, 33.40, 35.02, 50.67, 73.28 ppm.
GC-MS (EI): (m / z) ^<+> = 67, 85, 108, 121, 135, 153, 164, 182 (M ^<+> ).

  While stirring at room temperature under a nitrogen atmosphere, 172 ml of a 2.64M n-butyllithium-n-hexane solution was added dropwise to a mixture of 80.0 g of 6-ethylspiro [4.5] decan-6-ol and 300 g of tetrahydrofuran. After stirring at 50-60 ° C for 2 hours, the mixture was cooled to 10 ° C or lower. A mixture of 55 g of methacryloyl chloride and 220 ml of tetrahydrofuran was added dropwise and stirred overnight at room temperature. Saturated aqueous ammonium chloride solution was added under ice cooling to stop the reaction. After normal post-treatment operations such as extraction, washing and drying, distillation under reduced pressure yielded 80.2 g (yield 73%) of the desired product 6- (6-ethylspiro [4.5] decyl) methacrylate.

Methacrylic acid 6- (6-ethylspiro [4.5] decyl)
Colorless liquid Boiling point: 83 ° C / 20Pa
IR (film): ν = 2939, 2865, 1713, 1637, 1451, 1398, 1377, 1326, 1298, 1182, 1144, 1102, 1035, 1007, 934, 923, 891, 874, 813 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 0.89 (3H, t, J = 7.3 Hz), 1.26-1.32 (2H, m), 1.34-1.44 (5H, m), 1.46-1.64 (6H, m), 1.67-1.75 (1H, m), 1.84-2.00 (3H, m), 1.85 (3H , Br.s), 2.20-2.26 (1H, m), 5.58 (1H, br.s), 5.94 (1H, br.s) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 9.57, 18.30, 21.16, 21.46, 25.06, 25.43, 26.52, 30.60, 33.00. (Br), 34.08 (br), 35.33, 51.27, 88.93, 124.38, 133.59, 165.61 ppm.
GC-MS (EI): (m / z) ⁺ = 41, 69, 108, 135, 163, 221, 250 (M ⁺ ).

When the structure of the olefin generated by elimination was analyzed in the same manner as in Synthesis Example 1 above, the structure was identified as follows (the generation molar ratio in parentheses).

[Synthesis Example 3] Synthesis of 1- (1-methylspiro [4.4] nonyl) methacrylate (Monomer3)

  While stirring at 40 ° C. under a nitrogen atmosphere, 1.6 mol of a methylmagnesium chloride-tetrahydrofuran solution (prepared from 39 g of metal magnesium, 1,300 ml of tetrahydrofuran and chloromethane), 1,300 ml of toluene, and then spiro [4.4] nonane. -1-one (this was synthesized from cyclopentanone in the literature: AP Krapcho, Synthesis, 1974, p.383 and a method similar to the cited document) and a mixture of 1,300 ml of toluene was dropped. . The reaction mixture was stirred at 70 ° C. for 1.5 hours, then returned to room temperature, and 20% hydrochloric acid was added to stop the reaction. After ordinary post-treatment operations such as extraction, washing and drying, distillation under reduced pressure was performed to obtain 103 g (yield 83%) of the target product 1-methylspiro [4.4] nonan-1-ol.

1-methylspiro [4.4] nonan-1-ol colorless liquid Boiling point: 57 ° C./180 Pa
IR (film): ν = 3446, 2954, 2869, 1452, 1375, 1306, 1232, 1206, 1122, 1072, 1054, 1002, 969, 947, 934, 906, 853 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.05 (3H, s), 1.10-1.23 (2H, m), 1.35-1.75 (12H, m), 3.94 (1H, OH, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 18.68, 22.94, 24.62, 24.96, 31.75, 34.02, 37.18, 39.09, 56.03 79.47 ppm.

  A mixture of 88 g of methacryloyl chloride and 200 ml of acetonitrile in a mixture of 88 g of 1-methylspiro [4.4] nonan-1-ol, 114 g of triethylamine, 6.9 g of 4-dimethylaminopyridine and 300 ml of acetonitrile with stirring at 40 ° C. in a nitrogen atmosphere. Was dripped. After stirring at 50 ° C. overnight, the temperature was returned to room temperature, and a saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction. After the usual post-treatment operations for extraction, washing and drying, distillation under reduced pressure yielded 105 g (yield 84%) of the desired product 1- (1-methylspiro [4.4] nonyl) methacrylate.

Methacrylic acid 1- (1-methylspiro [4.4] nonyl)
Colorless liquid Boiling point: 61 ° C / 20Pa
IR (film): ν = 2955,2872,1713,1637,1469,1448,1400,1331,1304,1268,1169,1144,1117,1076,1051,1007,934,901,870,814 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.3-1.28 (1H, m), 1.35-1.40 (1H, m), 1.40 (3H, s), 1.48-1.66 (9H, m), 1.76-1.82 (1H, m), 1.82 (3H, br.s), 1.86-1.92 (1H, m), 2.22-2.29 (1H, m), 5.56 (1H, quint-like, J = 1.5 Hz), 5.91 (1H, q, J = 0.9 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 18.05, 18.09, 18.58, 24.57, 24.69, 32.19, 33.31, 34.41, 36.15. 57.02, 91.51, 124.51, 137.48, 165.71 ppm.
GC-MS (EI): (m / z) ^<+> = 41, 69, 95, 135, 153, 222 (M ^<+> ).

When the structure of the olefin generated by elimination was analyzed in the same manner as in Synthesis Example 1 above, the structure was identified as follows (the generation molar ratio in parentheses).

[Synthesis Example 4] Synthesis of 1- (1-ethylspiro [4.4] nonyl) methacrylate (Monomer4)

  While stirring at −10 ° C. to 0 ° C. under a nitrogen atmosphere, a mixture of 13.01 g of metallic lithium and 340 ml of tetrahydrofuran was added to 86.4 g of spiro [4.4] nonan-1-one, 102.2 g of ethyl bromide and 560 ml of tetrahydrofuran. Was added dropwise while maintaining the temperature at 0 ° C. or lower. After stirring overnight at room temperature, the reaction was stopped by cooling with ice and adding a saturated aqueous ammonium chloride solution. After the usual post-treatment operations of extraction, washing, and drying, the product is purified by silica gel column chromatography to obtain 53 g of the starting material spiro [4.4] nonan-1-one and the target product 1-ethylspiro [4.4] nonane. 34.3 g of -1-ol was obtained (yield 84% from the consumed raw material).

1-ethylspiro [4.4] nonan-1-ol colorless liquid IR (film): ν = 3484, 2955, 2870, 1462, 1450, 1376, 1311, 1266, 1199, 1128, 1076, 1040, 1028, 1009, 995,971,943,920,896,866 cm < ^-1 >.
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 0.87 (3H, t, J = 7.3 Hz), 1.117-1.12 (1H, m), 1.19-1.25 (1H, m), 1.35 (2H, q, J = 7.3 Hz), 1.35-1.65 (10H, m), 1.65-1.74 (2H, m), 3.68 (1H, OH, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 8.64, 18.71, 24.45, 25.01, 27.08, 31.96, 33.64, 35.17, 37.64. 56.86, 81.87 ppm.
GC-MS (EI): (m / z) ^<+> = 67, 85, 121, 139, 150, 168 (M ^<+> ).

  While stirring at 40 ° C. under a nitrogen atmosphere, 21 g of methacryloyl chloride and 20 ml of acetonitrile were added to a mixture of 19.9 g of 1-ethylspiro [4.4] nonan-1-ol, 24 g of triethylamine, 1.44 g of 4-dimethylaminopyridine, and 50 ml of acetonitrile. Was added dropwise. After stirring at 50 ° C. overnight, the temperature was returned to room temperature, and a saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction. After ordinary post-treatment operations such as extraction, washing and drying, distillation under reduced pressure yielded 21.2 g (yield 76%) of the desired product 1- (1-ethylspiro [4.4] nonyl) methacrylate.

Methacrylic acid 1- (1-ethylspiro [4.4] nonyl)
Colorless liquid Boiling point: 68 ° C / 10.6Pa
IR (film): ν = 2955, 2873, 1713, 1451, 1328, 1301, 1169, 1116, 935, 814 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 0.82 (3H, t, J = 7.3 Hz), 1.21-1.29 (1H, m), 1.32-1.40 (1H, m), 1.49-1.66 (9H, m) 1.76-1.83 (1H, m), 1.84 (3H, br.s), 1.84-1.92 ( 2H, m), 2.40-2.12 (1H, m), 2.30-2.36 (1H, m) 5.56 (1H, quint-like, J = 1.5 Hz), 5.93 ( 1H, s-like) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 8.97, 18.11, 18.75, 23.83, 24.20, 25.13, 33.08, 33.40, 34.66 37.80, 57.53, 94.65, 124.40, 137.37, 165.59 ppm.
GC-MS (EI): (m / z) ⁺ = 41, 69, 95, 121, 149, 167, 179, 207, 236 (M ⁺ ).

Synthesis Example 5 Synthesis of 1- (1-methylspiro [4.5] decyl) methacrylate (Monomer 5)

  While stirring at 40 ° C. under a nitrogen atmosphere, 0.95 mol of a methylmagnesium chloride-tetrahydrofuran solution (prepared from 23 g of metal magnesium, 500 ml of tetrahydrofuran and chloromethane), 500 ml of toluene and then spiro [4.5] decan-1-one (This was synthesized from cyclopentanone by a method similar to the literature: AP Krapcho, Synthesis, 1974, p.383 and the cited document) and a mixture of 73 g and 1,300 ml of toluene was added dropwise. The reaction mixture was stirred at 70 ° C. overnight, then returned to room temperature, and a saturated aqueous ammonium chloride solution was added to stop the reaction. After the usual post-treatment operations for extraction, washing and drying, distillation was performed under reduced pressure to obtain 50.2 g (yield 63%) of the target product 1-methylspiro [4.5] decan-1-ol.

1-methylspiro [4.5] decan-1-ol colorless liquid Boiling point: 68 ° C./146 Pa
IR (D-ATR): ν = 3446, 2925, 2853, 1450, 1375, 1235, 1142, 1120, 1089, 1050, 924, 899, 841 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 0.97-1.63 (19H, m), 3.82 (1H, OH, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 18.70, 22.21, 25.56, 23.07, 26.15, 29.95, 31.14, 31.28, 38.30 47.20, 80.55 ppm.
GC-MS (EI): (m / z) ⁺ = 43, 71, 94, 108, 121, 135, 153, 168 (M ⁺ ).

  While stirring at 40 ° C. under a nitrogen atmosphere, 34.5 g of methacryloyl chloride was added to a mixture of 37 g of 1-methylspiro [4.5] decan-1-ol, 43.8 g of triethylamine, 2.6 g of 4-dimethylaminopyridine, and 100 ml of acetonitrile. A mixture of 50 ml of acetonitrile was added dropwise. The mixture was stirred at 50 ° C. overnight, then returned to room temperature, and 5% hydrochloric acid was added to stop the reaction. After normal post-treatment operations such as extraction, washing and drying, distillation under reduced pressure yielded 47.4 g (yield 94%) of the desired product 1- (1-methylspiro [4.5] decyl) methacrylate.

Methacrylic acid 1- (1-methylspiro [4.5] decyl)
Colorless liquid Boiling point: 68 ° C / 13Pa
IR (D-ATR): v = 2927, 2856, 1709, 1637, 1449, 1376, 1328, 1303, 1169, 1148, 1135, 932, 812 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.02-1.11 (1H, m), 1.16-1.38 (5H, m), 1.38 (3H, s), 1.48-1.63 (7H, m), 1.65-1.72 (1H, m), 1.83 (3H, br.s), 1.84-1.91 (1H, m), 2.30-2.36 (1H, m), 5.56 (1H, t-like, J = 1.8 Hz), 5.91 (1H, s-like) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 17.24, 18.19, 18.43, 22.29, 22.73, 25.89, 29.71, 30.07, 30.36 33.18, 48.84, 92.77, 124.52, 137.66, 165.69 ppm.
GC-MS (EI): (m / z) ⁺ = 41, 69, 107, 149, 167, 236 (M ⁺ ).

[Synthesis Example 6] Synthesis of methacrylic acid (1'-ethyl-5-norbornane-2-spiro-1'-cyclopentane-2'-yl) (Monomer 6)

  A mixture of 63 g of 2-dimethylaminocyclopentanone and 40 g of cyclopentadiene was heated to reflux in an oil bath at 110 ° C. for 12 hours. The fraction obtained by distilling the reaction mixture and having a boiling point of 67 ° C./80 Pa or less was purified by silica gel column chromatography to obtain 25.7 g of the desired product exo-5-norbornene-2-spiro-1′-cyclopentane-2′-one (yield). Yield 39%) and a small amount of the isomer endo-5-norbornene-2-spiro-1′-cyclopentan-2′-one.

exo-5-norbornene-2-spiro-1′-cyclopentane-2′-one colorless liquid IR (film): ν = 2962, 2872, 1727, 1335, 1159, 933 cm ⁻¹ .
¹ H-NMR (400 MHz in CDCl ₃ ): δ = 0.85 (1H, dd, J = 2.9, 11.2 Hz) 1.24-1.31 (1H, m), 1.50-1. 66 (1H, m), 1.70-1.95 (4H, m), 2.01 (1H, dd, J = 3.6, 11.5 Hz), 2.14-2.42 (2H, m ), 2.70 (br.s), 2.87 (br.s), 6.12 (1H, dd, J = 2.9, 5.9 Hz), 6.26 (1H, dd, J = 2) .9, 5.4 Hz) ppm.

endo-5-norbornene-2-spiro-1′-cyclopentane-2′-one colorless liquid IR (film): ν = 2962, 2872, 1731, 1335, 1166, 1012 cm ⁻¹ .
¹ H-NMR (400 MHz in CDCl ₃ ): δ = 1.4-2.38 (10H, m), 2.76 (br.s), 2.86 (br.s), 5.85 (1H, dd, J = 2.9, 5.4 Hz), 6.24 (1H, dd, J = 2.9, 5.4 Hz) ppm.

Hydrogenation was carried out at a rate of 15 kg / cm ² to a mixture of 25.5 g of exo-5-norbornene-2-spiro-1′-cyclopentane-2′-one, 70 ml of tetrahydrofuran, and 5% palladium-carbon catalyst amount. The catalyst was filtered off and concentrated under reduced pressure to obtain 25.8 g (quantitative yield) of the desired product exo-norbornane-2-spiro-1′-cyclopentane-2′-one.

exo-norbornane-2-spiro-1′-cyclopentane-2′-one colorless liquid IR (film): ν = 2951,2872, 1732,1317,1155,1041 cm ⁻¹ .
¹ H-NMR (400 MHz in CDCl ₃ ): δ = 0.91 (1H, dd, J = 2.9, 11.7 Hz), 1.05-1.22 (2H, m), 1.32-1 .65 (3H, m), 1.67-2.35 (10H, m) ppm.

  While stirring at −35 ° C. under a nitrogen atmosphere, 26 g of exo-5-norbornane-2-spiro-1′-cyclopentane-2′-one (where exo represents norbornane) was added to a mixture of 3.2 g of metallic lithium and 150 ml of tetrahydrofuran. This represents the relative steric position of the ketone with respect to the ring, which was synthesized by hydrogenating the Diels-Alder adduct of 2-dimethylaminocyclopentanone and cyclopentadiene) and a mixture of 32.8 g of ethyl bromide. The solution was added dropwise while keeping the temperature below ℃. After stirring overnight at 5 ° C., the mixture was cooled with ice, and a saturated aqueous ammonium chloride solution was added to stop the reaction. After normal post-treatment operations such as extraction, washing and drying, the product is purified by silica gel column chromatography to obtain the target product 1′-ethyl-5-norbornane-2-spiro-1′-cyclopentane-2′-ol. 8 g (68% yield) was obtained.

exo-1'-ethyl-5-norbornane-2-spiro-1'-cyclopentane-2'-ol (mixture of diastereomers)
Colorless liquid IR (film): ν = 3479, 2949, 2870, 1458, 1296, 1130, 1105, 968, 887 cm ⁻¹ .
¹ H-NMR (400 MHz in CDCl ₃ ): δ = 0.81-0.90 (1H, m), 0.93-1.00 (3H, m), 1.08-1.21 (3H, m ), 1.24-1.43 (2.3 H, m), 1.44-1.65 (9.5 H, m), 1.64-1.73 (1 H, m), 1.80-1 .87 (0.3H, m), 1.96-2.06 (1H, m), 2.17-2.22 (1.7H, m) ppm (H number is 0.93-1.00) (Approximate relative value when the total integrated value of the CH ₃ signals of the two isomers appearing is 3H).

  While stirring at 5 ° C. under a nitrogen atmosphere, 13.8 g of exo-1′-ethyl-5-norbornane-2-spiro-1′-cyclopentane-2′-ol (diastereomer mixture), 13 ml of methacryloyl chloride, 4 -21 ml of triethylamine was added dropwise to a mixture of 120 ml of dimethylaminopyridine catalyst and 120 ml of methylene chloride. The mixture was stirred overnight at room temperature and quenched with saturated ammonium chloride. After ordinary post-treatment operations such as extraction, washing and drying, the product is concentrated under reduced pressure to give the target product exo- (1′-ethyl-5-norbornane-2-spiro-1′-cyclopentane-2′-yl). Obtained.

Synthesis Example 7 Synthesis of 6-methyl-6-dispiro [4.1.4.3] tetradecyl methacrylate (Monomer 7)

  While stirring at 50 ° C. in a nitrogen atmosphere, 0.43 mol of a methylmagnesium chloride-tetrahydrofuran solution (prepared from 10.45 g of magnesium metal, 150 ml of tetrahydrofuran and chloromethane) was added to dispiro [4.1.4.3] tetradecane-6- On (this was synthesized from spiro [4.5] decan-6-one in a manner similar to literature: AP Krapcho, Synthesis, 1974, p. 383 and references cited therein) and 43 ml of tetrahydrofuran. Was added dropwise at 60 ° C. or lower. After cooling to room temperature, a saturated aqueous ammonium chloride solution was added to stop the reaction. After the usual post-treatment operations of extraction, washing and drying, distillation under reduced pressure yielded 46.3 g (yield 97%) of the desired product 6-methyldispiro [4.1.4.3] tetradecan-6-ol.

6-Methyldispiro [4.1.4.3] tetradecan-6-ol Colorless liquid Boiling point: 86 ° C./13 Pa
IR (film): ν = 3625, 3520, 2948, 2866, 1444, 1377, 1305, 1111, 1090, 944, 902 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.06 (3H, s), 1.14-1.23 (6H, m), 1.28-1.55 (12H, m), 1.62-1.73 (2H, br), 1.79-1.86 (2H, m), 3.72 (1H, OH, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 18.69, 20.09 (CH ₃ , br), 23.41 (2C, br), 24.57 (2C), 30.12 (2C , Br), 33.86 (2C), 34.83 (2C, br), 51.40 (2C), 74.68 ppm.
GC-MS (EI): (m / z) ⁺ = 43, 67, 93, 108, 122, 135, 162, 189, 204, 222 (M ⁺ ).

  While stirring under ice-cooling in a nitrogen atmosphere, a mixture of 57.5 ml of a 2.64 M n-butyllithium-n-hexane solution and 60 ml of tetrahydrofuran was added to 6-methyldispiro [4.1.4.3] tetradecan-6-ol 32. .8 g was added dropwise at 20 ° C. or lower. After dropping, the mixture was stirred at 50 ° C. for 2 hours, and then ice-cooled again, and a mixture of 27 g of methacrylic acid pivalic acid mixed acid anhydride and 160 ml of tetrahydrofuran was added dropwise. After stirring at room temperature overnight, a saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction. After usual post-treatment operations such as extraction, washing and drying, the product was purified by silica gel column chromatography to obtain 18.8 g of the desired product 6-methyl-6-dispiro [4.1.4.3] tetradecyl methacrylate (44% yield). %).

6-methyl-6-dispiro methacrylate [4.1.4.3] tetradecyl colorless liquid IR (D-ATR): ν = 2939, 2866, 1709, 1637, 1455, 1385, 1320, 1297, 1170, 1145 1124,931,807 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.2-1.28 (2H, m), 1.30-1.60 (16H, m), 1.60-1.68 (2H) , M), 1.66 (3H, s), 1.85 (3H, br. S), 1.90-1.97 (2H, m) 5.55 (1H, quint-like, J = 1.2 Hz ), 5.91 (1H, s-like) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ , 60 ° C.): δ = 16.52 (CH ₃ , br), 18.10, 18.22, 23.92 (4C, br), 33.78 (2C ), 33.83 (2C, br), 34.19 (2C, br), 52.38 (2C), 93.01, 123.59, 138.05, 165.47 ppm.
^In the measurement at room temperature in the ¹³ C-NMR spectrum, since the disappearance of the signal due to the broadening of the peak (missing carbon) was observed, the measurement was performed by heating to 60 ° C. Even under warming, signal broadening, which is thought to be due to the suppression of steric hindrance to the equilibrium between the multiple conformations, was observed.

Using the NMR measurement sample, the structure of the olefin produced by adding a catalytic amount of trifluoromethanesulfonic acid and heating to 40 ° C. to advance the elimination reaction was analyzed by ¹ H- and ¹³ C-NMR. However, it was identified as follows (the molar ratio in parentheses is the production molar ratio). The production of decalin-type olefin with skeletal transition due to 1,2-alkyl shift was observed.

Synthesis Example 8 Synthesis of 6-dispiro methacrylate [4.1.4.3] tetradecyl (Monomer 8)

  Dispiro [4.1.4.3] tetradecane into a mixture of 14.5 g of sodium borohydride, 145 g of methanol, 0.3 g of 25% aqueous sodium hydroxide, 8 g of water and 73 g of tetrahydrofuran while stirring and cooling with ice water in a nitrogen atmosphere. -6-one 80g and tetrahydrofuran 73g were added. The reaction mixture was stirred at room temperature overnight, 300 ml of toluene was added, and the organic layer was separated. After usual washing / drying post-treatment operations, the mixture was concentrated under reduced pressure to obtain 81.0 g (yield 99%) of the desired product dispiro [4.1.4.3] tetradecan-6-ol. This product had sufficient purity and was used in the next step without further purification.

Dispiro [4.1.4.3] tetradecan-6-ol colorless solid IR (D-ATR): ν = 3481, 2926, 2861, 1449, 1060 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 0.99-1.07 (2H, m), 1.08-1.21 (4H, m), 1.25-1.35 (2H) M), 1.38-1.57 (10H, m), 1.57-1.63 (2H, m), 1.70-1.79 (2H, m), 3.11 (1H, d) , J = 5.9 Hz) 3.39 (1H, OH, d, J = 5.9 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 19.55, 23.96 (2C), 24.93 (2C), 30.19 (2C), 36.14 (2C), 38.06 (2C), 47.98, 77.92 (2C) ppm.
GC-MS (EI): (m / z) ⁺ = 41, 55, 67, 79, 94, 108, 121, 147, 190, 208 (M ⁺ ).

  While stirring at 40 ° C. under a nitrogen atmosphere, a mixture of 5.0 g of dispiro [4.1.4.3] tetradecan-6-ol, 4.80 g of triethylamine, 0.29 g of 4-dimethylaminopyridine, and 25 ml of acetonitrile was mixed with chloride. A mixture of 3.72 g of methacryloyl and 5 ml of acetonitrile was added dropwise. The reaction mixture was stirred at 40 ° C. overnight, and then the reaction was stopped by adding a saturated aqueous sodium hydrogen carbonate solution. After usual post-treatment operations such as extraction, washing and drying, purification by silica gel column chromatography gives 1.92 g (yield 29%) of the desired product 6-dispiro [4.1.4.3] tetradecyl methacrylate. It was.

Methacrylic acid 6-dispiro [4.1.4.3] tetradecyl colorless liquid IR (D-ATR): ν = 2948, 2865, 1712, 1452, 1292, 1161, 935, 810 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.25 to 1.55 (22H, m), 1.89 (3H, s), 4.77 (1H, s), 5.66 ( 1H, quint-like, J = 1.5 Hz), 6.04 (1H, s-like) ppm.
¹³ C-NMR (150 MHz in DMSO-d _6, 60 ° C.): δ = 17.71, 18.85, 23.39 (2C), 23.55 (2C), 33.12 (2C, br), 34 .31 (2C, br), 35.96 (2C, br), 47.10, 81.65 (2C), 124.85, 136.06, 166.18 ppm.
^In the measurement at room temperature in the ¹³ C-NMR spectrum, since the disappearance of the signal due to the broadening of the peak (missing carbon) was observed, the measurement was performed by heating to 60 ° C. Even under warming, signal broadening, which is thought to be due to the suppression of steric hindrance to the equilibrium between the multiple conformations, was observed.
GC-MS (EI): (m / z) ⁺ = 41, 55, 69, 94, 108, 133, 148, 162, 190, 234, 248, 262, 276 (M ⁺ ).

Synthesis Example 9 Synthesis of acrylic acid (6-methyl-6-spiro [4.5] decyl)

  To a mixture of 6-methylspiro [4.5] decan-6-ol 100 g, triethylamine 83 g and toluene 250 g, a toluene 50 g solution of acryloyl chloride 69 g was added dropwise at 60 ° C. over 1 hour. After stirring at the same temperature for 6 hours, the reaction solution was cooled to 0 ° C., and 50 g of water and 130 g of saturated aqueous sodium hydrogen carbonate were added dropwise to stop the reaction. 300 g of hexane was added, extracted, washed, dried, concentrated, and purified by distillation to obtain 105 g of acrylic acid (6-methyl-6-spiro [4.5] decyl) as a target product (yield) 82%).

Acrylic acid (6-methyl-6-spiro [4.5] decyl)
Colorless liquid Boiling point: 69 ° C / 20Pa
IR (D-ATR): ν = 2937, 2863, 1718, 1619, 1449, 1401, 1377, 1296, 1283, 1254, 1209, 1165, 1148, 1102, 1047, 1014, 984, 960, 912, 887, 865 810 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 12-14-11 (7H, m), 1.43 (3H, s), 1.46-1.63 (6H, m), 1.78 (1H, br), 1.86-1.92 (1H, m), 2.17 (1H, br), 5.84 (1H, dd, J = 1.6, 10.3 Hz), 6.04 (1H, dd, J = 10.1, 17.4 Hz), 6.19 (1H, dd, J = 1.9, 17.4 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 19.36, 21.39, 21.48, 25.67, 25.75, 32.04, 33.15, 34.04, 34.87 49.94, 129.82, 130.31, 164.51 ppm.
GC-MS (EI): (m / z) ⁺ = 27, 43, 55, 67, 81, 93, 108, 121, 135, 149, 165, 179, 193, 207, 222, 283 (M ⁺ ).

Synthesis Example 10 Synthesis of 5-norbornene-2-carboxylic acid (6-methyl-6-spiro [4.5] decyl)

Cyclopentadiene generated from 20 g of dicyclopentadiene was added dropwise to 50 g of acrylic acid (6-methyl-6-spiro [4.5] decyl) at 30 ° C. The internal temperature was gradually raised to 70 ° C., and the mixture was stirred for 12 hours. The reaction solution was directly purified by silica gel chromatography to obtain a diastereomeric mixture of 54 g of the desired product 5-norbornene-2-carboxylic acid (6-methyl-6-spiro [4.5] decyl) (yield 98). %).
5-norbornene-2-carboxylic acid (6-methyl-6-spiro [4.5] decyl), a mixture of two diastereomers of endo form and two diastereomers of exo form, endo form: exo form = 85:15
Colorless liquid IR (D-ATR): ν = 3061, 2939, 2864, 1725, 1570, 1445, 1376, 1335, 1296, 1271, 1252, 1203, 1165, 1147, 1132, 1103, 1063, 1016, 1000, 954 922, 904, 887, 866, 838, 815, 778, 759, 711 cm ⁻¹ .
This product was a mixture of two diastereomers in the endo form and two diastereomers in the exo form, and gave complex spectra in ¹ H-NMR and ¹³ C-NMR. The spectrum of major isomers is shown below.
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.20-1.45 (13H, m), 1.47-1.62 (6H, m), 1.63-1.84 (2H) , M), 1.85-1.94 (1H, m), 1.95-2.26 (1H, m), 2.83 (1H, br), 2.90-2.99 (1H, m ), 3.08 (1H, br), 5.90 (1H, dd, J = 4.6, 10.0 Hz), 6.14-6.18 (1H, m) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 19.25, 21.35, 21.44, 21.49, 21.55, 25.72, 25.80, 25.83, 28.17 28.20, 32.02, 32.22, 33.15, 33.36, 33.83, 34.10, 34.88, 34.94, 41.88, 43.84, 43.93, 45. 17, 45.30, 49.02, 49.23, 49.89, 49.92, 85.67, 85.76, 132.15, 132.30, 137.49, 133.54, 172.60. 172.66 ppm.
The GC-MS spectrum of the main isomer is shown.
GC-MS (EI): (m / z) ⁺ = 27, 43, 66, 81, 95, 121, 135, 150, 166, 190, 205, 223, 245, 259, 273, 288, 313, 326 ( M ⁺ ).

[Synthesis Comparative Example 1] Synthesis of methacrylic acid (8-methyl-8-spiro [4.5] decyl) (Monomer 9)

  4.8 g of 25% aqueous sodium hydroxide solution was added to 5.5 g of p- (4-chlorobutyl) phenol and stirred. The mixture is gradually heated under reduced pressure to remove water (120 ° C., up to 50 Pa), and then the temperature is raised to 180-200 ° C. to obtain a fraction, spiro [4.5] deca-6,9-diene- 2.11 g (47% yield) of 8-one was obtained.

Spiro [4.5] deca-6,9-dien-8-one colorless liquid IR (D-ATR): ν = 2955, 2868, 1655, 1621, 1406, 1254, 1174, 941, 856 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.70-1.75 (4H, m), 1.84-1.90 (4H, m), 6.06-6.11 (2H , M), 7.04-7.08 (2H, m) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 24.68 (2C), 37.24 (2C), 48.32, 126.40 (2C), 155.72 (2C), 185.17 ppm .
GC-MS (EI): (m / z) ^<+> = 91, 107, 120, 133, 148 (M ^<+> ).

Hydrogen was added at 12 kg / cm ² to a mixture of 12.8 g of spiro [4.5] dec-6,9-dien-8-one and 50 ml of ethyl acetate and 10% palladium-carbon catalyst amount. The catalyst was filtered off and concentrated under reduced pressure to obtain 13.5 g (quantitative yield) of the desired product 8-spiro [4.5] decanone. This product had sufficient purity and was used in the next step without further purification.

8-spiro [4.5] decanone colorless liquid IR (D-ATR): ν = 2946, 2856, 1714, 1446, 1336, 1231, 1143, 962 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.48-1.56 (4H, m), 1.59-1.64 (4H, m), 1.66 (4H, t, J = 6.9 Hz), 2.24 (4H, t, J = 6.9 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ , 60 ° C.): δ = 23.96 (2C), 36.64 (2C), 36.96 (2C), 38.55 (2C), 41.60, 211.22 ppm.
GC-MS (EI): (m / z) ^<+> = 55, 67, 81, 97, 108, 123, 152 (M ^<+> ).

Separate synthesis of 8-spiro [4.5] decanone Literature: Prepared using 221.84 g of cyclopentane carbaldehyde in place of cyclooctane carbaldehyde in a similar process to that described in Organic Synthesis, Collective Volume 7, page 473. Michael addition of piperidine enamine to methyl vinyl ketone, cyclization by aldol condensation, dehydration, hydrolysis, purification by vacuum distillation and 173.4 g of spiro [4.5] dec-6-en-8-one (yield) 54%).

Spiro [4.5] dec-6-en-8-one colorless liquid IR (D-ATR): ν = 2948, 2861, 1673, 1447, 1388, 1228, 1137, 927, 791 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.54-1.73 (8H, m), 1.81 (2H, t, J = 6.9 Hz), 2.31-2.35 (3H, m), 5.74 (1H, d, J = 9.6 Hz), 6.83 (1H, d, J = 10.1 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 24.03 (2C), 33.18, 34.98, 37.40 (2C), 43.76, 126.05, 159.64, 198 .73 ppm.
GC-MS (EI): (m / z) ⁺ = 53, 66, 79, 94, 108, 122, 150 (M ⁺ ).

Hydrogenation was carried out at 10 kg / cm ² to a mixture of spiro [4.5] dec-6-en-8-one (170 g) and tetrahydrofuran (400 ml), 10% palladium-carbon catalyst amount. The catalyst was filtered off and concentrated under reduced pressure to obtain 187 g (quantitative yield) of the desired product 8-spiro [4.5] decanone. The spectroscopic properties of this were consistent with those described above. Moreover, this thing had sufficient purity and was used for the following process, without further refine | purifying.

  While stirring at room temperature in a nitrogen atmosphere, 0.205 mol of a methylmagnesium chloride-tetrahydrofuran solution (prepared from 5.0 g of metal magnesium, 100 ml of tetrahydrofuran and chloromethane), 13.4 g of 8-spiro [4.5] decanone and tetrahydrofuran 80 ml of the mixture was added dropwise at 50 ° C. or lower. After cooling to room temperature, a saturated aqueous ammonium chloride solution was added to stop the reaction. After usual post-treatment operations such as extraction, washing and drying, the reaction mixture was concentrated under reduced pressure to obtain 14.43 g (yield 99%) of the desired product 8-methylspiro [4.5] decan-8-ol. This product had sufficient purity and was used in the next step without further purification.

8-Methylspiro [4.5] decan-8-ol colorless solid IR (D-ATR): ν = 3334, 2918, 2853, 1443, 1373, 1268, 1130, 993, 891 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.57 (3H, s), 1.13-1.18 (2H, m), 1.28-1.35 (6H, m), 1.36-1.41 (2H, m), 1.47-1.55 (6H, m), 3.94 (1H, OH, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ , 60 ° C.): δ = 23.51, 23.88, 29.23 (br), 33.44, 35.60 (2C, br), 36.24, 38.91 (2C, br), 41.33, 67.17 ppm.

  While stirring at room temperature under a nitrogen atmosphere, 14.4 g of 8-methylspiro [4.5] decan-8-ol, 13.5 g of triethylamine, a catalyst amount of 4-dimethylaminopyridine, a mixture of 150 ml of acetonitrile and 100 ml of tetrahydrofuran, methacryloyl chloride 13 .9 g was added dropwise. After stirring overnight at 50 ° C., the temperature was returned to room temperature, and water was added to stop the reaction. After normal post-treatment operations such as extraction, washing and drying, distillation under reduced pressure gave 17.0 g (yield 83%) of the desired product methacrylic acid (8-methyl-8-spiro [4.5] decyl).

Methacrylic acid (8-methyl-8-spiro [4.5] decyl)
Colorless liquid Boiling point: 78 ° C / 9.3Pa
IR (D-ATR): ν = 2933, 2854, 1711, 1637, 1445, 1327, 1306, 1176, 1148, 935 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.26-1.31 (2H, m), 1.31-1.35 (2H, m), 1.38-1.44 (4H) , M), 1.46 (3H, s), 1.47-1.61 (6H, m), 1.84-1.86 (3H, t-like, J = 0.9 Hz), 2.05- 2.10 (2H, m), 5.55-5.57 (1H, m), 5.93-5.95 (1H, m) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ , 60 ° C.): δ = 17.70, 23.39, 23.99, 24.71, 32.85, 33.12, 34.75 (2C), 39 .87 (2C) 40.95, 80.80, 123.96, 137.29, 165.42 ppm.

[Synthesis Comparative Example 2] Synthesis of methacrylic acid (7-methyl-7-spiro [4.5] decyl) (Monomer 10)

  Literature: Organic Synthesis, Collective Volume 5, similar to the method described on page 539, using 81.2 g of spiro [4.5] decane-7,9-dione instead of dihydroresorcinol and isobutyl alcohol instead of ethyl alcohol The corresponding isobutyl enol ether was prepared and purified by silica gel column chromatography to give 9-isobutyloxyspiro [4.5] dec-8-en-7-one (56% yield).

9-isobutyloxyspiro [4.5] dec-8-en-7-one colorless liquid IR (D-ATR): ν = 2954, 2873, 1655, 1603, 1471, 1381, 1362, 1213, 1146, 1002, 819 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 0.91 (6H, d, J = 6.4 Hz), 1.34-1.47 (4H, m), 1.56-1.63 (4H, m), 1.94 (1H, nonet, J = 6.4 Hz), 2.19 (1H, s), 2.36 (1H, s), 3.63 (2H, d, J = 6) .4 Hz), 5.26 (1H, s, OH) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 18.79 (2C), 23.60 (2C), 27.18, 37.48 (2C), 40.67, 42.89, 48. 67, 74.13, 101.54, 176.34, 197.82 ppm.
GC-MS (EI): (m / z) ⁺ = 41, 57, 69, 84, 96, 109, 125, 138, 151, 167, 222 (M ⁺ ).

While stirring at room temperature under a nitrogen atmosphere, a mixture of 59 g of 9-isobutyloxyspiro [4.5] dec-8-en-7-one and 150 ml of tetrahydrofuran was added dropwise to a mixture of 10.0 g of lithium aluminum hydride and 400 ml of tetrahydrofuran. . After stirring overnight at room temperature, the reaction was stopped by cooling with ice and dropwise addition of 20 ml of water and then 400 ml of 10% sulfuric acid. After stirring at room temperature for 1 hour, after normal washing and drying after-treatment, the mixture was concentrated under reduced pressure to give 8-spiro [4.5] decen-7-one and 8-spiro [4.5] decene-7-. 45.9 g of a mixture of nor were obtained. To 45.8 g of the obtained mixture, 50 ml of tetrahydrofuran, 10% palladium-carbon catalyst amount was added, and hydrogenated at 14 kg / cm ² . After the catalyst was filtered off and concentrated under reduced pressure, it was separated and purified by silica gel column chromatography to obtain 30.85 g (yield 79%) of 7-spiro [4.5] decanone and 8.92 g of 7-spiro [4.5] decanol. (Yield 23%) was obtained.

7-spiro [4.5] decanone colorless liquid IR (D-ATR): v = 2940, 2870, 1708, 1444, 1310, 1226, 1174, 1020 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.27-1.41 (4H, m), 1.52-1.58 (4H, m), 1.58-1.62 (2H) , M), 1.72-1.77 (2H, m), 2.17 (2H, s), 2.21 (2H, t, J = 6.4 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 2.18, 23.69 (2C), 35.74, 37.54 (2C), 40.52, 46.93, 52.49, 210 .62 ppm.
GC-MS (EI): (m / z) ⁺ = 41, 55, 67, 81, 94, 109, 123, 137, 152 (M ⁺ ).

7-spiro [4.5] decanol colorless solid IR (D-ATR): ν = 3326, 2925, 2856, 1449, 1364, 1091, 1052, 1019 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 0.96-1.10 (3H, m), 1.22-1.38 (6H, m), 1.47-1.61 (6H) , M), 1.73-1.79 (1H, m), 3.35-3.33 (1H, m), 4.33 (1H, OH, d, J = 4.6 Hz) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 2.34, 23.22, 24.41, 34.89, 35.56, 36.57, 41.70, 43.15, 47.31 66.74 ppm.
GC-MS (EI): (m / z) ⁺ = 41, 55, 67, 79, 94, 107, 121, 138, 154 (M ⁺ ).

  While stirring at −70 ° C. in a nitrogen atmosphere, 12.0 g of dimethyl sulfoxide was added to a mixture of 14.4 g of oxalyl chloride and 100 ml of methylene chloride, and the mixture was stirred for 10 minutes. Next, a mixture of 7.72 g of 7-spiro [4.5] decanol and 20 ml of methylene chloride was added dropwise at −55 ° C. or lower, and the mixture was stirred at −70 ° C. for 30 minutes. Further, 50 g of triethylamine was added, and the temperature was raised to -5 ° C. with stirring. The reaction mixture was poured into a saturated aqueous ammonium chloride solution, followed by normal washing, drying and concentration after-treatment, followed by separation and purification by silica gel column chromatography to give 8.22 g of 7-spiro [4.5] decanone (yield 96). %). The spectroscopic properties of this were consistent with those described above.

  While stirring at room temperature under a nitrogen atmosphere, 0.502 mol of a methylmagnesium chloride-tetrahydrofuran solution (prepared from 12.2 g of magnesium metal, 500 ml of tetrahydrofuran and chloromethane) was added to 39.1 g of 7-spiro [4.5] decanone and 100 ml of tetrahydrofuran. Was added dropwise. After stirring at room temperature overnight, a saturated aqueous ammonium chloride solution was added to stop the reaction. After ordinary post-treatment operations such as extraction, washing and drying, the reaction mixture was concentrated under reduced pressure to obtain 42.3 g (yield 95%) of the desired product 7-methylspiro [4.5] decan-7-ol. This product had sufficient purity and was used in the next step without further purification.

7-methylspiro [4.5] decan-7-ol colorless solid IR (D-ATR): ν = 3382, 2926, 2865, 1447, 1371, 1274, 1168, 1126, 962, 922 cm ⁻¹ .
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.2-1.09 (1H, m), 1.05 (3H, s), 1.17-1.65 (15 H, m), 3.76 (1H, OH, s) ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 19.46, 22.94, 24.02, 31.58, 36.50, 36.93, 39.22, 41.32, 42.24 49.77, 68.55 ppm.

  While stirring at 50 ° C. under a nitrogen atmosphere, methacryloyl chloride was added to a mixture of 42.0 g of 7-methylspiro [4.5] decan-7-ol, 40.2 g of triethylamine, a catalyst amount of 4-dimethylaminopyridine, 400 ml of acetonitrile and 50 ml of tetrahydrofuran. 41.0 g was added dropwise. The mixture was stirred at 50 ° C. for 1 hour, at room temperature overnight, and further at 50 ° C. for 1 hour, then returned to room temperature, and water was added to stop the reaction. After ordinary post-treatment operations such as extraction, washing and drying, distillation under reduced pressure yielded 43.7 g (yield 78%) of the desired product 7-methyl-7-spiro [4.5] decyl methacrylate.

Methacrylic acid 7-methyl-7-spiro [4.5] decyl colorless liquid Boiling point: 95 ° C./73 Pa
IR (D-ATR): [nu] = 2929,2866,1709,1637,1447,1331,1306,1174,1153,935 cm < ^-1 >.
¹ H-NMR (600 MHz in DMSO-d ₆ ): δ = 1.01-1.08 (1H, m), 1.15-1.22 (1H, m), 1.24-1.35 (3H) M), 1.40-1.56 (9H, m), 1.42 (3H, s), 1.83 (3H, d, J = 1.4 Hz), 2.06-2.11 (1H) M), 2.16-2.21 (1H, m), 5.58 (1H, dq-like, J = 0.9, 1.4 Hz), 5.94 (1H, q, J = 0.9 Hz) ) Ppm.
¹³ C-NMR (150 MHz in DMSO-d ₆ ): δ = 18.15, 18.82, 22.21, 23.97, 26.41, 34.94, 35.16, 37.02, 41.94 42.02, 45.08, 81.67, 124.62, 137.51, 165.88 ppm.

The polymer compound of the present invention was synthesized according to the formulation shown below.
[Synthesis Example 9-1] Synthesis of Polymer 1 Under a nitrogen atmosphere, 6.14 g of methacrylic acid (6-methyl-6-spiro [4.5] decyl), 5.12 g of 3-hydroxy-1-adamantyl methacrylate, methacryl Acid 4,8-dioxatricyclo [4.2.1.0 ^3,7 ] nonane-5-one-2-yl 8.74 g, 2,2′-azobisisobutyronitrile 0.57 g and 2 -A solution was prepared by dissolving 0.1 g of mercaptoethanol in 22.09 g of propylene glycol monomethyl ether acetate and 18.97 g of γ-butyrolactone. The solution was added dropwise over 6 hours to 6.28 g of propylene glycol monomethyl ether acetate and 5.39 g of γ-butyrolactone stirred at 80 ° C. in a nitrogen atmosphere. After completion of dropping, the mixture was stirred for 2 hours while maintaining 80 ° C., cooled to room temperature, and then the polymerization solution was added dropwise to 320 g of methanol. The precipitated solid was separated by filtration, washed twice with 120 g of methanol, and then vacuum-dried at 50 ° C. for 16 hours to obtain a white powder solid polymer compound (Polymer 1) represented by the following formula. The yield was 17.19 g, and the yield was 86%. In addition, Mw represents the weight average molecular weight measured using GPC in polystyrene conversion.

[Synthesis Examples 9-2 to 29, Synthesis Comparative Examples 3-1 to 10] Synthesis of Polymers 2 to 39 The same as [Synthesis Example 9-1] except that the types and blending ratios of the respective monomers were changed. According to the procedure, resins having the following structures and monomer composition ratios were produced.

[Synthesis Example 9-2]

[Synthesis Example 9-3]

[Synthesis Example 9-4]

[Synthesis Example 9-5]

[Synthesis Example 9-6]

[Synthesis Example 9-7]

[Synthesis Example 9-8]

[Synthesis Example 9-9]

[Synthesis Example 9-10]

[Synthesis Example 9-11]

[Synthesis Example 9-12]

[Synthesis Example 9-13]

[Synthesis Example 9-14]

[Synthesis Example 9-15]

[Synthesis Example 9-16]

[Synthesis Example 9-17]

[Synthesis Example 9-18]

[Synthesis Example 9-19]

[Synthesis Example 9-20]

[Synthesis Example 9-21]

[Synthesis Example 9-22]

[Synthesis Example 9-23]

[Synthesis Example 9-24]

[Synthesis Example 9-25]

[Synthesis Example 9-26]

[Synthesis Example 9-27]

[Synthesis Example 9-28]

[Synthesis Example 9-29]

[Synthesis Comparative Example 3-1]

[Synthesis Comparative Example 3-2]

[Synthesis Comparative Example 3-3]

[Synthesis Comparative Example 3-4]

[Synthesis Comparative Example 3-5]

[Synthesis Comparative Example 3-6]

[Synthesis Comparative Example 3-7]

[Synthesis Comparative Example 3-8]

[Synthesis Comparative Example 3-9]

[Synthesis Comparative Example 3-10]

[Examples and Comparative Examples]
Preparation of resist material [Examples 1-1 to 35, Comparative Examples 1-1 to 11]
Table 1 shows acid generators, basic compounds, and solvents 1 and 2 using the resins of the present invention (polymers 1 to 29) and comparative resins (polymers 30 to 39) prepared above as base resins. They were added in composition, mixed and dissolved, and then filtered through a Teflon (registered trademark) filter (pore size: 0.2 μm) to obtain the resist material (R-01 to 35) of the present invention and the resist material for comparison (R-36). To 46). In addition, all the solvents used what contained 0.01 mass% of KH-20 (Asahi Glass Co., Ltd. product) as surfactant.

In Table 1, the acid generators indicated by abbreviations are as follows.

In Table 1, the basic compounds and the solvents 1 and 2 indicated by abbreviations are as follows.
Base-1: 2-morpholinoethyl octanoate PGMEA: propylene glycol monomethyl ether acetate CyHO: cyclohexanone

Evaluation of Resist Material 1 Sensitivity Comparison [Examples 2-1 to 7 and Comparative Examples 2-1 to 5]
Of the resist materials (R-01 to 35) obtained in Example 1 and the resist materials (R-36 to 46) for comparative examples, the resist materials described in Table 2 below were used as antireflection films (Nissan Chemical Industries). A silicon wafer coated with ARC29A (78 nm, manufactured by Co., Ltd.) was spin-coated and heat-treated at 120 ° C. for 60 seconds to form a resist film having a thickness of 150 nm. This was exposed to an open frame using an ArF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.85), subjected to heat treatment (PEB) at 120 ° C. for 60 seconds, and then 2.38% by mass of tetramethyl. Paddle development was performed for 30 seconds using an aqueous ammonium hydroxide solution, and the minimum exposure (E ₀ ) at which the resist film thickness was zero was determined. It is considered that the smaller E ₀ is, the higher the sensitivity is, and the resist base resin is highly reactive.
Table 2 shows the evaluation results of each resist.

  From the results shown in Table 2, it is considered that the acid-eliminating ester type monomer having a spiro ring structure of the present invention is highly reactive. For example, comparing the results of Comparative Example 2-1 and Example 2-1, it can be confirmed that the spiro ring bond of Monomer 1 greatly contributes to the acid elimination reaction. Further, from the results of Comparative Example 2-2, Comparative Example 2-3, and Example 2-1, Monomer 1 in which the position of the spiro ring bond is adjacent to the acid elimination reaction point indicates that the position of the spiro ring bond is an acid elimination reaction. It is more reactive than Monomer 9 and Monomer 10 that are one carbon or two carbons away from the point, and it is confirmed that there is a difference in reactivity in the acid elimination reaction depending on the spiro ring bonding position. In addition, regarding the difference in reactivity slightly seen in the results of Comparative Example 2-2 and Comparative Example 2-3, Monomer 10 in which the spiro ring bond is located 1 carbon apart from the acid elimination reaction point on the six-membered ring. Then, the contribution of 1,3-diaxial interaction to the acid elimination reaction is considered, and therefore, it is considered that the reactivity is slightly higher than that of Monomer 9.

Evaluation of resist material 2 Pattern resolution performance comparison [Examples 3-1 to 35, Comparative examples 3-1 to 11]
The resist material (R-01 to 35) of the present invention and the comparative resist material (R-36 to 46) are applied onto a silicon wafer coated with an antireflection film (manufactured by Nissan Chemical Industries, Ltd., ARC29A, 90 nm). The film was spin-coated and heat-treated at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. On this resist film, a resist protective film material (SIOC-3, 50 nm, manufactured by Shin-Etsu Chemical Co., Ltd.) was spin-coated and heat-treated (90 ° C., 60 seconds), and this was applied to an ArF immersion excimer laser stepper (Co., Ltd.). Nikon, NA = 1.30) was used to transfer and expose a fixed pattern drawn on a 6% halftone phase difference mask, heat treatment (PEB) for 60 seconds, and 2.38 mass% tetra Paddle development was performed for 30 seconds using an aqueous solution of methylammonium hydroxide to form a line and space pattern. In PEB, a temperature optimized for each resist material was applied. The produced wafer with a pattern was observed with a sky SEM (scanning electron microscope), the line width was measured in a 40 nm 1: 1 line and space transfer pattern, and the dependency of the line width on the exposure amount was examined. The exposure amount at which a 40 nm line is formed is determined as the optimal exposure amount (mJ / cm ² ), then the exposure amount width within which the line width is within 40 nm ± 10% is obtained, and the exposure amount width is divided by the optimal exposure amount to obtain a percentage Displayed as the exposure margin. The larger the value, the smaller the dimensional change due to the exposure amount change, and the better the exposure margin. In order to obtain a measure of mask fidelity, the line width formed on the resist with respect to the mask line width is plotted at the optimum exposure amount, and the inclination is calculated by linear approximation, and this is used as a mask error enhancement factor (MEEF). It was. The smaller the MEEF value, the higher the mask fidelity and the better the effect of the mask pattern finish error, which is better. Further, in order to compare the roughness, the line width was measured at 100 points at equal intervals in a 40 nm 1: 1 line and space line length range of 2 μm. Next, 3σ values of these length measurement values were calculated and used as Line Width Roughness (LWR). The smaller the LWR value, the smaller the roughness and the better.
Table 3 shows the evaluation results of each resist material.

  From the results shown in Table 3, it was confirmed that the resist material of the present invention was excellent in resolution performance in ArF excimer laser exposure. For example, Comparative Example 3-1, Comparative Example 3-2, Comparative Example 3-3, Comparative Example 3-4 and Example 3-1, Example 3-2, Example 3-3, Example 3-4, Comparing the results of Example 3-5 and Example 3-6, the difference in resolution performance is caused by the presence or absence of the spiro ring structure and the spiro ring bonding position in the acid-eliminating monomer. It is confirmed that the resolution is further improved by combining with the acid generator of the invention.

Evaluation of Resist Material 3 PEB Temperature Dependency [Examples 4-1 to 3 and Comparative Examples 4-1 to 3]
Under the 40 nm 1: 1 line and space evaluation conditions of Examples 3-1 to 35 and Comparative Examples 3-1 to 11, the dependency of the line width on the optimum exposure amount on the PEB temperature was examined.
Of the resist materials (R-01 to 35) obtained in Example 1 and the resist materials for comparative examples (R-36 to 46), the resist materials listed in Table 4 were selected for each resist in Table 4. Change the PEB temperature in increments of 2 ° C within the optimum PEB temperature range of ± 4 ° C, plot the line width against the PEB temperature, perform the least square fitting of the linear approximation formula, and compare the slope (nm / ° C) did. The smaller the inclination, the smaller the PEB temperature dependency, which is preferable because the dimensional change caused by the difference in thermal history on the wafer surface is suppressed.
The evaluation results are shown in Table 4.

  From the results shown in Table 4, it was confirmed that the resist material of the present invention has small PEB temperature dependency.

Claims (6)

An acid-eliminating ester-type monomer having a spiro ring structure represented by the following general formula (1).

(In the formula, Z represents a monovalent group having a polymerizable double bond. X represents a divalent group which forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ² represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom or 1 to 1 carbon atom. 10 linear, branched or cyclic monovalent hydrocarbon groups, or R ³ and R ⁴ are bonded to each other and substituted or unsubstituted cyclopentane ring or cyclohexane ring together with the carbon atom to which they are bonded Represents a divalent group forming n. N represents 1 or 2.) An acid-eliminating ester type monomer having a spiro ring structure represented by the following general formula (2) or (3).

(In the formula, X represents a divalent group which forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trivalent group. Represents a fluoromethyl group, R ² represents a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ and R ⁴ each independently represents a hydrogen atom or carbon Represents a linear, branched or cyclic monovalent hydrocarbon group of 1 to 10, or R ³ and R ⁴ are bonded to each other and substituted or unsubstituted cyclopentane ring together with the carbon atom to which they are bonded; Or a divalent group that forms a cyclohexane ring, R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, and p represents 0 or 1.) It contains a repeating unit obtained from an acid-eliminating ester-type monomer having a spiro ring structure according to claim 1 or 2 represented by the following general formulas (1a) to (3a). High molecular compound.

(In the formula, Za is derived from a monovalent group Z having a polymerizable double bond, and represents a trivalent group generated by polymerization. X represents a substituted or unsubstituted cyclopentane ring, cyclohexane together with the carbon atom to which it is bonded. R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R ² represents a hydrogen atom, or a straight chain having 1 to 10 carbon atoms. Represents a branched or cyclic monovalent hydrocarbon group, R ³ and R ⁴ each independently represent a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, Or R ³ and R ⁴ represent a divalent group which forms a substituted or unsubstituted cyclopentane ring or cyclohexane ring together with the carbon atom to which they are bonded, and R ⁵ represents a hydrogen atom or a methyl group N represents 1 or 2. p It represents 0 or 1.)   A resist material comprising the polymer compound according to claim 3 as a base resin and a compound that generates an acid in response to actinic rays or radiation. The resist material according to claim 4, wherein the compound that generates an acid in response to actinic rays or radiation is a sulfonium salt compound represented by the following general formula (4).

(Wherein R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, each of which may contain a hetero atom, carbon C 1 -C 10 alkoxy group, or, .R ¹⁰ indicating a halogen atom .R ⁹ is carbon atoms which may contain a heteroatom 1-30 linear, monovalent hydrocarbon group branched or cyclic Represents a hydrogen atom or a trifluoromethyl group.)   A step of applying the resist material according to claim 4 or 5 on a substrate, a step of exposing to high energy rays or an electron beam through a photomask after heat treatment, a heat treatment if necessary, and a developer And a step of developing using a pattern.