TWI438189B - Acid-labile ester monomer having spirocyclic structure, polymer, resist composition, and patterning process - Google Patents

Description

Acid dissociable ester type monomer having a spiro ring structure, polymer compound, photoresist material and pattern forming method

The present invention relates to an acid-dissociable ester type monomer (monomer, that is, a polymerizable compound) having a spiro ring structure which can be used as a raw material of a functional material. The acid dissociable ester type monomer having the spiro ring structure has excellent transparency for radiation having a wavelength of 500 nm or less, particularly a wavelength of 300 nm or less, such as KrF laser light, ArF laser light, F ₂ laser light, and The dissociation reaction in the presence of an acid produces a carboxylic acid, and is very useful as a raw material monomer for a polymer of a base resin for producing a radiation-sensitive photoresist material excellent in resolution and susceptibility.

Furthermore, the present invention relates to a polymer (polymer compound) having a repeating unit derived from the acid dissociable ester type monomer having a spiro structure, a photoresist material containing the polymer compound, and the use of the photoresist The method of forming the pattern of the material.

In recent years, with the increase in the integration and speed of LSI, and the refinement of the pattern pattern, the far-ultraviolet lithography is expected to be regarded as the next-generation microfabrication technology. Among them, the photolithography technology using KrF laser light, ArF laser light, and F ₂ laser light as a light source is an indispensable technology in ultra-fine processing of 0.3 μm or less, and its realization is urgently desired. The base resin of the photoresist materials uses various alkali-soluble resins.

The base resin which is a KrF photoresist material is in fact a polyhydroxystyrene resin. As a base resin for an ArF photoresist material, a resin which uses a poly(meth)acrylic resin or an orthoquinone or the like as a polymerization unit using a carboxyl group as an alkali-soluble group has been examined, and among them, poly(methyl) Acrylates have been provided for practical use due to their ease of polymerization.

As for the poly(meth) acrylate, the methyl adamantyl (meth) acrylate exemplified in JP-A-9-90637 is proposed as a repeating unit having an acid labyrinth (acid-unstable unit). And a combination of a (meth) acrylate having a lactone ring as a repeating unit having an adhesive group. Further, an acid labile group having an alkylcycloalkyl type tertiary alkyl group is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-73173. Further, an acid unstable group having an exo isomer of an alkylbicyclo[2.2.1]heptanol-tertiary alkyl group is described in JP-A-2000-327633. Since this has high acid dissociation property and low activation energy of acid dissociation, high resolution and low exposure post-baking (PEB) dependence can be obtained. Further, the (meth) acrylate having the borneol alkanolide or the oxabornane lactone listed in the patent document 4: JP-A-2000-26446, JP-A-2000-159758 The unit serves as a dense base for enhancing etching resistance. By such discussion, the resolution of the ArF photoresist is greatly improved. In addition to the acid-unstable base unit and the lactone unit, a repeating unit having a hydroxyl group such as 3-hydroxy-1-adamantyl (meth)acrylate is also added as a control in the patent document 6: JP-A-2003-113213. A unit of a ternary polymer derived from a photoacid generator which is diffused by an acid generated by exposure in a photoresist film is used as a base resin of a photoresist material.

In the acid catalyst dissociation reaction in the photoresist film, when the dissociation reactivity of the acid unstable unit is high, since the dissociation reaction can also be carried out at a low temperature, the post-exposure bake (PEB) temperature can be lowered, and the PEB process can be suppressed. The thermal diffusion of acid. Further, by imparting a moderate fat solubility to the acid-unstable unit, the exposure-dependent contrast ratio to the dissolution rate of the developing solution can be improved. The extremely high contrast of low acid diffusivity contributes to the improvement of resolution, that is, the enlargement of various process latitudes such as exposure margin (EL) or depth of focus (DOF) in the fine pattern, and mask faith. Moreover, it is also possible to effectively minimize the roughness of the pattern (line edge roughness or line width roughness in the line and space pattern, circuitability in the overall pattern, etc.). Further, the high-dissociation acid-stable unstable unit can reduce the PEB temperature dependence of the pattern size, and it is expected to suppress the dimensional deviation due to a small difference in thermal history between different positions on the wafer surface. From the above, a highly dissociated reactive acid unstable unit having moderate fat solubility is strongly required.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-9-90637

[Patent Document 2] Japanese Patent Publication No. 9-73173

[Patent Document 3] JP-A-2000-327633

[Patent Document 4] JP-A-2000-26446

[Patent Document 5] JP-A-2000-159758

[Patent Document 6] JP-A-2003-113213

SUMMARY OF THE INVENTION An object of the present invention is to provide an acid dissociable ester type monomer having a spiro ring structure for obtaining a base resin of a photoresist material having high resolution and low temperature dependence of PEB, using an acid dissociation property having a spiro ring structure A polymer compound of an ester type monomer, a photoresist material containing the polymer compound as a base resin, and a pattern forming method using the photoresist material.

The inventors of the present invention have conducted various investigations on photo-resistance materials which achieve high resolution and low PEB temperature dependence in lithography etching using a high-energy line such as ArF excimer laser light as a light source, and have found that a specific snail has a specific snail. The acid dissociable ester type monomer of the ring structure is extremely useful as a monomer for a photoresist base resin.

In other words, the present inventors have found that an acid dissociable ester type monomer having a spiro ring structure represented by the following general formula (1) can be easily produced, and an acid dissociable ester type monomer having a spiro ring structure can be used. The obtained polymer compound has high contrast as a photoresist material of a base resin, and the polymer compound is extremely effective as a photoresist material in precision microfabrication, and thus the present invention has been completed.

Accordingly, the present invention provides an acid-dissociable ester type monomer having a spiro ring structure represented by the following general formula (1) or the following general formula (2) or (3):

(wherein Z represents a valence group having a polymerizable double bond, and X represents a substituted or unsubstituted cyclopentane ring, a cyclohexane ring or an original norbornane ring together with the carbon atom to which it is bonded. a valent group, 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 a linear or branched carbon number of 1 to 10. a monovalent or cyclic monovalent hydrocarbon group, or R ³ and R ⁴ represent a bond between them and a carbon atom to which they are bonded to form a substituted or unsubstituted cyclopentane ring or a divalent group of a cyclohexane ring, n Indicates 1 or 2),

(wherein X represents a divalent group of a substituted or unsubstituted cyclopentane ring, a cyclohexane ring or an original norbornane ring together with a carbon atom to which it is bonded, and R ¹ represents a hydrogen atom, a fluorine atom, Methyl or trifluoromethyl, 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 a carbon number of 1 to 10. a linear, branched or cyclic monovalent hydrocarbon group, or R ³ and R ⁴ represent a mutual bond with a carbon atom to which they are bonded to form a substituted or unsubstituted cyclopentane ring or a cyclohexane ring. A divalent group, R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, and p represents 0 or 1).

Further, the present invention provides a polymer compound comprising a repeating unit obtained by the above-described acid-dissociable ester type monomer having a spiro ring structure represented by the following general formulae (1a) to (3a):

(wherein, Za represents a trivalent group derived from a valence group Z having a polymerizable double bond and produced by polymerization, and X represents a substituted or unsubstituted cyclopentane together with a carbon atom to which it is bonded a divalent group of a ring, a cyclohexane ring or an ornidyl ring, 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 or branched carbon number of 1 to 10. a 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 mutual bond and the like. The bonded carbon atoms together form a divalent group of a substituted or unsubstituted cyclopentane ring or a cyclohexane ring, R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, and p represents 0 or 1) .

Furthermore, the present invention provides a photoresist material comprising the above polymer compound as a base resin and a compound which is induced by active light or radiation to generate an acid.

In this case, the above-mentioned compound which is induced by active light or radiation to generate an acid is an onium salt compound represented by the following formula (4):

(wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom, and a carbon number of 1 to 10; The alkoxy group or a halogen atom, and R ⁹ represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, and R ¹⁰ represents a hydrogen atom or a trifluoromethyl group.

Moreover, the present invention provides a pattern forming method, which comprises the steps of applying the photoresist material on a substrate, heating the film through a mask with a high energy line or an electron beam, and optionally heating. After that, use the steps of imaging liquid imaging.

The acid dissociable ester type monomer having a spiro ring structure of the present invention can be used as a raw material of a functional material, etc., and has excellent transparency for radiation having a wavelength of 500 nm or less, particularly a wavelength of 300 nm or less, in an acid dissociation reaction. It has extremely high reactivity and is extremely useful as a monomer for producing a base resin of a radiation-sensitive photoresist material having good resolution. The polymer compound of the present invention can be used as a base resin for a radiation-sensitive photoresist material. . In addition, the photoresist material of the present invention has high resolution, exhibits excellent performance with respect to exposure margin or depth of focus, mask faith, and has the advantage of having a small roughness. Furthermore, the PEB temperature dependence of the pattern size is small, which can effectively improve the yield of actual production.

The invention is described in detail below.

Further, in the following chemical formula, the present invention has a chemical structure in the presence of an enantiomer or a diastereomer, and any chemical formula is used in any case unless otherwise specified. Represents all of these stereoisomers. Further, the stereoisomers may be used singly or as a mixture.

The acid dissociable ester type single system having a spiro ring structure of the present invention is represented by the following formula (1):

(wherein Z represents a valence group having a polymerizable double bond, and X represents a substituted or unsubstituted cyclopentane ring, a cyclohexane ring or an original norbornane ring together with the carbon atom to which it is bonded. a valent group, 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 a linear or branched carbon number of 1 to 10. a monovalent or cyclic monovalent hydrocarbon group, or R ³ and R ⁴ represent a bond between them and a carbon atom to which they are bonded to form a substituted or unsubstituted cyclopentane ring or a divalent group of a cyclohexane ring, n Indicates 1 or 2), and Z represents a valence group having a polymerizable double bond. Specific examples of Z are vinyl, ethynyl, 1-propenyl, isopropenyl, 3,3,3-trifluoro-2-propenyl, allyl, 1,3-butadienyl, 2-methyl a group containing a plurality of bonds, such as a 1-propenyl group, a 5-norbornene-2-yl group, a tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-8-en-3-yl group, Or containing acrylate, methacrylate, α-trifluoromethacrylate, vinyl ether, allyl ether, raw borneol, tricyclo [5.2.1.0 ^2,6 ] decane, tetracyclic [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecene or the like as a partial structure group, for example, acryloxymethyl, methacryloxymethyl, α-trifluoromethylpropenylmethyl, 1 -(Protonium oxy)ethyl, 1-(methacryloxy)ethyl, 1-(α-trifluoromethylpropenyloxy)ethyl, 2-(acryloxy)ethyl , 2-(methacryloxy)ethyl, 2-(α-trifluoromethylpropenyloxy)ethyl, 3-(acryloxy)propyl, 3-(methacryloxy) Propyl, 3-(α-trifluoromethylpropenyloxy)propyl, 4-(acryloxy)butyl, 4-(methacryloxy)butyl, 3-(α -trifluoromethylpropenyloxy)butyl, 2-vinyloxyethyl , 2-vinyloxypropyl, 3-vinyloxypropyl, 2-allyloxyethyl, 2-allyloxypropyl, 3-allyloxypropyl, 5 - norbornene-2-carbonyloxymethyl, 2-(5-formoprene-2-carbonyloxy)ethyl, 5-norbornene-2-ylmethyl, 2-(5-original borneol Alken-2-yl)ethyl, 5-propenyloxy-nebornane-2-carbonyloxymethyl, 2-(5-acryloxy-norbornane-2-carbonyloxy)ethyl, 5 - propylene decoxy oxabornane-2-ylmethyl, 2-(5-propenyloxy orthoen-2-yl)ethyl, 5-methylpropenyloxy ornithyl-2-carbonyl Oxymethyl, 2-(5-methylpropenyloxybornane-2-carbonyloxy)ethyl, 5-methylpropenyloxy ornithyl-2-ylmethyl, 2-( 5-methylpropenyloxy-nebornane-2-yl)ethyl, 5-(α-trifluoromethylpropenyloxy)-bornane-2-carbonyloxymethyl, 2-(5- (α-Trifluoromethylpropenyloxy)-formane-2-carbonyloxy)ethyl, 5-(α-trifluoromethylpropenyloxy)-bornane-2-ylmethyl, 2 -(5-(α-trifluoromethylpropenyloxy)-formane-2-yl)ethyl, (tricyclo[5.2.1.0 ^2,6 ]癸-8 - alkene-4-carbonyloxy)methyl, 2-(tricyclo[5.2.1.0 ^2,6 ]non-8-ene-4-carbonyloxy)ethyl, (tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-8-en-3-carbonyloxy)methyl, 2-(tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-8-ene-3 -carbonyloxy)ethyl and the like.

The best of these are vinyl, isopropenyl, 3,3,3-trifluoro-2-propenyl or 5-orthoen-2-yl, tetracyclic [4.4.0.1 ^2,5 .1 ^{7 , 10} ] dodec-8-en-3-yl, in which case the acid dissociable ester type single system having a spiro structure is represented by the following general formulae (2), (3):

(wherein X represents a divalent group of a substituted or unsubstituted cyclopentane ring, a cyclohexane ring or an original norbornane ring together with a carbon atom to which it is bonded, and R ¹ represents a hydrogen atom, a fluorine atom, Methyl or trifluoromethyl, 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 a carbon number of 1 to 10. a linear, branched or cyclic monovalent hydrocarbon group, or R ³ and R ⁴ represent a mutual bond with a carbon atom to which they are bonded to form a substituted or unsubstituted cyclopentane ring or a cyclohexane ring. A divalent group, R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, and p represents 0 or 1).

X together with the carbon atoms to which they are bonded represents a divalent group which forms a substituted or unsubstituted cyclopentane ring, a cyclohexane ring, or a norbornane ring. That is, the following parts are constructed:

(wherein the dotted line represents a bond), which is a substituted or unsubstituted cyclopentane ring, a cyclohexane ring or an ornidyl ring, that is, a ring structure represented by the following partial structure:

(wherein the dotted line represents a bond), or may be a condensed ring containing the same. The single or plural hydrogen atoms in the structures may be substituted by an alkyl group having 1 to 3 carbon atoms, a hydroxyl group (-OH) or a halogen atom, and a single or plural methyl group (-CH ₂ -) in the structures. It may also be substituted with a hetero atom such as a carbonyl [-(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 the linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms may be exemplified by methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group and third group. Butyl, third amyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentylmethyl, ring Amyl ethyl, cyclopentylbutyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, methylcyclohexylmethyl, ethylcyclohexylmethyl, ethylcyclohexylethyl, Bicyclo [2.2.1] heptyl, bicyclo [2.2.1] heptylmethyl, bicyclo [2.2.1] heptylethyl, bicyclo [2.2.1] heptyl butyl, methyl bicyclo [2.2.1] Heptylmethyl, ethylbicyclo[2.2.1]heptylmethyl, ethylbicyclo[2.2.1]heptylethyl, bicyclo[2.2.2]octyl, bicyclo[2.2.2]octylmethyl Bicyclo[2.2.2]octylethyl, bicyclo[2.2.2]octylbutyl, methylbicyclo[2.2.2]octylmethyl, ethylbicyclo[2.2.2]octylmethyl, B Bicyclo[2.2.2]octylethyl, tricyclo[5.2.1.0 ^2,6 ]decyl, tricyclo[5.2.1.0 ^2,6 ]nonylmethyl, tricyclo[5.2.1.0 ^2,6 ] Mercaptoethyl, three [5.2.1.0 ^2,6] dec-methylbutyl, methyl-tricyclo [5.2.1.0 ^2,6] decyl methyl, ethyl tricyclo [5.2.1.0 ^2,6] decyl methyl, ethyl trimethyl Ring [5.2.1.0 ^2,6 ]decylethyl, adamantyl, adamantylmethyl, adamantylethyl, adamantylbutyl, methyladamantylmethyl, ethyladamantyl Ethyl, ethyladamantylethyl, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecyl, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecyl Base, tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] dodecylethyl, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodecyl butyl, tetracyclo[4.4 .0.1 ^2,5 .1 ^7,10 ]dodecylmethyl, ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecylmethyl, ethyltetracycline [4.4.0.1 ^2,5 .1 ^7,10 ] A linear, branched or cyclic monovalent hydrocarbon group such as dodecylethyl, phenyl, tolyl or naphthyl. Also, the groups may contain unsaturated bonds. Among these, R ^{2 is} 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. Specific examples of the case where R ³ and R ⁴ are a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms are exemplified as a linear, branched or cyclic ring having a carbon number of 1 to 10 and R ^{2 .} Specific examples of the monovalent hydrocarbon group are the same. The best among these is a hydrogen atom and a methyl group. Further, R ³ and R ⁴ may be bonded to each other to form a substituted or unsubstituted cyclopentane ring or a cyclohexane ring together with the carbon atom to which they are bonded, or may be a condensed ring containing the same. The single or plural hydrogen atoms in the structures may also be substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxyl group (-OH) or a halogen atom, and a single or plural methyl group (-CH ₂ - in the structures). It can also be substituted with a hetero atom such as a carbonyl group or an oxygen atom (-O-).

The acid-dissociable ester type monomer having a spiro ring structure of the present invention can be specifically exemplified as follows, but is not limited thereto.

(wherein R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group).

(wherein R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group).

(wherein R ⁵ represents a hydrogen atom or a methyl group, and p represents 0 or 1).

(wherein R ⁵ represents a hydrogen atom or a methyl group, and p represents 0 or 1).

The design concept of the acid dissociable ester type monomer having a spiro ring structure represented by the general formula (1) of the present invention will be described.

The acid dissociable ester type single system having a spiro ring structure of the present invention is used as a repeating unit of a polymer compound, and the polymer compound is used as a base material resin of a radiation-sensitive photoresist material to be described later. In the acid catalyst dissociation reaction in the photoresist film, the dissociation reaction of the olefin from the acid dissociable ester is initiated by an acid catalyst to form a carboxylic acid (this causes solubility in a developing solution for realizing the solubility contrast of the photoresist). Variety). An acid labile group having an alkylcycloalkyl type tertiary alkyl group is disclosed in JP-A-9-73173, and a spiro ring structure is exemplified, but there is no description about the position or pattern of substitution. . The acid dissociable ester type monomer having a spiro ring structure represented by the general formulae (1), (2), and (3) of the present invention is configured by a specific position of the spiro ring structure to improve performance. The high reactivity is achieved in the acid catalyst dissociation reaction.

When the acid catalyst dissociation reaction in the photoresist film, a carbon cation is generated on the carbon atom bonded to the polymerizable ester, and the olefin is produced by dissociating the proton from the generated carbon cation. The more stable the carbon cation formed in the reaction, the higher the activation energy of the acid catalyst dissociation reaction, and the higher the reactivity. The most characteristic feature of the acid dissociable ester type monomer having a spiro ring structure of the present invention is that the bonding carbon atom of the polymerizable ester is directly bonded to the quaternary carbon atom of the spiro ring, and it is considered that high reactivity is achieved based on the following three points. .

1) a carbon atom adjacent to a carbon atom of a polymerizable ester (hereinafter referred to as a carbon atom at the 1st position), that is, a carbon atom bonded to X (= snail carbon atom, hereinafter referred to as second position) The alkyl group having a cyclopentane ring, a cyclohexane ring, or an ornidyl ring is substituted on the carbon atom, and it is considered that the first place is due to the electron supply effect (Electron donating effect) of the alkyl group. The cation on the carbon atom is stabilized. Further, the carbon atom (hereinafter referred to as the carbon atom at the 2'-position) to which R ³ and R ⁴ adjacent to the 1-position carbon atom are bonded may have an alkyl group substitution. In this case, the first carbon can be expected. The cation on the atom is stabilized.

2) It is considered that the substitution of the alkyl group at the 2nd carbon atom (which also contains a carbon atom at the 2' position when substituted at the 2nd position) causes the surrounding carbon atom to become a sterically hindered state due to cation formation and Steric hindrance caused by subsequent olefin formation is digested, making the energy of the generating system more stable and making the reaction easier. When a specific example showing a large steric hindrance is listed, the ¹³ C-NMR signal broadening which suppresses the balance between the ligands at room temperature is observed in detail later in the examples.

3) It is considered that the carbocation intermediate formed on the first carbon atom causes a transfer reaction (1,2-transalkylation) of the alkyl group at the 2nd (or 2'-position), and it is more stable. In the case of carbocations, the balance between the carbocations contributes to the stabilization of the cations and reduces the activation energy of the reaction. When a specific example is enumerated, it is described in detail later in the examples that a plurality of olefin formations are observed as a result of obtaining a cation transfer as seen in the following chemical reaction formula in the case of a 6-methylspiro[4.5]decyl ester compound.

In the acid-dissociable ester type monomer having a spiro ring structure represented by the formula (1) of the present invention, an appropriate structure can be selected to adjust the dissociation reactivity. For example, depending on the type of the bonded alicyclic ring of the polymerizable ester (n is 1 or 2) and the type of the substituent R ² bonded to the 1st carbon atom (which is a hydrogen atom or a monovalent hydrocarbon group, at one price) The choice of a hydrocarbon group for its kind, etc., can be achieved by adjusting the moderate dissociation reactivity in the photoresist film. Further, the acid diffusion distance in the photoresist film can be appropriately adjusted by selecting the alicyclic structure bonded to the second spiro carbon atom or the type of R ³ and R ⁴ .

A method for producing an acid-dissociable ester type monomer having a spiro structure represented by the general formulae (1), (2), and (3) of the present invention will be described.

A typical but non-limiting example of the acid dissociable ester type monomer having a spiro ring structure represented by the general formulae (1), (2), and (3) of the present invention can be synthesized by the deuteration reaction of the corresponding alcohol compound. . The corresponding alcohol compound can be synthesized by alkylation of a ketone compound (or reduction when R ² is a hydrogen atom).

(wherein Z represents a valence group having a polymerizable double bond, and X represents a substituted or unsubstituted cyclopentane ring, a cyclohexane ring or an original norbornane ring together with the carbon atom to which it is bonded. a valent group, 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 of which 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 mutual bond with a carbon atom bonded thereto to form a substituted or unsubstituted a substituted cyclopentane ring or a divalent group of a cyclohexane ring, R ⁵ represents a hydrogen atom, or a methyl group, n represents 1 or 2, p represents 0 or 1), and a method of producing a conventional ester can be used for the esterification reaction. For example, a reaction with a hydrating agent, a reaction with a carboxylic acid, and a transesterification reaction. The reaction using a oxime agent is preferably selected from chlorine-based solvents such as dichloromethane, chloroform and trichloroethylene, and hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene, dibutyl ether and Ethers such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, nitriles such as acetonitrile, ketones such as acetone and 2-butanone, ethyl acetate and acetic acid An ester such as n-butyl ester, a single aprotic polar solvent such as N,N-dimethylformamide, dimethyl sulfonium or trimethylamine hexamethylamine or a mixture of two or more solvents. Adding the alcohol compound of the raw material sequentially or simultaneously, and propylene fluorene chloride, methacrylic acid chloro, propylene hydrazine bromine, methacryl hydrazine bromine, α-trifluoromethyl propylene fluorene chloride, bicyclo [2.2.1] g-5 -ene-2-carboxyindole chloride, bicyclo[2.2.1]hept-5-ene-2-methyl-2-carboxyindole chloride, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane a fluorene compound such as 8-ene-3-carboxyindole chloride or tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane-8-en-3-methyl-3-carboxyindole chloride, or Acrylic anhydride, methacrylic anhydride, α-trifluoromethylacrylic anhydride, bicyclo [2.2.1] hept-5-ene-2-carboxylic anhydride, bicyclo [2.2.1] g -5-en-2-methyl-2-carboxylic anhydride, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane-8-ene-3-carboxylic anhydride, tetracyclo[4.4.0.1 ^{2 ,5} .1 ^7,10 ]dodecane-8-en-3-methyl-3-carboxylic anhydride, mixed acid anhydride of trifluoroacetic acid, mixed acid anhydride of trifluoroacetic acid methacrylate, α-trifluoromethacrylic acid Fluorine acetic 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-ene-2-methyl-2-carboxylic acid trifluoro Acetic acid mixed anhydride, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodecane-8-en-3-carboxylic acid trifluoroacetic acid mixed anhydride, tetracyclo[4.4.0.1 ^2,5 .1 ^{7, 10} ] Dodecane-8-en-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 methacrylate Acid mixed acid anhydride, bicyclo[2.2.1]hept-5-ene-2-carboxylic acid pivalic acid mixed acid anhydride, bicyclo[2.2.1]hept-5-ene-2-methyl-2-carboxylic acid pivalic acid Mixed anhydride, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodecane-8-ene-3-carboxylic acid pivalic acid mixed anhydride, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 Dodecane-8-en-3-methyl-3-carboxylic acid pivalic acid mixed anhydride, p-nitrobenzene acrylate Acid mixed acid anhydride, mixed acid anhydride of p-nitrobenzoic acid methacrylate, mixed acid anhydride of ethyl acrylate carbonate, mixed acid anhydride of ethyl methacrylate, p-nitrophenyl acrylate, p-nitrophenyl methacrylate, α-Trifluoromethyl methacrylate p-alkenyl phenyl ester, acrylic acid p-toluene sulfonic acid mixed acid anhydride, methacrylic acid p-toluene sulfonic acid mixed acid anhydride, α-trifluoromethacrylic acid p-toluene sulfonic acid mixed acid anhydride, double ring [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 p-toluenesulfonic acid mixture Anhydride, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodecane-8-en-3-carboxylic acid p-toluenesulfonic acid mixed anhydride, tetracyclo[4.4.0.1 ^2,5 .1 ^{7, 10} ] a deuterated agent such as dodecane-8-en-3-methyl-3-carboxylic acid p-toluenesulfonic acid mixed acid anhydride or the like, and triethylamine, diisopropylethylamine, N, N a base such as dimethylaniline, pyridine or 4-dimethylaminopyridine, which is reacted. In the reaction using a hydrating agent such as an acid anhydride, an inorganic acid selected from the group consisting of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid may be used instead of the base. The reaction is carried out under an acid catalyst such as an organic acid. The temperature of the oximation reaction may be appropriately selected depending on the type of the hydrating agent to be used and the reaction conditions, but it is usually preferably from -50 ° C to the boiling point of the solvent, more preferably from about -20 ° C to room temperature. The amount of the oximation agent used is related to the structure, but the amount of the alcohol compound 1 relative to the raw material is 1 to 40 moles, preferably 1 to 5 moles.

The reaction with a carboxylic acid is the corresponding carboxylic acid, that is, acrylic acid, methacrylic acid, α-trifluoromethacrylic acid, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid, bicyclo [2.2.1 Gh-5-en-2-methyl-2-carboxylic acid, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane-8-ene-3-carboxylic acid, tetracyclo[4.4. The dehydration reaction of any of 0.1 ^2,5 .1 ^7,10 ]dodecane-8-en-3-methyl-3-carboxylic acid with a starting alcohol compound is usually carried out under an acid catalyst. The amount of the carboxylic acid used is related to the structure, but the molar amount of the alcohol compound 1 is from 1 to 40 moles, preferably from 1 to 5 moles. Examples of the acid catalyst can be exemplified by 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, which may be used alone or in combination. use. The amount of the acid catalyst used is 0.001 to 1 mol, preferably 0.01 to 0.05 mol, based on the amount of the alcohol compound 1 of the raw material. The solvent may be exemplified by the same reaction as the above-mentioned esterification agent, but it is usually preferably from -50 ° C to the boiling point of the solvent. A solvent containing a hydrocarbon such as hexane, heptane, benzene, toluene, xylene or cumene may be used, and the water produced by azeotropy may be excluded from the system to carry out the reaction. In this case, water may be distilled off while refluxing at the boiling point of the solvent under normal pressure, but the distillation of water may be carried out at a temperature lower than the boiling point under reduced pressure.

In the transesterification reaction, the corresponding carboxylic acid ester is obtained in the presence of a catalyst, that is, acrylate, methacrylate, α-trifluoromethacrylate, bicyclo [2.2.1] hept-5-ene. 2-carboxylate, bicyclo[2.2.1]hept-5-en-2-methyl-2-carboxylate, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]癸-8-ene Any one of a 3-carboxylate or a tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]non-8-en-3-methyl-3-carboxylate is reacted with a starting alcohol compound by removing The alcohol produced is implemented. The carboxylic acid ester to be used is preferably a primary alkyl ester, and is preferably a methyl ester, an ethyl ester or a n-propyl ester in terms of price and ease of reaction. The amount of the carboxylic acid ester used is related to the structure, but it is 1 to 40 moles, preferably 1 to 5 moles, per mole of the alcohol compound 1 of the raw material. Examples of the catalyst 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 and sodium ethoxide; Bases such as potassium butoxide, 4-dimethylaminopyridine, sodium cyanate, potassium cyanate, sodium acetate, potassium acetate, calcium acetate, tin acetate, aluminum acetate, aluminum acetoxyacetate, alumina, etc. Classes, aluminum trichloride, acetyl chloride, isopropyl alumina, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin Lewis acids such as methoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) oxide, titanium (IV) oxide, titanium isopropoxide (IV), and titanium oxide (IV). These may be used alone or in combination. The amount of the catalyst used is 0.001 to 20 moles, preferably 0.01 to 0.05 moles of the catalyst amount relative to the alcohol compound 1 of the raw material. The reaction can be carried out in the absence of a solvent (the carboxylic acid ester itself of the reaction reagent can also be used as a solvent), since it is not necessary to carry out subsequent concentration and recovery of the solvent, etc., but in order to prevent the polymerization of the target or the reaction reagent, The solvent can be used in an auxiliary manner. In this case, it is preferred to use a hydrocarbon such as hexane, heptane, benzene, toluene, xylene or cumene alone or in combination, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether. An ether such as tetrahydrofuran or 1,4-dioxane. The reaction temperature is selected according to the kind of the carboxylic acid ester used and the reaction conditions, but is usually carried out under heating, and the low-boiling alcohol produced in the transesterification reaction, that is, methanol, ethanol, 1-propanol A good result can be obtained by carrying out the reaction in the vicinity of the same boiling point and distilling off the produced alcohol. The distillation of the alcohol can also be carried out under reduced pressure and at a temperature lower than the boiling point.

The alcohol compound of the above deuterated raw material can be synthesized by an addition reaction of an organometallic reagent to a corresponding ketone compound or a reduction reaction of a corresponding ketone compound. The organometallic reagent used in the addition reaction is exemplified by an organolithium reagent, an organic sodium reagent, an organic potassium reagent, an organomagnesium reagent (for example, a Grignard reagent), an organozinc reagent, an organotin reagent, an organoboron reagent, an organic hydrazine reagent, and the like. Among them, the organolithium reagent and the Grignard reagent are the best. As the reaction solvent, it is preferred to use an ether such as dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or 1,4-dioxane alone or in combination, hexane or heptane. Hydrocarbons such as benzene, toluene, xylene and cumene. The reducing agent used in the reduction reaction is exemplified by a metal hydride such as sodium hydride, potassium hydride, calcium hydride, aluminum hydride, borane or diisobutylaluminum hydride, a metal hydrogen hydride such as sodium borohydride or lithium aluminum hydride or the like. Alkyl, alkoxy derivative. The reaction solvent is preferably an alcohol such as water, methanol, ethanol or isopropanol, alone or in combination, in addition to those exemplified in the addition reaction of the organometallic reagent.

The monomer and the synthetic intermediate of the present invention can be purified and used according to usual methods such as distillation, crystallization, recrystallization, chromatography, etc., as needed.

The polymer compound of the present invention is characterized by containing a polymer compound having a repeating unit obtained from an acid-dissociable ester type monomer having a spiro ring structure represented by the following general formulae (1a) to (3a).

(wherein, Za represents a trivalent group derived from a valence group Z having a polymerizable double bond and produced by polymerization, and X represents a substituted or unsubstituted cyclopentane together with a carbon atom to which it is bonded a divalent group of a ring, a cyclohexane ring or an ornidyl ring, 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 or branched carbon number of 1 to 10. a 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 mutual bond and the like. The bonded carbon atoms together form a divalent group of a substituted or unsubstituted cyclopentane ring or a cyclohexane ring, R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, and p represents 0 or 1, Further, specific examples of X and R ² to R ^{4 are} as described above.

In addition to the above repeating unit, the polymer compound of the present invention may contain any one or more of repeating units represented by the following general formulae (5a) to (8a).

(In the formula, Za is the same as above, R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydroxyl group, Rx represents an acid labile group, Ry represents a substituent having a lactone structure, and Rz represents a hydrogen atom and contains a carbon number of 1~ a fluoroalkyl group of 15 or a substituent of a fluoroalcohol having 1 to 15 carbon atoms).

Wherein, Za is derived from a valence group Z having a polymerizable double bond as described above, and the Z system is as described above, and specific examples thereof are as described above, but Z is preferably a vinyl group, an isopropenyl group, or a 3,3,3- Trifluoro-2-propenyl or 5-norbornene-2-yl, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]non-8-en-3-yl. According to this, for example

It can be expressed by the following formula:

(wherein R ¹ , R ⁵ and p are as defined above).

The polymer containing the repeating unit represented by the above formula (5a) is decomposed by the action of an acid to produce a carboxylic acid, so that the polymer becomes alkali-soluble. As the acid-labile group Rx, various kinds may be used, and specific examples thereof include a group represented by the following general formulae (L1) to (L4), a carbon number of 4 to 20, preferably 4 to 15 tertiary alkyl groups, each of which The alkyl group is a trialkylalkylene group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

Among them, the broken line indicates a keying key (the same applies hereinafter). 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, and specific examples thereof include a methyl group, an ethyl group and a propyl group. , isopropyl, n-butyl, t-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl, borneol, tricyclodecyl, tetracyclododecane Base, adamantyl and the like. R ^L03 represents a monovalent hydrocarbon group having a carbon number of 1 to 18, preferably 1 to 10, which may have a hetero atom such as an oxygen atom, and may be exemplified by a linear, branched or cyclic alkyl group, and a part of the hydrogen atom. The substitution with a hydroxyl group, an alkoxy group, an oxo group, an amine group, an alkylamine group or the like can be specifically exemplified by the following substituted alkyl group and the like:

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 or oxygen atom to which they are bonded, and R ^L01 , R related to the formation of the ring when forming a ring. ^L02 and R ^L03 each represent a linear or branched alkyl group having 1 to 18 carbon atoms, preferably 1 to 10.

R ^L04 is a carbon number of 4 to 20, preferably 4 to 15 of a tertiary alkyl group, and each alkyl group represents a trialkylsulfonyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or The above formula (L1) represents a group, and the tertiary alkyl group can be specifically exemplified by a third butyl group, a third pentyl group, a 1,1-diethylpropyl group, a 2-cyclopentylpropan-2-yl group, 2-cyclohexylpropan-2-yl, 2-(bicyclo[2.2.1]hept-2-yl)propan-2-yl, 2-(adamantan-1-yl)propan-2-yl, 1-B Cyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl , 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, etc., and the trialkyldecyl group is specifically exemplified by trimethyldecyl, triethyldecyl, dimethyl- The third butyl fluorenyl group and the like, and the oxoalkyl group can be specifically exemplified by 3-oxocyclohexyl group, 4-methyl-2-oxooxetan-4-yl group, 5-methyl-2- Oxo oxacyclo-5-yl and the like. y is an integer from 0 to 6.

R ^L05 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or a substituted aryl group having 6 to 20 carbon atoms, and the alkyl group which may be substituted may be specifically exemplified as a methyl group. , linear, branched, etc., such as ethyl, propyl, isopropyl, n-butyl, t-butyl, tert-butyl, third pentyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl Or a cyclic alkyl group, one of which is substituted with a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an oxo group, an amine group, an alkylamino group, a cyano group, a decyl group, an alkylthio group, As the sulfo group or the like, the aryl group which may be substituted may be specifically exemplified by a phenyl group, a methylphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group or the like. In the formula (L3), m is 0 or 1, and n is any one of 0, 1, 2, and 3, and is a number satisfying 2m+n=2 or 3.

R ^L06 represents a linear, branched or cyclic alkyl group having a carbon number of 1 to 8, or a substituted aryl group having 6 to 20 carbon atoms, and specific examples thereof are the same as those of R ^L05 . R ^L07 ~ R ^L16 independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms, and specifically may be exemplified by methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group and third group. Base, third amyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-decyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl a linear, branched or cyclic alkyl group such as a cyclohexylmethyl group, a cyclohexylethyl group or a cyclohexylbutyl group, or a part of the hydrogen atoms is substituted with a hydroxyl group, an alkoxy group, a carboxyl group or an alkoxycarbonyl group. An oxo group, an amine group, an alkylamino group, a cyano group, a decyl group, an alkylthio group, a sulfo group or the like. R ^L07 ~R ^L16 may also bond to each other to form a ring with the carbon atoms 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 ,} and the like, in which case the group related to the formation of the ring represents a divalent hydrocarbon group having 1 to 15 carbon atoms, and specifically exemplified by removing one hydrogen from the exemplified in the above monovalent hydrocarbon group. Atom. Further, R ^L07 to R ^L16 may be bonded to adjacent carbon atoms without being bonded to each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and RL ¹⁵ , RL ¹³ and RL ¹ t, etc. ).

The linear or branched form of the acid restless group represented by the above formula (L1) can be specifically exemplified as the following group.

The ring in the acid restless group represented by the above formula (L1) can be specifically exemplified as tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, 2-methyl Tetrahydropyran-2-yl and the like.

The acid restless group of the above formula (L2) may specifically be exemplified by a third butoxycarbonyl group, a third butoxycarbonylmethyl group, a third pentyloxycarbonyl group, a third pentyloxycarbonylmethyl group, 1,1- Diethylpropoxycarbonyl, 1,1-diethylpropoxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2 -cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl , 2-tetrahydrofuranyloxycarbonylmethyl and the like.

The acid restless group of the above formula (L3) can be specifically exemplified by 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1- n-Butylcyclopentyl, 1-t-butylcyclopentyl, 1-cyclohexylcyclopentyl, 1-(4-methoxy-n-butyl)cyclopentyl, 1-methylcyclohexyl, 1 -ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexen-3-yl , 3-ethyl-1-cyclohexen-3-yl and the like.

The acid labile group of the above formula (L4) is preferably a group represented by the following formulas (L4-1) to (L4-4).

In the above formulae (L4-1) to (L4-4), the broken line indicates the bonding position and the bonding 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, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a second group. Butyl, tert-butyl, third pentyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl and the like.

The above formula (L4-1) to (L4-4) exist as enantiomers or diastereomers, but the above formulas (L4-1) to (L4-4) represent these. All of the stereoisomers. These stereoisomers may be used singly or as a mixture.

For example, the above formula (L4-3) is a group representing a mixture of one or two selected from the group consisting of the following formulas (L4-3-1) and (L4-3-2).

(wherein R ^L41 is the same as described above).

In addition, the above formula (L4-4) is a group representing one or a mixture of two or more selected from the group consisting of the following formulas (L4-4-1) to (L4-4-4).

(wherein R ^L41 is the same as described above).

The above formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2), and (L4-4-1) to (L4-4-4) are also representative of And a mixture of enantiomers and diastereomers.

Also, by making the keys of (L4-1)~(L4-4), (L4-3-1), (L4-3-2), and (L4-4-1)~(L4-4-4) The junction direction is a high reactivity in the acid catalyst dissociation reaction with respect to the exo side of each bicyclo[2.2.1] heptane ring (refer to JP-A-H09-336121). In the production of a monomer having a tertiary ring-alkyl group as a substituent of the bicyclo[2.2.1] heptane skeleton, there is a formula containing the following formula (L4-1-endo)~( L4-4-bridge) is a case of a bridge-alkyl-substituted monomer, but in order to achieve reactivity, the ratio of the hanging body is preferably 50% or more, and the ratio of the better hanging body is 80% or more.

(wherein R ^L41 is the same as described above).

The acid restless group of the above formula (L4) can be specifically exemplified as the following group.

Further, the alkyl group having 4 to 20 carbon atoms and the alkyl group each having a C1 to 6-trialkylsulfanyl group and a C 4 to 20 oxoalkyl group can be specifically exemplified as listed in R ^L04 . The same person and so on.

The partial structure O-Rx of the repeating unit represented by the above formula (5a) can be specifically exemplified as follows, but is not limited thereto.

The partial structure O-Ry of the repeating unit represented by the above formula (7a) can be specifically exemplified as follows, but is not limited thereto.

(wherein Me represents a methyl group).

The partial structure O-Rz of the repeating unit represented by the above formula (8a) can be specifically exemplified as follows, but is not limited thereto.

The polymer compound of the present invention may further comprise, in addition to the above, a repeating unit obtained from a monomer having a carbon-carbon double bond, for example, methyl methacrylate, methyl crotonate, dimethyl maleate, and clothing. Substituted acrylates such as dimethyl benzoate, maleic acid, fumaric acid, itaconic acid unsaturated carboxylic acid, raw borneol, norbornene derivatives, tetracyclic [4.4.0.1 ^2,5 .17 ^7,10 ] A cyclic olefin such as a dodecene derivative, a repeating unit obtained by obtaining an unsaturated acid anhydride such as maleic anhydride or itaconic anhydride, an oxime imine or the like.

In addition, the weight average molecular weight of the polymer compound of the present invention is from 1,000 to 500,000, preferably from 3,000 to 100,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene. When the ratio is outside the range, the etching resistance is extremely lowered, and the difference in the dissolution rate before and after the exposure cannot be ensured, and the resolution is lowered.

In the polymer compound of the present invention, the preferred content ratio of each repeating unit obtained from each monomer may be, for example, the range (mol%) shown below, but is not limited thereto.

(I) Formula (1a) based on the monomer of the above formula (1) containing more than 0 mol% and 100 mol% or less, preferably 2 to 70 mol%, more preferably 5 to 50 mol% (or a constituent unit represented by the formula (2a) or (3a)) based on the monomer of the formula (2) or (3), and (II) contains 0 mol% or more and 100 mol% or less, preferably 1~ 95% by mole, more preferably 20 to 80% by mole, one or more of the constituent units represented by the above formulas (5a) to (8a), and optionally (III), containing 0 to 80% by mole. Preferably, 0 to 70 mol%, more preferably 0 to 50 mol%, based on one or more of the constituent units of the other monomers.

In this case, the total of the repeating units of the formula (1a) (or the formula (2a) or (3a)) and the formula (5a) preferably contains 1 to 95 mol%, preferably 20 to 80 mol%. The repeating unit of (6a) is preferably 0 to 95 mol%, preferably 0 to 50 mol%, and the repeating unit of formula (7a) is preferably 0 to 95 mol%, preferably 20 to 80 mol. The ear %, the repeating unit of the formula (8a) is preferably from 0 to 95 mol%, preferably from 0 to 50 mol%.

The polymer compound of the present invention is produced by using a compound represented by the above formula (1), (2) or (3) as a first monomer, and a compound containing a polymerizable double bond as a second and subsequent monomer. The copolymerization reaction is carried out in the middle. The monomer of the present invention (1), (2) or (3) and the second and subsequent monomers of the first monomer used in the copolymerization preferably have an oligomer or a high molecular weight of 10 mol%. Hereinafter, it is preferably 3 mol% or less, more preferably 1 mol% or less.

The copolymerization reaction for producing the polymer compound of the present invention can be exemplified by various examples, but is preferably a radical polymerization, an anionic polymerization or a coordination polymerization.

The conditions of the radical polymerization reaction are (a) use of a hydrocarbon such as benzene or an ether such as tetrahydrofuran, an alcohol such as ethanol or a ketone such as methyl isobutyl ketone as a solvent, and (b) use 2,2'-azobis. An azo compound such as isobutyronitrile or a peroxide such as benzammonium peroxide or a lauricium ruthenium peroxide is used as a polymerization initiator. (C) The reaction temperature is maintained at about 0 to 100 ° C, and the reaction is carried out. The time is preferably about 0.5 to 48 hours, but it is not excluded from the range.

The reaction conditions for the anionic polymerization reaction are preferably (a) using a hydrocarbon such as benzene or an ether such as tetrahydrofuran or liquid ammonia as a solvent, and (b) using a metal such as sodium or potassium, n-butyllithium or t-butyllithium. An alkyl metal, a ketone radical or a Grenner reactant is used as a polymerization initiator, and the reaction temperature is maintained at about -78 ° C to 0 ° C, and the reaction time is set to about 0.5 to 48 hours. (e), a proton-donating compound such as methanol, a halide such as methyl iodide, or another electron-trapping substance is used as a stopper, but the cases other than those ranges are not excluded.

The reaction conditions for the coordination polymerization are preferably (a) using a hydrocarbon such as n-heptane or toluene as a solvent, and (b) using a Ziegler-Natta composed of a transition metal such as titanium and an aluminum alkyl (Ziegler-Natta). a catalyst, a Philips catalyst supported on a metal oxide, a olefin-metathesis mixed catalyst typified by a tungsten and ruthenium mixed catalyst, and the like. The reaction temperature is maintained at about 0 to 100 ° C, and the (but) reaction time is set to 0.5 to 48 hours, but the conditions outside the ranges are not excluded.

The polymer compound of the present invention is suitable as a base material for a photoresist material, in particular, a chemically amplified positive-type photoresist material. The present invention provides a photoresist material containing the above polymer compound, in particular, a chemically amplified positive-type photoresist. material. In this case, the photoresist material preferably contains the following:

(A) the above polymer compound as a base resin,

(B) an acid generator,

(C) organic solvents,

As needed

(D) Nitrogen-containing organic compounds

(E) Surfactant.

As the base resin of the above component (A), in addition to the polymer compound of the present invention, other resins which increase the dissolution rate of the alkali developing solution by the action of an acid may be added as needed. It may, for example, be i) a poly(meth)acrylic acid derivative, ii) a copolymer of a raw borneol derivative-maleic anhydride, iii) a hydrogenated ring-opening metathesis polymer, iv) a vinyl ether-Malay A copolymer of an acid anhydride-(meth)acrylic acid derivative or the like, but is not limited thereto.

Among them, a method for synthesizing a hydride of a ring-opening metathesis polymer is specifically described in the examples of JP-A-2003-66612. Further, specific examples are exemplified as having the following repeating units, but are not limited thereto.

The compounding ratio of the polymer compound of the present invention to other polymer compounds is in the range of 100:0 to 10:90, preferably 100:0 to 20:80. When the compounding ratio of the polymer compound of the present invention is less than the above, the preferable properties as a photoresist material cannot be obtained. The performance of the photoresist material can be adjusted by appropriately changing the above-described blending ratio.

Further, the polymer compound is not limited to one type, and two or more types may be added. The properties of the photoresist can be adjusted by using a plurality of polymer compounds.

When a photoacid generator is added as the acid generator of the component (B) used in the present invention, any compound which can generate an acid by irradiation with a high energy ray may be used. The photoacid generator which is suitable for use is a cerium salt or iodonium. Salt, N-sulfonyloxyimide, 肟-O-sulfonate type acid generator, and the like. The details are as follows, but these may be used singly or in combination of two or more.

The phosphonium salt is exemplified by a salt of a phosphonium cation and a sulfonate or a bis(substituted alkylsulfonyl) quinone imine or a hydrazine (substituted alkylsulfonyl) methide. Is triphenylphosphonium, 4-tert-butoxyphenyldiphenylphosphonium, bis(4-tert-butoxyphenyl)phenylphosphonium, ginseng (4-tert-butoxyphenyl)fluorene, 3-tert-butoxyphenyldiphenylphosphonium, bis(3-tert-butoxyphenyl)phenylhydrazine, cis(3-tert-butoxyphenyl)fluorene, 3,4-di- Third butoxyphenyl diphenyl hydrazine, bis(3,4-di-t-butoxyphenyl)phenyl fluorene, ginseng (3,4-di-t-butoxyphenyl) fluorene, Diphenyl (4-thiophenoxyphenyl) fluorene, 4-tert-butoxycarbonylmethyloxyphenyl diphenyl hydrazine, ginseng (4-tert-butoxycarbonylmethyloxyphenyl) ), (4-tert-butoxyphenyl) bis(4-dimethylaminophenyl) fluorene, ginseng (4-dimethylaminophenyl) fluorene, 4-methylphenyldiphenyl fluorene , 4-tert-butylphenyldiphenylphosphonium, bis(4-methylphenyl)phenylhydrazine, bis(4-t-butylphenyl)phenylhydrazine, ginseng (4-methylphenyl) ) 鋶, ginseng (4-tert-butylphenyl) fluorene, ginseng (phenylmethyl) fluorene, 2-naphthyl Base, dimethyl (2-naphthyl) anthracene, 4-hydroxyphenyl dimethyl hydrazine, 4-methoxyphenyl dimethyl hydrazine, trimethyl hydrazine, 2-oxocyclohexyl cyclohexyl Base, trinaphthyl fluorene, tribenzyl hydrazine, diphenylmethyl hydrazine, dimethylphenyl hydrazine, 2-oxopropyl thiolane, 2-oxobutylthiolane , 2-oxo-3,3-dimethylbutylthiolane, 2-oxo-2-phenylethylthiolane, 4-n-butoxynaphthyl-1-sulfide Heterocyclic pentamidine, 2-n-butoxynaphthyl-1-thiolane, etc., sulfonates are exemplified by trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluoro Butane sulfonate, decafluorotrifluorosulfonate, perfluoro(4-ethylcyclohexane)sulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate Acid salt, pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate, 4-fluorobenzenesulfonate, mesitylene sulfonate, 2,4,6-triisopropyl Benzobenzenesulfonate, tosylate, benzenesulfonate, 4-(p-toluenesulfonyloxy)benzenesulfonate, 6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate , 4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate, 5-( -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- (Orbornane-2-yl)ethanesulfonate, 1,1,2,2-tetrafluoro-2-(tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodeca-3- Alkene-8-yl)ethanesulfonate, 2-benzylideneoxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro- 2-(4-Phenylbenzylideneoxy)propane sulfonate, 1,1,3,3,3-pentafluoro-2-pentyloxypropane sulfonate, 2-cyclohexanecarbonyloxyl Base-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furanylmethoxypropane sulfonate, 2-naphthoquinone Baseoxy-1,1,3,3,3-pentafluoropropane sulfonate, 2-(4-t-butylbenzylideneoxy)-1,1,3,3,3-pentafluoropropane Sulfonate, 2-(1-adamantylcarbonyloxy)-1,1,3,3,3-pentafluoropropane sulfonate, 2-ethyloxyl-1,1,3,3,3 - pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-toluenesulfonyloxypropane Sulfonate, 1,1-di -2-toluenesulfoxy ethane sulfonate, adamantane methoxycarbonyldifluoromethanesulfonate, 1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate, A Oxycarbonyldifluoromethanesulfonate, 1-(hexahydro-2-oxo-3,5-methyl bridge-2H-cyclopenta[b]furan-6-yloxycarbonyl)difluoromethanesulfonic acid a salt, a 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate or the like, and a bis(substituted alkylsulfonyl) quinone imide is exemplified as bis(trifluoromethanesulfonyl)anthracene Imine, bis(pentafluoroethanesulfonyl) quinone imine, bis(heptafluoropropanesulfonyl) quinone imine, perfluoro(1,3-propionylbissulfonyl) ruthenium, etc. The (substituted alkylsulfonyl) methide is exemplified by gin(trifluoromethylsulfonyl)methide, and examples thereof include the phosphonium salts of the combinations.

The iodonium salt is exemplified by a salt of an iodonium cation and a sulfonate or a bis(substituted alkylsulfonyl) quinone imine or a hydrazide (substituted alkylsulfonyl) methide. Is diphenyl iodonium, bis(4-t-butylphenyl) iodonium, 4-tert-butoxyphenyl phenyl iodonium, 4-methoxyphenyl phenyl iodonium, etc., sulfonic acid The salts are exemplified by trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, decafluorotrifluorosulfonate, perfluoro(4-ethylcyclohexane). Sulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate, 4- Fluorobenzenesulfonate, mesitylene sulfonate, 2,4,6-triisopropylbenzenesulfonate, tosylate, benzenesulfonate, 4-(p-toluenesulfonyloxy)benzene Sulfonate, 6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate, 4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate, 5-(p-toluenesulfonate) Oxy)naphthalene-1-sulfonate, 8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecyl Benzene sulfonate, butane Acid salt, methane sulfonate, 1,1-difluoro-2-naphthylethanesulfonate, 1,1,2,2-tetrafluoro-2-(albornane-2-yl)ethanesulfonate Acid salt, 1,1,2,2-tetrafluoro-2-(tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dode-3-ene-8-yl)ethanesulfonate, 2-benzylideneoxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-(4-phenylbenzylideneoxy Propane sulfonate, 1,1,3,3,3-pentafluoro-2-pentyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3- Pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furanylmethoxypropane sulfonate, 2-naphthylmethyloxy-1,1,3,3, 3-pentafluoropropane sulfonate, 2-(4-t-butylbenzylideneoxy)-1,1,3,3,3-pentafluoropropane sulfonate, 2-(1-adamantyl) Carbonyloxy)-1,1,3,3,3-pentafluoropropane sulfonate, 2-acetoxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1, 3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-toluenesulfonyloxypropane sulfonate, 1,1-difluoro-2 -toluenesulfoxy ethanesulfonate, adamantylmethoxycarbonyldifluoromethanesulfonate, 1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate, methoxy Carbonyl Difluoromethanesulfonate, 1-(hexahydro-2-oxo-3,5-methyl bridge-2H-cyclopenta[b]furan-6-yloxycarbonyl)difluoromethanesulfonate, 4 - oxo-1-adamantyloxycarbonyldifluoromethanesulfonate, etc., as for the bis(substituted alkylsulfonyl) quinone imide, exemplified by bis(trifluoromethanesulfonyl) quinone imine, Bis(pentafluoroethanesulfonyl) quinone imine, bis(heptafluoropropanesulfonyl) quinone imine, perfluoro(1,3-propane bissulfonyl) ruthenium, etc. The sulfonyl) methide is exemplified by gin(trifluoromethylsulfonyl)methide, exemplified by the combination of such iodonium salts.

The N-sulfonyloxydicarboxy quinone imine type photoacid generator is exemplified by succinimide succinate, naphthalene dicarboxy quinone imine, phthalic acid imide, cyclohexyl carbodiimide, 5- Iridium imine skeleton such as norbornene-2,3-dicarboxylimine imine, 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxylimine, and trifluoromethanesulfonic acid Salt, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, decafluorotrifluorosulfonate, perfluoro(4-ethylcyclohexane)sulfonate, heptafluorosilane Octanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate, 4-fluorobenzenesulfonate, uniform Tosylate, 2,4,6-triisopropylbenzenesulfonate, tosylate, benzenesulfonate, 4-(p-toluenesulfonyloxy)benzenesulfonate, 6-(pair -toluenesulfonyloxy)naphthalene-2-sulfonate, 4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate, 5-(p-toluenesulfonyloxy)naphthalene-1-sulfonate Acid salt, 8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate Acid salt, methane sulfonate, 1,1-difluoro-2-naphthyl Alkane sulfonate, 1,1,2,2-tetrafluoro-2-(albornane-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-benzylideneoxy-1,1,3,3,3-pentafluoro Propane sulfonate, 1,1,3,3,3-pentafluoro-2-(4-phenylbenzylideneoxy)propane sulfonate, 1,1,3,3,3-pentafluoro-2 - pentyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro- 2-furoylmercaptooxypropane sulfonate, 2-naphthylmethyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2-(4-t-butylbenzene醯oxy)-1,1,3,3,3-pentafluoropropane sulfonate, 2-(1-adamantylcarbonyloxy)-1,1,3,3,3-pentafluoropropane sulfonic acid Salt, 2-acetoxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1 ,3,3,3-pentafluoro-2-toluenesulfonyloxypropane sulfonate, 1,1-difluoro-2-toluenesulfonyloxyethane sulfonate, adamantane methoxycarbonyldifluoride Methanesulfonate, 1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1-(hexahydro-2-oxo-3 , 5- a compound of a combination of bridge-2H-cyclopenta[b]furan-6-yloxycarbonyl)difluoromethanesulfonate, 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate, and the like .

As for the O-arylsulfonylhydrazine compound or the O-alkylsulfonylsulfonium compound (hydrazine sulfonate) type photoacid generator, the stability of the compound is increased by an electro attractor group such as a trifluoromethyl group. The oxime sulfonate represented by the following formula (Ox-1).

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

Specifically listed are 2-(2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxyimino)pentyl)indole, 2-(2, 2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxyimino)butyl)pyrene, 2-(2,2,3,3,4,4,5, 5,6,6-decafluoro-1-(nonafluorobutylsulfonyloxyimino)hexyl)indole, 2-(2,2,3,3,4,4,5,5-octafluoro- 1-(nonafluorobutylsulfonyloxyimino)pentyl)-4-biphenyl, 2-(2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonate) Nonyloxyimino)butyl)-4-biphenyl, 2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonate)醯oxyimino)hexyl)-4-biphenyl, etc., and further substituted 2-benzylideneoxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1 on the above skeleton ,3,3,3-pentafluoro-2-(4-phenylbenzylideneoxy)propane sulfonate, 1,1,3,3,3-pentafluoro-2-pentyloxypropane sulfonate Acid salt, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furanyl decyloxy Propane sulfonate, 2-naphthylmethyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2-(4-t-butylbenzylideneoxy)-1,1 , 3,3,3-pentafluoropropane sulfonate, 2-(1-adamantylcarbonyloxy)-1,1,3,3,3-pentafluoropropane sulfonate, 2-ethyl hydrazine Oxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3 - pentafluoro-2-toluenesulfonyloxypropane sulfonate, 1,1-difluoro-2-toluenesulfonyloxyethane sulfonate, adamantylmethoxycarbonyldifluoromethanesulfonate , 1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1-(hexahydro-2-oxo-3,5-A A compound of bridge-2H-cyclopenta[b]furan-6-yloxycarbonyl)difluoromethanesulfonate or 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

Among them, a preferred user is an acid generator represented by the following formula (4).

(wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom, and a carbon number of 1 to 10; The alkoxy group or a halogen atom, and R ⁹ represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, and R ¹⁰ represents a hydrogen atom or a trifluoromethyl group.

In the formula, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom, and a carbon number of 1 to 2; The alkoxy group of 10, or a halogen atom, and specific examples of the hydrocarbon group which may contain a hetero atom may be exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a t-butyl group, Third amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethylcyclohexyl, butylcyclohexyl, adamantyl, ethyladamantyl , butyl hydroxyalkyl, and any carbon-carbon bond between the groups -O-, -S-, -SO-, -SO ₂ -, -NH-, -C(=O)-, -C (=O) a group formed by a hetero atom such as O- or -C(=O)NH-, or an arbitrary hydrogen atom is substituted with a functional group such as -OH, -NH ₂ , -CHO or -CO ₂ H The basis. R ⁹ represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, and is specifically exemplified below, but is not limited thereto.

More specifically, it can be exemplified as the following:

(wherein R ¹⁰ represents a hydrogen atom or a trifluoromethyl group).

(wherein R ¹⁰ represents a hydrogen atom or a trifluoromethyl group).

Since the anion portion of the acid generator represented by the above formula (4) has an ester moiety, it is easy to introduce a high volume sulfhydryl group, a benzamidine group, a naphthylmethyl group, a fluorene carbonyl group or the like from a low volume sulfhydryl group. It is possible to have a large molecular design range, and it is also easy to adjust the solubility of the solvent or the transmittance, and thereby the diffusion control of the acid. In addition, since the sulfonic acid produced by the acid generator represented by the general formula (4) has the same strong acidity as the perfluoroalkanesulfonic acid and has a low fluorine content, it is expected to have high compatibility with the base resin and dispersibility. Good and suppresses low roughness. In particular, it was found that the roughness became extremely small by combining the acid generator represented by the formula (4) with the photoresist substrate resin having the specific spiro ring structure of the present invention as a constituent component. . Further, the acid generator represented by the general formula (4) can be used without any problem in the coating production step, the pre-exposure firing, the exposure, the post-exposure firing, and the development step. In addition, ArF immersion exposure not only inhibits dissolution in water, but also has little effect on the residual water on the wafer, and can also suppress defects. Since the ester moiety is treated by alkali hydrolysis after the production of the photoresist by the alkali, it can be converted into a low-molecular-weight low-accumulation compound, and the fluorine substitution rate can be reduced by burning and waste, so that high combustibility can be expected. The load on the environment is small.

The amount of the photoacid generator to be added as the component (B) in the chemically amplified photoresist of the present invention may be any amount within a range that does not impair the effects of the present invention, but is 100 parts per part of the base resin in the photoresist material ( The mass fraction, the same below) is 0.1 to 40 parts, preferably 2 to 30 parts. When the ratio of the photoacid generator of the component (B) is too large, the resolution may be deteriorated, or the problem of foreign matter may be caused when the development/resistance is peeled off. The photoacid generator of the above component (B) may be used singly or in combination of two or more. Further, by using a photoacid generator having a low transmittance at an exposure wavelength, the transmittance in the photoresist film can be controlled by the amount of addition.

Further, when two or more photoacid generators are used in combination, one of the photoacid generators may have a function of controlling acid diffusion when a so-called weak acid sulfonium salt is produced. That is, when a photoacid generator which produces a strong acid (for example, a fluorine-substituted sulfonic acid) and a phosphonium salt which generates a weak acid (for example, a sulfonic acid or a carboxylic acid which is not substituted by fluorine) are used, the high energy ray is irradiated from the photoacid. When the strong acid produced by the agent collides with the unreacted sulfonium salt having a weak acid anion, a sulfonium salt having a strong acid anion which releases a weak acid is produced via salt exchange. In this process, since it is found that the strong acid is exchanged to a weak acid which is lower in the catalyst, the acid can be deactivated and the acid diffusion can be controlled.

Here, when the photoacid generator which produces the strong acid is a cerium salt, a strong acid produced by irradiation with a high energy ray as described above can be exchanged into a weak acid, but a weak acid generated by irradiation with a high energy ray cannot produce a strong acid with unreacted. The salt exchange is carried out after the salt conflict. These are due to the fact that the phosphonium cations readily form ion pairs with the anions of the stronger acids.

Further, a compound (acid-proliferating compound) which generates an acid by acid decomposition may be added to the photoresist material of the present invention. Such compounds are described in J. Photopolym. Sci. and Tech., 8. 43-44, 45-46 (1995), J. Photopolym. Sci. and Tech., 9. 29-30 (1996).

Examples of acid-proliferating compounds are exemplified by tert-butyl-2-methyl-2-toluenesulfonyloxymethylacetamidoacetate, 2-phenyl-2-(2-toluenesulfonyloxyethyl) - 1,3-dioxolane, etc., but is not limited thereto. Most of the conventional photoacid generators have stability, especially poor thermal stability, which will show the properties of acid-proliferating compounds.

The addition amount of the acid-proliferating compound in the photoresist material of the present invention is preferably 2 parts or less (0 to 2 parts), more preferably 1 part or less, based on 100 parts of the base resin in the photoresist material (0 to 1). Share). When the amount of addition is too large, there is a case where diffusion is difficult to control, the resolution is deteriorated, and the shape of the pattern is deteriorated.

The organic solvent of the component (C) used in the present invention may be any one of organic solvents which can dissolve a base resin, an acid generator, other additives, and the like. These organic solvents are exemplified by ketones such as cyclohexanone and methyl amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, and 1-methoxy-2-propane. Alcohol, alcohol such as 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, Ethers such as diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-methoxypropionic acid Ester such as methyl ester, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, lactones such as γ-butyrolactone, These may be used alone or in combination of two or more, but are not limited thereto. In the present invention, among these organic solvents, diethylene glycol dimethyl ether or 1-ethoxy-2-propanol or propylene glycol monomethyl which is most excellent in solubility of the acid generator in the photoresist component is preferably used. Ethyl ether acetate and its mixed solvent.

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

In particular, in the photoresist material of the present invention, one or two or more kinds of nitrogen-containing organic compounds may be formulated as the component (D).

The nitrogen-containing organic compound is preferably a compound which inhibits the diffusion rate of the acid generated from the acid generator when it diffuses into the photoresist film. By blending a nitrogen-containing organic compound, the acid diffusion rate in the photoresist film can be suppressed, the resolution can be improved, the sensitivity change after exposure can be suppressed, and the substrate or environmental dependency can be reduced, and the exposure margin or pattern profile can be improved.

The nitrogen-containing organic compounds are listed as primary, secondary, tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, A nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcohol-containing nitrogen-containing compound, a guanamine, a quinone imine, or a urethane.

Specifically, the primary aliphatic amines are exemplified by methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, and tert-butylamine. , pentylamine, third amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, decylamine, decylamine, dodecylamine, hexadecylamine , methyldiamine, ethylenediamine, tetraethylamamine, etc., secondary aliphatic amines are exemplified by dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butyl Amine, diisobutylamine, dibutylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine , dimethylamine, di-dodecylamine, di-hexadecylamine, N,N-dimethyldiamine, N,N-dimethylethylenediamine, N,N-dimethyl Base tetraethylamine, etc., tertiary aliphatic amines are exemplified by trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine , three second butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, Heptylamine, trioctylamine, tridecylamine, tridecylamine, tri-dodecylamine, tri-hexadecylamine, N,N,N',N'-tetramethylformamide Amine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylamine and the like.

Further, examples of the mixed amines are, for example, dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like. Specific examples of the aromatic amines and the heterocyclic amines are aniline derivatives (for example, 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, methyldi Phenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2, 5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (such as oxazole, isoxazole, etc.), thiazole derivatives (such as thiazole, isothiazole, etc.), imidazole derivatives (such as imidazole, 4 -methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline, etc.), pyrrole Pyridine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.) An imidazoline derivative, an imidazolium derivative, a pyridine derivative (for example, pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, lutidine, Trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxy Pyridine, dimethoxypyridine, 4-pyrrolidylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine Derivatives, pazoline derivatives, prazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, anthracene derivatives, isoindole derivatives, 1H-carbazole derivatives, hydrazine a porphyrin derivative, a quinoline derivative (for example, a quinoline, a 3-quinoline carbonitrile derivative, etc.), an isoquinoline derivative, a porphyrin derivative, a quinazoline derivative, a quinoxaline derivative, or a pyridazine derivative. , porphyrin derivative, phenidine derivative, carbazole derivative, phenanthroline derivative, aziridine derivative, phenanthridine derivative, 1,10-phenanthroline Adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, urea derivatives glycosides.

Further, the nitrogen-containing compound having a carboxyl group is exemplified by, for example, an aminobenzoic acid, an anthracenecarboxylic acid, or an amino acid derivative (for example, nicotinic acid, alanine, arginine, aspartic acid, aminoglycolic acid, glycine) , histidine, isoleucine, leucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxy Alkalamine) and the like. The nitrogen-containing compound having a sulfonyl group is exemplified by 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, etc., a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, and an alcoholic nitrogen-containing compound are exemplified as 2 Hydroxypyridine, amino cresol, 2,4-quinolinediol, 3-mercaptomethanol water, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethyl Ethanolamine, 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, piperazine Pyridineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidone, 3-piperidinyl-1,2-propanediol, 3-pyrrolidinyl-1 , 2-propanediol, 8-hydroxydoniarin, quinuclidine, 3-tropinol, 1-methyl-2-pyrrolidineethanol, 1-aziridine Ethanol, N-(2-hydroxyethyl)benzimine, N-(2-hydroxyethyl)isonicotinamine, and the like. The amidoxime is exemplified by formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamidine. Amine, acrylamide, benzamide, 1-cyclohexyl pyrrolidone, and the like. The quinone imines are exemplified by phthalimide, amber imine, maleimide and the like. The urethanes are exemplified by N-tert-butoxycarbonyl-N,N-dicyclohexylamine, N-tert-butoxycarbonylbenzimidazole, oxazolidinone and the like.

Further, a nitrogen-containing organic compound represented by the following formula (B)-1 is exemplified.

N(X) _n (Y) _3-n (B)-1

(In the above formula, n is 1, 2 or 3, and the side chain X may be the same or different, and may be represented by the following general formula (X)-1, (X)-2 or (X)-3. Side chain Y The same or different, it represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may also contain an ether group or a hydroxyl group. Further, X may be bonded to each other to form a ring).

(In the above formula, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are a hydrogen atom or a linear or branched carbon number of 1 to 20. a cyclic or cyclic alkyl group, which may also contain one or more hydroxyl, ether, ester, lactone rings, R ³⁰³ as a single bond or a linear or branched alkyl group having 1 to 4 carbon atoms, R ³⁰⁶ It is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may also contain one or more hydroxyl groups, ether groups, ester groups or lactone rings).

Specific examples of the compound represented by the above formula (B)-1- are exemplified as stilbene (2-methoxymethoxyethyl)amine, and {2-(2-methoxyethoxy)ethyl} Amine, ginseng {2-(2-methoxyethoxymethoxy)ethyl}amine, gin {2-(1-methoxyethoxy)ethyl}amine, gin {2-(1- Ethoxyethoxy)ethyl}amine, gin {2-(1-ethoxypropoxy)ethyl}amine, gin[2-{2-(2-hydroxyethoxy)ethoxy] Ethyl]amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]dihexadecene, 4,7,13,18-tetraoxa -1,10-diazabicyclo[8.5,5]octadecene, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecenene, 1-aza-12 - Crown ether-4, 1-aza-15-coronate-5, 1-aza-18-coronal ether-6, ginseng (2-methyloxyethyl)amine, ginseng (2-ethyl oxime) Base ethyl)amine, ginseng (2-propionyloxyethyl)amine, ginseng (2-butenyloxyethyl)amine, ginseng (2-isobutylphosphonyloxyethyl)amine, ginseng (2-pentyl) Nonyloxyethyl)amine, ginseng (2-pentylmethoxyethyl)amine, N,N-bis(2-acetoxyethyl)2-(ethoxypropoxyacetoxy) Ethylamine, ginseng (2-methoxycarbonyloxyethyl)amine, ginseng (2-tert-butoxycarbonyl) Base ethyl)amine, ginseng [2-(2-oxopropoxy)ethyl]amine, gin[2-(methoxycarbonylmethyl)oxyethyl]amine, gin [2- (third Butoxycarbonylmethyloxy)ethyl]amine, gin[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine, ginseng (2-methoxycarbonylethyl)amine, ginseng (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-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-B Ethoxyethyl) 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-[(A Oxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N- Bis(2-hydroxyethyl)2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2- Ethyloxyethyl) 2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-(tetrahydrofuranyloxycarbonyl)ethylamine, N, N-bis(2-acetoxyethyl) 2-(tetrahydrofuranyloxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-[(2-oxotetrahydrofuran-3- Ethyloxycarbonyl]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-methylmethoxyethyl) 2-(4-methyloxyoxybutoxylate Ethylcarbonyl)ethylamine, N,N-bis(2-methylmethoxyethyl) 2-(2-formyloxyethoxycarbonyl)ethylamine, N,N-bis(2-methoxy 2-ethyl(methoxycarbonyl)ethylamine, N-(2-hydroxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl) Bis[2-(methoxycarbonyl)ethyl]amine, N-(2-hydroxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(2-ethyloxy) Ethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(3- Ethyloxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl) bis[ 2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(2-methoxyethoxycarbonyl) Ethyl]amine, N-methylbis(2-acetoxyethyl)amine, N-ethylbis(2-acetoxyethyl)amine, N-methylbis(2-propionamidine) Oxyethyl)amine, N-ethylbis[2-(methoxycarbonyloxy)ethyl]amine, N-ethylbis[2-(t-butoxycarbonyloxy)ethyl]amine , ginseng (methoxycarbonylmethyl)amine, ginseng (ethoxycarbonylmethyl)amine, N-butylbis(methoxycarbonylmethyl)amine, N-hexylbis(methoxycarbonylmethyl) Amine, β-(diethylamino)-δ-valerolactone.

Further, a nitrogen-containing organic compound having a cyclic structure represented by the following general formula (B)-2 is exemplified.

(In the above formula, X is as defined above, and R ³⁰⁷ is a linear or branched alkyl group having 2 to 20 carbon atoms, and may further contain one or more carbonyl groups, ether groups, ester groups or thioethers).

Specific examples of the above formula (B)-2 are exemplified by 1-[2-(methoxymethoxy)ethyl]pyrrolidine and 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, acetic acid 2 -(1-pyrrolidinyl)ethyl ester, 2-piperidinylethyl acetate, 2-morpholinylethyl acetate, 2-(1-pyrrolidyl)ethyl formate, 2-piperidinylpropionate Ester, 2-morpholinylethyl acetoxyacetate, 2-(1-pyrrolidyl)ethyl methoxyacetate, 4-[2-(methoxycarbonyloxy)ethyl]morpholine, 1-[2-(Tertidinoxycarbonyloxy)ethyl]piperidine, 4-[2-(2-methoxyethoxycarbonyloxy)ethyl]morpholine, 3-(1- Pyrrolidinyl)methyl propionate, methyl 3-piperidylpropionate, methyl 3-morpholinylpropionate, methyl 3-(thiomorpholinyl)propionate, 2-methyl-3-( 1-pyrrolidinyl)propionic acid methyl ester, 3-morpholinylpropionic acid ethyl ester, 3-piperidylpropionic acid methoxycarbonyl methyl ester, 3-(1-pyrrolidinyl)propionic acid 2-hydroxyethyl Ester, 3-morpholinylpropionic acid 2-ethenyloxy Ester, 3-oxotetrahydrofuran-3-yl 3-(1-pyridolidinyl)propionate, 4-morpholinylpropionic acid tetrahydrofuran ester, 3-piperidylpropionic acid glycidyl ester, 3-morpholinyl 2-methoxyethyl propionate, 2-(2-methoxyethoxy)ethyl 3-(1-pyridolidinyl)propionate, butyl 3-morpholinylpropionate, 3-piperidine Cyclohexyl propionate, α-(1-pyrrolidinyl)methyl-γ-butyrolactone, β-piperidinyl-γ-butyrolactone, β-morpholinyl-δ-valerolactone, 1 - methyl pyrrolidinyl acetate, methyl piperidinyl acetate, methyl morpholinyl acetate, methyl thiomorpholinyl acetate, ethyl 1-pyrrolidinyl, 2-methoxyethyl morpholinyl acetate , 2-morpholinyl 2-methoxyacetate, 2-morpholinylethyl 2-(2-methoxyethoxy)acetate, 2-[2-(2-methoxyethoxy) Ethyloxy]acetate 2-morpholinylethyl acetate, 2-morpholinylethyl hexanoate, 2-morpholinylethyl octanoate, 2-morpholinylethyl citrate, 2-morpholinyl laurate Ethyl ester, 2-morpholinylethyl myristate, 2-morpholinyl palmitate, 2-morpholinylethyl stearate.

Further, the nitrogen-containing organic compound containing a cyano group represented by the following general formulae (B)-3 to (B)-6 is exemplified.

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

The nitrogen-containing organic compound containing a cyano group represented by the above formula (B)-3 to (B)-6 is specifically exemplified by 3-(diethylamino)propionitrile and N,N-bis(2-hydroxyethyl). --3-Aminopropionitrile, N,N-bis(2-ethoxymethoxyethyl)-3-aminopropionitrile, N,N-bis(2-methyloxyethyl)-3- Aminopropionitrile, N,N-bis(2-methoxyethyl)-3-aminopropionitrile, N,N-bis[2-(methoxymethoxy)ethyl]-3-amine Methylpropionitrile, methyl N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropanoate, N-(2-cyanoethyl)-N-( Methyl 2-hydroxyethyl)-3-aminopropionate, methyl N-(2-acetoxyethyl)-N-(2-cyanoethyl)-3-aminopropanoate, N -(2-cyanoethyl)-N-ethyl-3-aminopropionitrile, N-(2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropionitrile, N-(2-Ethyloxyethyl)-N-(2-cyanoethyl)-3-aminopropionitrile, N-(2-cyanoethyl)-N-(2-carbomethoxy) Benzyl)-3-aminopropionitrile, N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropionitrile, N-(2-cyanoethyl) -N-[2-(methoxymethoxy)ethyl]-3-aminopropionitrile, N-(2-cyanoethyl)-N-(3-hydroxy-1-propyl) 3-aminopropionitrile, N-(3-acetoxy-1-propyl)-N-(2-cyanoethyl)-3-amine Propionitrile, N-(2-cyanoethyl)-N-(3-methylindol-1-propyl)-3-aminopropionitrile, N-(2-cyanoethyl)-N- Tetrahydrofuranyl-3-aminopropionitrile, N,N-bis(2-cyanoethyl)-3-aminopropionitrile, diethylaminoacetonitrile, N,N-bis(2-hydroxyethyl)amine Acetonitrile, N,N-bis(2-ethoxymethoxyethyl)aminoacetonitrile, N,N-bis(2-methylmethoxyethyl)aminoacetonitrile, N,N-bis (2-A Oxyethyl)aminoacetonitrile, N,N-bis[2-(methoxymethoxy)ethyl]aminoacetonitrile, N-cyanomethyl-N-(2-methoxyethyl) Methyl 3-aminopropionate, methyl N-cyanomethyl-N-(2-hydroxyethyl)-3-aminopropanoate, N-(2-ethyloxyethyl)-N - methyl cyanomethyl-3-aminopropanoate, N-cyanomethyl-N-(2-hydroxyethyl)aminoacetonitrile, N-(2-acetoxyethyl)-N- (cyanomethyl)aminoacetonitrile, N-cyanomethyl-N-(2-methyloxyethyl)aminoacetonitrile, N-cyanomethyl-N-(2-methoxyethyl Aminoacetonitrile, N-cyanomethyl-N-[2-(methoxymethoxy)ethyl]aminoacetonitrile, N-(cyanomethyl)-N-(3-hydroxy-1- Propyl)aminoacetonitrile, N-(3-acetoxy-1-propyl)-N-(cyanomethyl)aminoacetonitrile, N-cyanomethyl-N-(3-formamidine Alkyl-1-propyl)aminoacetonitrile, N,N-bis(cyanomethyl)aminoacetonitrile, 1-pyrrolidinepropionitrile, 1-piperidinepropionitrile, 4-morpholinepropionitrile, 1-pyrrole Pyridylacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, cyanomethyl N,N-bis(2-hydroxyethyl)-3-aminopropionate Ester, N,N-bis(2-acetoxyethyl)-3-aminopropionic acid cyanomethyl ester, N,N-bis(2-methylmethoxyethyl)-3-aminopropyl Acid cyanomethyl ester, N,N-bis(2-methoxyethyl)-3-aminopropionic acid cyanomethyl ester, N,N-bis[2-(methoxymethoxy)ethyl ] 3-amino-propionic acid cyanomethyl ester, 3-diethylaminopropionic acid (2-cyanoethyl ester), N,N-bis(2-hydroxyethyl)-3-aminopropionic acid ( 2-cyanoethyl ester), N,N-bis(2-ethoxymethoxyethyl)-3-aminopropionic acid (2-cyanoethyl ester), N,N-bis(2-methyloxanium) Base ethyl)-3-aminopropionic acid (2-cyanoethyl ester), N,N-bis(2-methoxyethyl)-3-aminopropionic acid (2-cyanoethyl ester), N,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropionic acid (2-cyanoethyl ester), 1-pyrrolidine propionate cyanomethyl ester, 1-piperidine Cyanomethyl propionate, cyanomethyl 4-morpholinepropionate, 1-pyrrolidinepropionic acid (2-cyanoethyl ester), 1-piperidinepropionic acid (2- Ethyl-yl), 4-morpholinyl acid (2-cyanoethyl).

Further, 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 a linear, branched or cyclic alkyl group having a polar functional group of 2 to 20 carbon atoms, and contains one or more hydroxyl groups, a carbonyl group, an ester group, an ether group, a thioether. a carbonate group, a cyano group or an acetal group as a polar functional group. R ³¹¹ , R ³¹² , and R ³¹³ are a hydrogen atom, a linear one having a carbon number of 1 to 10, a branched or cyclic alkyl group, an aryl group or Aralkyl).

Further, 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 one having a carbon number of 1 to 10, a branched or cyclic alkyl group, an aryl group or an aralkyl group, and R ³¹⁵ is a linear or branched having a carbon number of 1 to 20. a cyclic or cyclic alkyl group having a polar functional group, and having more than one ester group, acetal group or cyano group as a polar functional group, and may further contain one or more hydroxyl groups, a carbonyl group, an ether group, or a thioether group. Or carbonate based).

Further, a nitrogen-containing heterocyclic compound having a polar functional group represented by the following general formulae (B)-9 and (B)-10 is exemplified.

(In the above formula, A is a nitrogen atom or ≡CR ³²² , B is a nitrogen atom or ≡CR ³²³ , and R ³¹⁶ is a linear, branched or cyclic alkyl group having a polar functional group having 2 to 20 carbon atoms, The polar functional group contains one or more hydroxyl groups, a carbonyl group, an ester group, an ether group, a thioether group, a carbonate group, a cyano group or an acetal group, and R ³¹⁷ , R ³¹⁸ , R ³¹⁹ and R ³²⁰ are a hydrogen atom. a linear, branched or cyclic alkyl or aryl group having 1 to 10 carbon atoms, or R ³¹⁷ and R ³¹⁸ , R ³¹⁹ and R ³²⁰ may be bonded to each other to form a benzene ring together with the carbon atoms to which they are bonded. a naphthalene ring or a pyridine ring, R ³²¹ is a hydrogen atom, a linear or branched alkyl or aryl group having 1 to 10 carbon atoms, and R ³²² and R ³²³ are a hydrogen atom or a carbon number of 1 to 10. A linear, branched or cyclic alkyl or aryl group, and R ³²¹ and R ³²² may be bonded to form a benzene ring or a naphthalene ring together with the carbon atom to which they are bonded.

Further, a nitrogen-containing organic compound having an aromatic carboxylic acid ester structure represented by the following general formulae (B)-11 to (B)-14 is exemplified.

(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 a part or all of a hydrogen atom may be a halogen atom or a linear chain having a carbon number of 1 to 20, Branched or cyclic alkyl group, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkoxy group having 1 to 10 carbon atoms, decyloxy group having 1 to 10 carbon atoms, or carbon number Substituted by an alkylthio group of 1 to 10. R ³²⁵ is CO ₂ R ³²⁶ , OR ³²⁷ or a cyano group, and R ³²⁶ is a part of a methyl group having a carbon number of 1 to 10 which may be substituted by an oxygen atom, R ³²⁷ A part of a methyl group substituted with an oxygen atom and substituted with an alkyl group or a fluorenyl group having 1 to 10 carbon atoms. R ³²⁸ is a single bond, a methyl group, an ethyl group, a sulfur atom or O(CH ₂ CH ₂ O). _n - group, n = 0, 1, 2, 3 or 4, R ³²⁹ is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, X is a nitrogen atom or CR ³³⁰ , Y is a nitrogen atom or CR ³³¹ , Z is nitrogen An atom or CR ³³² , R ³³⁰ , R ³³¹ , 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 with the carbon atom to which they are bonded. An aromatic ring having a carbon number of 6 to 20 or a heterocyclic ring having a carbon number of 2 to 20 is formed.

Further, a nitrogen-containing organic compound having a 7-oxaborane-2-carboxylate structure represented by the following general formula (B)-15 is exemplified.

(In the above formula, R ³³³ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and R ³³⁴ and R ^{335 are} each independently one or more ethers, carbonyl groups, esters, and alcohols. a aryl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a part of a hydrogen atom of a polar functional group such as a thioether, a nitrile, an amine, an imine or a guanamine It may also be substituted by a halogen atom. R ³³⁴ and R ³³⁵ may be bonded to each other to form a heterocyclic or heteroaromatic ring having 2 to 20 carbon atoms together with the nitrogen atom to which they are bonded.

Further, the amount of the nitrogen-containing organic compound is from 0.001 to 20 parts, preferably from 0.01 to 10 parts, per 100 parts of the base resin. When the amount is less than 0.001 parts, there is no blending effect, and when it is more than 20 parts, the sensitivity is too low.

In addition to the above components, the photoresist of the present invention may contain, as an optional component, a conventional surfactant (E) for improving coatability. Further, the amount of the optional component added may be a general amount within a range not impairing the effects of the present invention.

Here, the surfactant is preferably nonionic, and is exemplified by, for example, perfluoroalkyl polyoxyethyl alcohol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, A fluorine-containing organic siloxane compound or the like. For example, FLUORAD "FC-430" "FC-431" (both manufactured by Sumitomo 3M), SURFLON "S-141", "S-145", "KH-10", "KH-20" , "KH-30", "KH-40" (made by Asahi Glass Co., Ltd.), UNIDYNE "DS-401", "DS-403", "DS-451" (both manufactured by Daikin Industries Co., Ltd.) MEGAFAC "F-8151" (manufactured by Dainippon Ink Industries Co., Ltd.), "X-70-092", and "X-70-093" (all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferred examples are FLUORAD "FC-430" (manufactured by Sumitomo 3M Co., Ltd.), "KH-20", "KH-30" (made by Asahi Glass Co., Ltd.), and "X-70-093" (Shin-Etsu Chemical industry (stock) manufacturing).

In the photoresist material of the present invention, as an optional component other than the above components, it may be added locally to the upper portion of the coating film to have a balance between the hydrophilicity of the surface and the hydrophobicity, and the water repellency or the coating film and water or other liquid may be added. A polymer compound that prevents the function of the outflow or inflow of a low molecular component upon contact. Further, the amount of the polymer compound to be added may be a normal amount within a range not inhibiting the effects of the present invention, but is preferably 15 parts or less, preferably 10 parts or less, per 100 parts of the base resin. The lower limit is preferably one part or more from the viewpoint of exerting the effect.

Among them, the polymer compound partially distributed on the upper portion of the coating film is preferably a polymer composed of one or two or more fluorine-containing units, a copolymer, and a copolymer composed of a fluorine-containing unit and other units. Specific examples of the fluorine-containing unit and other units can be exemplified as the following, but are not limited thereto.

The weight average molecular weight of the polymer compound partially distributed on the upper portion of the coating film is preferably from 1,000 to 50,000, more preferably from 2,000 to 20,000. When it is outside this range, the effect of surface modification is insufficient, and there is a flaw in the development of image defects. Further, the above weight average molecular weight means a polystyrene equivalent value by gel permeation chromatography (GPC).

The basic constituent component of the photoresist material of the present invention is the above-mentioned polymer, acid generator, organic solvent, and nitrogen-containing organic compound. However, other components such as a dissolution inhibitor, an acidic compound, a stabilizer, and a dye may be added as the above components as necessary. Any component. Further, the amount of the optional component added may be a general amount within a range not impairing the effects of the present invention.

Forming the pattern using the photoresist material of the present invention can be carried out by using conventional lithography techniques, and undergoing various steps of coating, heat treatment (prebaking), exposure, heat treatment (post exposure bake, PEB), and development. Achieved. Additional steps can be added as needed.

When the pattern formation is performed, first, a coating method suitable for spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, or the like is applied so that the coating film thickness is 0.01 to 2.0 μm. The photoresist of the present invention is applied to a substrate for manufacturing an integrated circuit (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, Cr, CrO, CrON, MoSi, etc.). Prebaking on a hot plate at 50~150 °C for 1~10 minutes, preferably at 60~140 °C for 1~5 minutes. Since the thinning of the photoresist and the etching selectivity of the substrate to be processed are severely processed, the underlying film containing the germanium is laminated under the photoresist, and the underlying film having a high carbon density and high etching resistance is laminated thereon. The three-layer process of laminating the substrate to be processed is discussed. When the etching selectivity ratio of the fluorine-containing interlayer film using oxygen, hydrogen, ammonia, or the like to the underlayer film is high, the ruthenium-containing interlayer film may be thinned. The single-layer photoresist and the ruthenium-containing intermediate layer have higher etching options, and it is also possible to thin the single-layer photoresist. In this case, a method of forming the underlayer film is exemplified by a method of coating and baking and a CVD method. In the coating type, a resin obtained by polymerizing a phenol resin or an olefin having a condensed ring or the like is used, and a gas such as butane, ethane, propane, ethylene or acetylene is used for the production of the CVD film. For the ruthenium-containing intermediate layer, a coating type and a CVD type are also exemplified, and as for the coating type, sesquioxane, a cage oligo-sesquioxane or the like is used as a raw material, and for CVD, various decane are exemplified. Gas is used as a raw material. The ytterbium-containing intermediate layer may also have an anti-reflection function with light absorption, and may also be a light absorbing group such as a phenyl group or a SiON film. An organic film may also be formed between the ruthenium containing interlayer film and the photoresist film. In this case, the organic film may also be an organic antireflection film.

After the photoresist film is formed, an acid generator or the like from the surface of the film is extracted by pure water washing (post-soaking), or the particles may be washed, or a protective film may be applied.

Next, exposure is performed by a specific reticle for forming a target pattern using a light source selected from the group consisting of ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, gamma rays, synchrotron rays, and the like. The exposure amount is preferably from about 1 to 200 mJ/cm ² , preferably from about 10 to 100 mJ/cm ² . Then, after baking at 60-150 ° C on a hot plate, it is baked (PEB) for 1 to 5 minutes, preferably after baking at 80 to 120 ° C for 1 to 3 minutes. Further, a developing solution of an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) of 0.1 to 5% by mass, preferably 2 to 3% by mass, is used, and a puddle is used by using a dip method. A conventional method such as a method or a spray method is used for imaging for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, to form a target pattern on a substrate. Moreover, the photoresist material of the present invention can be used for better utilizing ultraviolet rays having a wavelength of 254 to 193 nm, vacuum ultraviolet rays having a wavelength of 157 nm, electron beams, soft X-rays, X-rays, excimer lasers, gamma rays, synchrotron rays. It is better to use the fine patterning of high energy lines in the wavelength range of 180 to 200 nm.

Further, the photoresist material of the present invention can also be used in liquid immersion lithography. A liquid having a refractive index of 1 or more, which is high in transparency or the like, is used as a liquid immersion solvent in ArF liquid immersion lithography. In liquid immersion lithography, pure water or other liquid is inserted between the pre-baked photoresist film and the projection lens. Thereby, the lens design of the NA system of 1.0 or more can be obtained, 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 has been accelerated. In the case of liquid immersion exposure, pure water cleaning (post-immersion) may be performed after exposure to remove residual water droplets remaining on the photoresist film, and in order to prevent the elution from the photoresist film and improve the water slidability of the film surface, pre-baking A protective film can also be formed on the photoresist film after baking. The photoresist film for use in liquid immersion lithography is preferably insoluble in water and soluble in an alkali developing solution to have 1,1,1,3,3,3-hexafluoro-2-propanol residues. The polymer compound is used as a substrate, and is dissolved in an alcohol solvent having 4 or more carbon atoms, an ether solvent having 8 to 12 carbon atoms, and a material in the mixed solvent.

The resolution at the highest NA of the liquid immersion lithography using the NA1.35 lens is 40 to 38 nm, which is not possible to reach 32 nm. Therefore, development of a material having a high refractive index which is useful for further improving NA is performed. The limit of the NA of the lens is determined by the minimum refractive index of the projection lens, liquid, and photoresist film. When water immersed, the refractive index of water is the lowest compared to the projection lens (refractive index of 1.5 for synthetic quartz) and the photoresist film (which is the conventional methacrylate system). The refractive index determines the NA of the projection lens. Recently, a highly transparent liquid having a refractive index of 1.65 has been developed. In this case, the projection lens formed of synthetic quartz has the lowest refractive index, so it is necessary to develop a projection lens material having a high refractive index. LUAG (Lu ₃ Al ₅ O ₁₂ ) is a material most expected to have a refractive index of 2 or more.

The photoresist of the present invention can also be applied to lithography using a high refractive index liquid.

In addition, as a long-life technology of ArF lithography, the most recent attention is the formation of a pattern by the first exposure and imaging, and the second exposure to form a double pattern between the first patterns. Modeling process (Proc. SPIE. vol. 5754, p1508 (2005)). As for the dual patterning process, there are multiple processes for the proposal. For example, by the first exposure and imaging to form a photoresist pattern with a space of 1:3, the underlying hard mask is processed by dry etching, and a hard mask is placed on the first layer again. The space portion of the exposure is formed by exposure and development of the photoresist film to form a line pattern, and the hard mask is processed by dry etching to form a half line and space pattern of the initial pattern pitch. Moreover, by the first exposure and development to form a photoresist pattern with a space of 1:3, the underlying hard mask is processed by dry etching, and a photoresist film is coated thereon to leave a hard mask. The second part of the cover is subjected to a second spatial pattern exposure, and the hard mask is processed by dry etching. The hard mask is processed by two dry etchings.

In the foregoing method, it is necessary to lay two hard masks, and the latter method can be completed by one layer, but it is necessary to form a groove pattern which is more difficult to resolve than the line pattern. In the latter method, the formation of the pattern is formed by using a negative photoresist material. Although the contrast light of the same pattern can be formed by the positive pattern, the negative photoresist material has a lower contrast ratio than the positive photoresist material, and the line is formed by the positive photoresist material. In the case of comparing the pattern of the same size with a negative photoresist material, the resolution of the negative photoresist material is low. In the latter method, it is considered to be suitable for the use of a positive photoresist material to form a wider groove pattern, to heat the substrate to shrink the pattern of the heat flow method, or to apply water solubility on the groove pattern after development. Post-film heating is a RELACS method in which the groove is shrunk by crosslinking the surface of the photoresist film, but there is a disadvantage that the defects of adjacent via holes are deteriorated or the process is more complicated and the yield is lowered.

In the former and the latter method, since it is necessary to perform the etching of the substrate processing twice, there are also problems of a decrease in yield and pattern distortion or positional shift due to two etchings.

In order to complete the etching in one pass, there is a method of using a negative photoresist material for the first exposure and a positive photoresist material for the second exposure. A positive-type photoresist material is also used for the first exposure, and a negative-type photoresist material dissolved in a higher alcohol having a carbon number of 4 or more which does not dissolve the positive-type photoresist material is used for the second exposure. In these cases, resolution is deteriorated using a negative-type photoresist material having low resolution.

If the second exposure is performed at a position where only the half of the pitch is offset adjacent to the first exposure, the first time and the second energy are offset, and the contrast becomes zero. When a contrast enhancement film (CEL) is used on the photoresist film, the light incident on the photoresist film becomes non-linear, and the first and second light do not collide, forming a half-pitch image (Jpn. J. Appl. Phy Vol. 33 (1994) P6874-6877). Further, as the acid generator for photoresist, a 2-photon absorption acid generator is used, and the same effect can be expected by generating a nonlinear contrast.

The most important problem in the dual patterning is the alignment accuracy of the first pattern and the second pattern. Since the line size is disordered due to the positional shift size, for example, a line of 32 nm is formed with a precision of 10%, and alignment precision of 3.2 nm or less is necessary. Since the scanning alignment accuracy of the current situation is about 8 nm, it is necessary to greatly improve the accuracy.

It has been explored how to incinerate the pattern in the photoresist solvent and the alkali imaging solution after forming the first photoresist pattern, and apply the second photoresist to the space of the first photoresist pattern. Part of the photoresist pattern freezing technology that forms the second photoresist pattern. If this method is used, since the etching of the substrate can be completed in one time, the amount of processing can be increased and the problem of positional displacement caused by stress relaxation of the hard mask of the etching can be avoided. As for the freezing technique, in order to investigate a method of forming a film on a first photoresist pattern or a method of insolubilizing a photoresist pattern by photothermal heat, the photoresist material of the present invention can also be applied to such a process. The light used for freezing is preferably a wavelength of 300 nm or less, more preferably a wavelength of 200 nm or less, a wavelength of 193 nm, an ArF excimer laser light, a wavelength of 172 nm Xe ₂ excimer laser light, a 157 nm F ₂ excimer electroluminescence, a 146 nm Kr. ₂ excimer laser light, 126 nm Ar ₂ excimer laser light, exposure amount, in the case of light, is an exposure amount of 10 mJ / cm ² ~ 10 J / cm ² range. Irradiation of a quasi-molecular laser or a quasi-molecular laser lamp having a wavelength of 200 nm or less, particularly 193 nm, 172 nm, 157 nm, 146 nm, and 122 nm, not only generates an acid from a photo-acid generator, but also promotes a crosslinking reaction by light irradiation. Further, 0.001 to 20 parts, preferably 0.01 to 10 parts, of a thermal acid generator as an ammonium salt of a photoresist material may be added to 100 parts of the base resin of the photoresist material to generate an acid by heating. In this case, the occurrence of acid proceeds simultaneously with the crosslinking reaction. The heating condition is 100 to 300 ° C, and particularly the temperature range of 130 to 250 ° C is preferably in the range of 10 to 300 seconds. Thereby, a crosslinked photoresist film insoluble in a solvent and an alkali developing solution is formed.

[Examples]

The present invention is specifically illustrated by the following examples and comparative examples, but the present invention is not limited by the following examples. Further, Me in the following examples represents a methyl group.

The monomers of the present invention were synthesized by the formulations shown below.

[Synthesis Example 1] Synthesis of methacrylic acid (6-methyl-6-spiro[4.5]decyl ester) (monomer 1)

Stirring from cyclohexanone in a similar manner to the literature cited in the literature: AP Krapcho, Synthesis, 1974, p. 383, while stirring at room temperature under a nitrogen atmosphere. A mixture of 100 g and 200 ml of tetrahydrofuran was added dropwise at 60 ° C or less to 1.28 mol of a methylmagnesium chloride-tetrahydrofuran solution (31.1 g of magnesium metal and 400 ml of tetrahydrofuran and methyl chloride). After the reaction mixture was refluxed for 30 minutes, the reaction was quenched by the addition of saturated aqueous ammonium chloride. After the usual extraction, washing, and drying, the mixture was dried under reduced pressure to give 93.3 g (yield: 87%) of the desired compound 6-methylspiro[4.5]indole-6-ol.

6-methylspiro[4.5]non-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), 1.26-1.62 (12H, m), 1.85 (1H, dt, 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 [width (hereinafter referred to 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 in a nitrogen atmosphere, a mixture of 142.4 g of methacrylic acid ruthenium chloride and 300 ml of acetonitrile was added dropwise to 6-methylspiro[4.5]indole-6-ol 156.22 g, triethylamine 183.8 g, 4 - a mixture of dimethylaminopyridine 11 g and acetonitrile 500 ml. After stirring at 40 ° C for 4 hours, at 50 ° C for 20 hours, and further at 60 ° C for 5 hours, the reaction was terminated by the addition of a saturated aqueous solution of sodium hydrogencarbonate. After the usual extraction, washing, drying, and the like, the mixture was evaporated under reduced pressure to give 163 g (yield: 74%) of the desired methacrylic acid (6-methyl-6-spiro[4.5] decyl ester).

Methacrylic acid (6-methyl-6-spiro[4.5]decyl ester)

Colorless liquid

Boiling point: 77 ° C / 10.6 Pa

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 = 1.23-1.30 (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, J = 7, 13 Hz), 2.21 (1H, br), 5.58 (1H, like five peaks, J = 2 Hz), 5.93 (1H, like s) 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.

^{In the 13} C-NMR spectrum, a broad peak (Broadening) was observed for a part of the carbon atom signal. In general, when the balance between the ligands (conformation) is sufficiently early, since the average position corresponding to the existence probability of each ligand gives a steep peak, the broad peak shows the spatial balance between the complex ligands. Obstacles are suppressed.

GC-MS (EI): (m/z) ⁺ = 41, 69, 108, 135, 149, 236 (M ⁺ ).

Using the above-mentioned NMR measurement sample, the trifluoromethanesulfonic acid containing the amount of catalyst added was analyzed by ¹ H- and ¹³ C-NMR, and the structure of the olefin produced by the dissociation reaction was heated to 40 ° C, and then identified as follows (in brackets) Moir is generated for it). Formation of a decahydronaphthalene type olefin due to skeleton transfer caused by 1,2-alkyl shift was observed.

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

While stirring under a nitrogen atmosphere at -8 ° C, a mixture of 73.21 g of spiro[4.5]pyridin-6-one and 103.3 g of ethyl bromide and 500 g of tetrahydrofuran was added dropwise to the metal lithium 13.16 g and tetrahydrofuran while maintaining the temperature below 0 ° C. In a mixture of 270 g. The reaction was quenched by the addition of a saturated aqueous solution of ammonium chloride under ice cooling. After the usual extraction, washing, and drying, the mixture was dried under reduced pressure to give 71.1 g (yield: 81%) of 6-ethylspiro[4.5]indole-6-ol.

6-ethylspiro[4.5]indole-6-ol

Colorless liquid

Boiling point: 68 ° C / 16 Pa

1R (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, 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 2.64 M n-butyllithium-n-hexane solution was added dropwise to a mixture of 80.0 g of 6-ethylspiro[4.5]indole-6-ol and 300 g of tetrahydrofuran. After stirring at 50-60 ° C for 2 hours, it was cooled to below 10 ° C. A mixture of 55 g of methacrylic acid ruthenium chloride and 220 ml of tetrahydrofuran was added dropwise, and the mixture was stirred at room temperature overnight. The reaction was quenched by the addition of a saturated aqueous solution of ammonium chloride under ice cooling. After the usual extraction, washing, drying, and the like, the mixture was distilled under reduced pressure to give 80.2 g (yield: 73%) of the desired compound 6-(6-ethylspiro[4.5] decyl ester.

6-(6-ethylspiro[4.5]decyl methacrylate)

Colorless liquid

Boiling point: 83 ° C / 20 Pa

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, 137.59 , 165.61ppm.

GC-MS (EI): (m/z) ⁺ = 41, 69, 108, 135, 163, 221, 250 (M ⁺ ).

In the same manner as in the above-mentioned Synthesis Example 1, after the structure of the olefin produced by dissociation was analyzed, it was identified as follows (the molar ratio was generated in parentheses).

[Synthesis Example 3] Synthesis of 1-(1-methylspiro[4.4]decyl methacrylate) (monomer 3)

While stirring at 40 ° C in a nitrogen atmosphere, 1,300 ml of toluene was added dropwise to 1.6 mol of a methylmagnesium chloride-tetrahydrofuran solution (prepared from magnesium metal 39 g and 1,300 ml of tetrahydrofuran and dichloromethane), followed by dropping of snails [ 4.4] Indole-1-one (which is synthesized by the literature: AP Krapcho, Synthesis, 1974, p. 383, similar to the method, synthesized from cyclopentanone), a mixture of 111 g and 1,300 ml of toluene. After the reaction mixture was stirred at 70 ° C for 1.5 hours, it was returned to room temperature, and the reaction was quenched by the addition of 20% hydrochloric acid. After the usual extraction, washing, and drying, the mixture was dried under reduced pressure to give 103 g (yield: 83%) of the desired product 1-methylspiro[4.4]indole-1-ol.

1-methylspiro[4.4]non-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.

While stirring at 40 ° C in a nitrogen atmosphere, a mixture of 88 g of methacrylic acid ruthenium chloride and 200 ml of acetonitrile was added dropwise to 1-methylspiro[4.4]nonan-1-ol 88 g, triethylamine 114 g, 4-dimethyl A mixture of pyridine 6.9 g and acetonitrile 300 ml. After stirring overnight at 50 ° C, it was returned to room temperature, and the reaction was quenched by the addition of saturated aqueous sodium hydrogen carbonate. After the usual extraction, washing, drying, and the like, the mixture was evaporated under reduced pressure to give 105 g (yield: 84%) of the desired product 1-(1-methylspiro[4.4] decyl methacrylate.

1-(1-methylspiro[4.4]decyl methacrylate)

Colorless liquid

Boiling point: 61 ° C / 20 Pa

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=1.23-1.28 (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, like five peaks, 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 ⁺ ).

In the same manner as in the above-mentioned Synthesis Example 1, after the structure of the olefin produced by dissociation was analyzed, it was identified as follows (the molar ratio was generated in parentheses).

[Synthesis Example 4] Synthesis of 1-(1-ethylspiro[4.4]decyl methacrylate) (monomer 4)

While stirring at -10 ° C to 0 ° C in a nitrogen atmosphere, a mixture of 86.4 g of spiro [4.4] inden-1-one and 102.2 g of ethyl bromide and 560 ml of tetrahydrofuran was added dropwise to the metal lithium 13.01 while remaining below 0 ° C. A mixture of g and 340 ml of tetrahydrofuran. After stirring overnight at room temperature, the reaction was quenched by ice-cooled and saturated aqueous ammonium chloride. After general extraction, ‧ washing, drying, and post-treatment, it is purified by silica gel column chromatography to obtain the starting material of snail [4.4] 壬-1-one 53 g and the target 1-ethyl snail [4.4] 壬-1-ol 34.3 g (yield 84% from the consumed raw material).

1-ethylspiro[4.4]nonanol

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), 1.17-1.12 (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 in a nitrogen atmosphere, a mixture of 21 g of methacrylic acid chloride and 20 ml of acetonitrile was added dropwise to 1-ethyl spiro[4.4]nonanol 19.9 g, triethylamine 24 g, 4- A mixture of 1.44 g of dimethylaminopyridine and 50 ml of acetonitrile. After stirring overnight at 50 ° C, it was returned to room temperature, and the reaction was quenched by the addition of saturated aqueous sodium hydrogen carbonate. After the usual extraction, washing, drying, and the like, the mixture was evaporated under reduced pressure to give 21.2 g (yield: 76%) of the desired product, 1-(1-ethylspiro[4.4] decyl methacrylate.

1-(1-ethylspiro[4.4]decyl methacrylate)

Colorless liquid

Boiling point: 68 ° C / 10.6 Pa

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 , like five peaks, J = 1.5 Hz), 5.93 (1H, like s) 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, 500 ml of toluene was added dropwise to 0.95 mol of a methylmagnesium chloride-tetrahydrofuran solution (prepared from 23 g of magnesium metal and 500 ml of tetrahydrofuran and dichloromethane), followed by dropping of snails [4.5]. Indole-1-one (which is synthesized by the literature: AP Krapcho, Synthesis, 1974, a method similar to that cited in p. 383, synthesized from cyclopentanone), a mixture of 73 g and 1,300 ml of toluene. After the reaction mixture was stirred at 70 ° C overnight, it was returned to room temperature, and then a saturated aqueous ammonium chloride solution was added to terminate the reaction. After the usual extraction, washing, drying, and the like, the mixture was evaporated under reduced pressure to give 50.2 g (yield: 63%) of the desired product 1-methylspiro[4.5]indole-1-ol.

1-methylspiro[4.5]nonanol

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 (600MHz 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, 22.11, 22.56, 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 in a nitrogen atmosphere, a mixture of 34.5 g of methacrylic acid ruthenium chloride and 50 ml of acetonitrile was added dropwise to 1-methylspiro[4.5]nonan-1-ol 37 g, triethylamine 43.8 g, 4- A mixture of 2.6 g of dimethylaminopyridine and 100 ml of acetonitrile. After stirring at 50 ° C overnight, it was returned to room temperature, and the reaction was quenched by the addition of 5% hydrochloric acid. After the usual extraction, washing, drying, and the like, the mixture was distilled under reduced pressure to give 47.4 g (yield: 94%) of the desired product of 1-(1-methylspiro[4.5] decyl methacrylate.

1-(1-methylspiro[4.5]decyl methacrylate)

Colorless liquid

Boiling point: 68 ° C / 13 Pa

IR (D-ATR): ν = 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, J = 1.8 Hz), 5.91 ( 1H, like s) 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-orbornane-2-spiro-1'-cyclopentane-2'-ester) (monomer 6)

A mixture of 63 g of 2-dimethylaminocyclopentanone and 40 g of cyclopentadiene was heated under reflux in an oil bath at 110 ° C for 12 hours. The distillation reaction mixture was purified by silica gel column chromatography to obtain a fraction having a boiling point of 67 ° C / 80 Pa or less, to obtain 25.7 g (yield 39%) of the target product - 5 - borneol-2-spiro-1'. - cyclopentane-2'-one with a small amount of the isomer bridge-5-formobenyl-2-spiro-1'-cyclopentane-2'-one.

Hang-5-原bornerene-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.

Bridge-5-原bornerene-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 = 1.42 - 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 15 kg/cm ² in a mixture of 25.5 g of norbornene-2-spiro-1'-cyclopentane-2'-one, 70 ml of tetrahydrofuran, and 5% palladium-carbon catalyst. The catalyst was filtered and concentrated under reduced pressure to give 25.8 g (y.

Hang-original hafnyl-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, the pendant -5-orbornane-2-spiro-1'-cyclopentane-2'-one 26 g (wherein the hanging system is relative to the original borneol ring) The relative stereo position of the ketone which is obtained by hydrogenation of 2-dimethylaminocyclopentanone with a Diels-Alder adduct of cyclopentadiene) and a mixture of 32.8 g of ethyl bromide It was added dropwise to a mixture of 3.2 g of metallic lithium and 150 ml of tetrahydrofuran while maintaining the temperature below 0 °C. After stirring at 5 ° C overnight, the reaction was quenched by ice-cooled and saturated aqueous ammonium chloride. After general extraction, ‧ washing, drying, and post-treatment, it was purified by silica gel column chromatography to obtain 20.8 g (yield 68%) of the desired product 1'-ethyl-5-formane-2-pyringe -1'-cyclopentane-2'-ol.

Hanging-1'-ethyl-5-oribornane-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 (2.3H, m), 1.44-1.65 (9.5H, m), 1.64-1.73 (1H, m), 1.80-1.87 (0.3H, m), 1.96-2.06 (1H, m), 2.17-2.22 (1.7H, m) ppm (in number of H occurs at about its relative value when the value of the two isomers of 3H 0.93-1.00 of the total signal integral CH _3).

While stirring at 5 ° C under a nitrogen atmosphere, 21 ml of triethylamine was added dropwise to the suspension containing -1 '-ethyl-5-oribornane-2-spiro-1'-cyclopentane-2'-ol ( A mixture of diastereomers) was used in a mixture of 13.8 g, 13 ml of methacrylium chloride, a catalyst amount of 4-dimethylaminopyridine, and 120 ml of dichloromethane. Stir at room temperature overnight and stop the reaction by the addition of a saturated aqueous solution of ammonium chloride. After general extraction, ‧ washing, drying, and post-treatment, concentrated under reduced pressure to obtain the desired product methacrylic acid--(1'-ethyl-5-orinetane-2-spiro-1'-cyclopentane -2'-base ester).

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

While stirring at 50 ° C under a nitrogen atmosphere, the snail [4.1.4.3] tetradecane-6-one (which is similar to the literature cited in the literature: AP Krapcho, Synthesis, 1974, p. 383, From snail [4.5] 癸-6-one synthesis) a mixture of 44.3 g and 50 ml of tetrahydrofuran was added dropwise to a solution of 0.43 mol of methylmagnesium chloride-tetrahydrofuran solution at 60 ° C or less (from magnesium metal 10.45 g with tetrahydrofuran 150 ml and methyl chloride) in. After cooling to room temperature, the reaction was quenched by the addition of a saturated aqueous solution of ammonium chloride. After the usual extraction, washing, and drying, the mixture was dried under reduced pressure to give 46.3 g (yield: 97%) of the desired compound 6-methyldispiro[4.1.4.3]tetradecane-6-ol.

6-methyldispiro[4.1.4.3]tetradecane-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 (600MHz 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 under a nitrogen atmosphere, 6-methyl snail [4.1.4.3] was added dropwise to a mixture of 2.75 M of n-butyllithium-n-hexane solution 57.5 ml and tetrahydrofuran 60 ml below 20 ° C. Tetraline-6-alcohol 32.8 g. After the dropwise addition, the mixture was stirred at 50 ° C for 2 hours, and then cooled again with ice. A mixture of 27 g of methacrylic acid pyruvic acid mixed anhydride and 160 ml of tetrahydrofuran was added dropwise. After stirring overnight at room temperature, a saturated aqueous solution of sodium hydrogencarbonate was added to stop the reaction. After general extraction, ‧ washing, drying, and post-treatment, it was purified by silica gel column chromatography to obtain 18.8 g (yield 44%) of the desired product 6-methyl-6-dispiro[4.1. 4.3] Myristyl ester.

6-methyl-6-dispiro[4.1.4.3]tetradecyl methacrylate

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 = 1.21-1.28 (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, like five peaks, J = 1.2 Hz), 5.91 (1H, s) ppm.

¹³ C-NMR (150MHz in _{DMSO-d 6, 60 ℃)} : 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.

Since it was found in the ¹³ C-NMR spectrum that the signal disappeared due to the broadening of the peak measured at room temperature (carbon disappearance), it was measured by heating to 60 °C. Even under heating, it was observed that the signal that the balance of the complexes was considered to be suppressed by the steric hindrance was widened.

The measurement sample of the above NMR was used, and the structure of the olefin produced by the dissociation reaction was analyzed by ¹ H- and ¹³ C-NMR, and after heating to 40 ° C, the structure of the olefin produced by the dissociation reaction was identified as follows (in brackets The Mohr ratio it generates). Formation of a decahydronaphthalene type olefin due to skeleton transfer caused by 1,2-alkyl shift was observed.

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

While stirring under ice cooling in a nitrogen atmosphere, 80 g of dispiro[4.1.4.3]tetradecane-6-one and 73 g of tetrahydrofuran were added to 14.5 g of sodium borohydride, 145 g of methanol, and 0.3 g of a 25% aqueous sodium hydroxide solution. A mixture of 8 g of water and 73 g of tetrahydrofuran. After the reaction mixture was stirred at room temperature overnight, 300 ml of toluene was added and the organic layer was recovered. After the usual washing and drying, the reaction was concentrated under reduced pressure to give 81.0 g (yield: 99%) of the desired compound snail. It is of sufficient purity to be used in subsequent steps without the above purification.

Two snail [4.1.4.3] tetradecane-6-ol

Colorless solid

IR (D-ATR): ν = 3481,2926,2861,1449,1060cm -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 3.72 g of methacrylic acid ruthenium chloride and 5 ml of acetonitrile was added dropwise to 5.0 g of dispiro[4.1.4.3]tetradecane-6-ol and 4.80 g of triethylamine. A mixture of 0.29 g of 4-dimethylaminopyridine and 25 ml of acetonitrile. After the reaction mixture was stirred at 40 ° C overnight, the reaction was quenched with saturated aqueous sodium hydrogen carbonate. After general extraction, ‧ washing, drying, and post-treatment, it was purified by silica gel column chromatography to obtain 1.92 g (yield 29%) of the desired product methacrylic acid 6-dispiro[4.1.4.3]tetradecane ester.

6-dispiro[4.1.4.3]tetradecyl methacrylate

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 - 1.55 (22H, m), 1.89 (3H, s), 4.77 (1H, s), 5.66 (1H, like five peaks, J = 1.5 Hz) , 6.04 (1H, s) 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.

Since the signal caused by the broadening of the peak measured at room temperature was observed to disappear in the ¹³ C-NMR spectrum (carbon disappearance), the temperature was measured to 60 ° C. Even under heating, it was observed that the signal that is considered to be a balance between the complexes of the plural is suppressed by the steric hindrance.

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 ester)

To a mixture of 100 g of 6-methylspiro[4.5]indole-6-ol, 83 g of triethylamine, and 250 g of toluene, was added dropwise to a solution of 69 g of propylene chloride in 50 g of toluene at 60 ° C over 1 hour. After stirring at the same temperature for 6 hours, the reaction liquid was cooled to 0 ° C, and 50 g of water and 130 g of a saturated aqueous sodium hydrogencarbonate solution were added dropwise to terminate the reaction. 300 g of hexane was added, and the mixture was extracted, washed, dried, and concentrated and purified by distillation to obtain 105 g (yield: 82%) of the desired material (6-methyl-6-spiro[4.5] decyl ester).

Acrylic acid (6-methyl-6-spiro[4.5]decyl ester)

Colorless liquid

Boiling point: 69 ° C / 20 Pa

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 , 810cm ^-1 .

¹ H-NMR (600 MHz in DMSO-d ₆ ): δ=1.21-1.41 (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 (150MHz in _{DMSO-d 6): δ =} 19.36,21.39,21.48,25.67,25.75,32.04,33.15,34.04,34.87,49.94,129.82,130.31,164.51ppm.

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 ester)

The cyclopentadiene produced from 20 g of dicyclopentadiene was added dropwise to 50 g of acrylic acid (6-methyl-6-spiro[4.5]decyl ester) at 30 °C. The internal temperature was slowly raised to 70 ° C, and stirring was carried out for 12 hours. The reaction solution was directly purified by silica gel chromatography to obtain a mixture of diastereomers of 54 g of the desired product of 5-norbornene-2-carboxylic acid (6-methyl-6-spiro[4.5] decyl ester). (Yield 98%).

5-Ornirolene-2-carboxylic acid (6-methyl-6-spiro[4.5]decyl ester), two diastereomers of the bridge and two diastereomers of the hanging body Mixture, bridge body: hanging body = 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 sample is a mixture of two diastereomers of the bridge body and two diastereomers of the hanging body. Complex spectra were generated in ¹ H-NMR and ¹³ C-NMR. The spectrum of the main 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, 137.54, 172.60, 172.66 ppm.

The GC-MS spectra of the major isomers are listed.

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 ester) (monomer 9)

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

Snail [4.5] 癸-6,9-diene-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 containing 12.8 g of spiro[4.5]indole-6,9-dien-8-one and 50 ml of ethyl acetate and 10% palladium-carbon in a catalytic amount. The catalyst was filtered and concentrated under reduced pressure to give 13.5 g (yield yield) of the desired product, 8-spiro[4.5] fluorenone. These are of sufficient purity and are therefore not used in the subsequent steps by the above purification.

8-spiro[4.5]nonanone

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 +).

Other synthesis of 8-spiro[4.5]fluorenone

Using the method described in the literature: Organic Synthesis, Collective volume 7, page 473 and similar procedures, using 228.44 g of cyclopentane formaldehyde in place of the cyclooctane formaldehyde-treated piperidenamine methyl vinyl ketone for the Michael (Michael) addition, aldol condensation, cyclization, dehydration, hydrolysis, and purification by distillation under reduced pressure gave 173.4 g (yield 54%) of spiro[4.5]indole-6-en-8-one.

Snail [4.5] 癸-6-ene-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.

GC-MS (EI): (m/z) ⁺ = 53, 66, 79, 94, 108, 122, 150 (M ⁺ ).

Hydrogen was added at 10 kg/cm ² to a mixture containing 170 g of spiro[4.5]non-6-en-8-one and 400 ml of tetrahydrofuran in a catalyst amount of 10% palladium-carbon. The catalyst was filtered and concentrated under reduced pressure to give 187 g (quant. The optical properties of this person are consistent with those described above. In addition, the person has sufficient purity and thus does not need to be purified for use in the subsequent steps.

While stirring under a nitrogen atmosphere at room temperature, a mixture of 13.4 g of 8-spiro[4.5]fluorenone and 80 ml of tetrahydrofuran was added dropwise at 50 ° C or less to 0.205 mol of methylmagnesium chloride-tetrahydrofuran solution (from magnesium metal 5.0). g is prepared with 100 ml of tetrahydrofuran and methyl chloride. After cooling to room temperature, the reaction was quenched by the addition of a saturated aqueous solution of ammonium chloride. After general extraction, washing, drying, and work-up, the mixture was concentrated under reduced pressure to give 14.43 g (yield: 99%) of the desired product, 8-methylspiro[4.5]indole-8-ol. It was of sufficient purity and was used in the next step without the above purification.

8-methylspiro[4.5]dec-8-ol

Colorless solid

IR (D-ATR): ν = 3334, 2918, 2853, 1443, 1373, 1268, 1130, 993, 891 cm ^-1 .

¹ H-NMR (600MHz 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, 13.9 g of methacrylic acid hydrazine was added dropwise to 14.4 g of 8-methylspiro[4.5]dec-8-ol, 13.5 g of triethylamine, and the amount of the catalyst was 4 a mixture of dimethylaminopyridine, 150 ml of acetonitrile and 100 ml of tetrahydrofuran. After stirring at 50 ° C overnight, it was returned to room temperature, and the reaction was terminated by adding water. After the usual extraction, washing, and drying, the mixture was subjected to a vacuum distillation to obtain 17.0 g (yield: 83%) of the desired product methacrylic acid (8-methyl-8-spiro[4.5] decyl ester).

Methacrylic acid (8-methyl-8-spiro[4.5]decane ester)

Colorless liquid

Boiling point: 78 ° C / 9.3 Pa

IR (D-ATR): ν = 2933, 2854, 1711, 1637, 1445, 1327, 1306, 1176, 1148, 935 cm ^-1 .

¹ H-NMR (600MHz 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, like t, J=0.9Hz), 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 ester) (monomer 10)

Substituting 81.2 g of snail [4.5] 癸-7,9-dione for dihydroisophthalenol by the method described in the literature: Organic Synthesis, Collective Volume 5, page 539, and the like. The corresponding isobutyl enol ether was prepared by using isobutanol instead of ethanol, and purified by silica gel column chromatography to obtain 9-isobutyloxyspiro[4.5]dec-8-ene-7-one (yield 56%).

9-isobutyloxyspiro[4.5]dec-8-ene-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, non Et, 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]decan-8-en-7-one and 150 ml of tetrahydrofuran was added dropwise to lithium hydride 10.0 g and tetrahydrofuran. In a mixture of 400 ml. After stirring overnight at room temperature, the mixture was ice-cooled, and water (20 ml) was added dropwise, followed by dropwise addition of 400 ml of 10% sulfuric acid to terminate the reaction. After stirring at room temperature for 1 hour, it was washed with usual ‧ dry and then treated, and concentrated under reduced pressure to obtain 45.9 g of 8-spiro[4.5]nonene-7-one and 8-spiro[4.5]decene. a mixture of -7-alcohols. 50 ml of tetrahydrofuran and a catalyst amount of 10% palladium-carbon were added to 45.8 g of the resulting mixture, and hydrogenated at 14 kg/cm ² . After filtering the catalyst and concentrating 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]nonanone and 8.92 g (yield 23%) of 7- Snail [4.5] sterol.

7-spiro[4.5]nonanone

Colorless liquid

IR (D-ATR): ν = 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=21.18, 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] sterol

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=21.34, 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 under a nitrogen atmosphere, 12.0 g of dimethyl hydrazine was added to a mixture of 14.4 g of chloroform and 100 ml of dichloromethane, and the mixture was stirred for 10 minutes. Next, a mixture of 8.72 g of 7-spiro[4.5]nonanol and 20 ml of dichloromethane was added dropwise at -55 ° C or lower, and stirred at -70 ° C for 30 minutes. Further, after adding 50 g of triethylamine, the temperature was raised to -5 ° C while stirring. The reaction mixture was poured into a saturated aqueous solution of ammonium chloride, and then washed, washed, dried, concentrated, and concentrated, and then purified by silica gel column chromatography to obtain 8.22 g (yield: 96%) of 7-spiral [ 4.5] Anthrone. Its optical properties are consistent with those described above.

While stirring under a nitrogen atmosphere at room temperature, a mixture of 39.1 g of 7-spiro[4.5]fluorenone and 100 ml of tetrahydrofuran was added dropwise to a solution of methylmagnesium chloride-tetrahydrofuran 0.502 mol (from magnesium metal 12.2 g and tetrahydrofuran). 500ml and methyl chloride modulation). After stirring overnight at room temperature, the reaction was quenched by the addition of a saturated aqueous solution of ammonium chloride. After general extraction, washing, drying, and work-up, the mixture was concentrated under reduced pressure to give 42.3 g (yield: 95%) of the desired product, 7-methylspiro[4.5]indole-7-ol. It was of sufficient purity and was used in the next step without the above purification.

7-methylspiro[4.5]dec-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 = 1.02-1.09 (1H, m), 1.05 (3H, s), 1.17-1.65 (15H, m), 3.76 (1H, OH, s) ppm.

^{1 3} 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, 41.0 g of methacrylic acid ruthenium chloride was added dropwise to 42.0 g of 7-methylspiro[4.5]indole-7-ol, 40.2 g of triethylamine, and the amount of catalyst 4-2-4. A mixture of methylaminopyridine, 400 ml of acetonitrile and 50 ml of tetrahydrofuran. The mixture was stirred at 50 ° C for 1 hour, stirred at room temperature overnight, further stirred at 50 ° C for 1 hour, returned to room temperature, and quenched by the addition of water. After general extraction, washing, and drying, the mixture was subjected to a vacuum distillation to obtain 43.7 g (yield: 78%) of the desired material, 7-methyl-7-spiro[4.5] decyl methacrylate.

7-methyl-7-spiro[4.5]decyl methacrylate

Colorless liquid

Boiling point: 95 ° C / 73 Pa

IR (D-ATR): ν = 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, 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, 22.11, 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 by the following formulation.

[Synthesis Example 9-1] Synthesis of Polymer-1

6.14 g of methyl propyl acid (6-methyl-6-spiro[4.5] oxime ester), 5.12 g of 3-hydroxy-1-adamantyl methacrylate, and methacrylic acid 4 under a nitrogen atmosphere. 8-dioxatricyclo[4.2.1.0 ^3,7 ]non-5-one-2-yl ester 8.74g, 2,2'-azobisisobutyronitrile 0.57g and 2-mercaptoethanol 0.1g dissolved in A solution was prepared by using 22.09 g of propylene glycol monomethyl ether acetate and 18.97 g of γ-butyrolactone. The solution was stirred at 80 ° C under a nitrogen atmosphere, and added dropwise to 6.28 g of propylene glycol monomethyl ether acetate and 5.39 g of γ-butyrolactone over 4 hours. After completion of the dropwise addition, the mixture was stirred at 80 ° C for 2 hours, and after cooling to room temperature, the polymerized droplets were added to 320 g of methanol. The precipitated solid component was filtered, 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%. Further, Mw represents a weight average molecular weight measured by GPC in terms of polystyrene.

[Synthesis Example 9-2 to 29, Synthesis Comparative Example 3-1 to 10] Synthesis of Polymer 2 to 39

The resin having the following structure and each monomer composition ratio was produced in the same manner as in the above [Synthesis Example 9-1] except that the type of each monomer and the blending ratio were changed.

[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, Comparative Examples]

Modulation of photoresist materials

[Examples 1-1 to 35, Comparative Examples 1-1 to 11]

The resin of the present invention (polymers 1 to 29) and the resin (polymer 30 to 39) of the comparative examples produced above were used as a base resin, and an acid generator, a basic compound and a solvent were added in the composition shown in Table 1. ,2. After being mixed and dissolved, it was filtered through a filter (pore size: 0.2 μm) manufactured by Teflon (registered trademark) to obtain a photoresist material (R-01 to 35) of the present invention, that is, a photoresist material for a comparative example (R-36). ~46). Further, the solvent is a KH-20 (manufactured by Asahi Glass Co., Ltd.) containing 0.01% by mass of a surfactant.

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

Further, in Table 1, the basic compound and the solvents 1 and 2 shown by abbreviations are as follows.

Base-1: 2-morpholinyl ethyl octanoate

PGMEA: propylene glycol monomethyl ether acetate

CyHO: cyclohexanone

Evaluation of photoresist materials 1 sensitivity comparison

[Examples 2-1 to 7 and Comparative Examples 2-1 to 5]

In the photoresist materials (R-01 to 35) obtained in Example 1 and the photoresist materials (R-36 to 46) used in the comparative examples, the photoresist materials described in Table 2 below were coated by spin coating. The film was heat-treated at 120 ° C for 60 seconds on a silicon wafer coated with an anti-reflection film (manufactured by Nissan Chemical Industries, Inc., ARC29A, 78 nm) to form a photoresist film having a thickness of 150 nm. The open frame exposure was performed using an ArF excimer laser stepper (manufactured by Nikon Co., Ltd., NA = 0.85), and heat treatment (PEB) was performed at 120 ° C for 60 seconds, and then using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. After oscillating the image for 30 seconds, the minimum exposure amount (E ₀ ) at which the thickness of the photoresist film became zero was obtained. The smaller the E ₀ is, the higher the sensitivity, and the photoresist base resin is considered to be highly reactive.

The evaluation results of the respective photoresists are shown in Table 2.

From the results described in Table 2, the acid dissociable ester type monomer having a spiro ring structure of the present invention is considered to be highly reactive. For example, comparing the results of Comparative Example 2-1 with Example 2-1, it was confirmed that the spiro ring bond of the monomer 1 is helpful for the acid acid dissociation reaction. Further, as a result of Comparative Example 2-2, Comparative Example 2-3, and Example 2-1, the position of the spiro bond was adjacent to the monomer 1 of the acid dissociation reaction point, and the acid dissociation reaction was closer than the spiro bond position. When one or two carbon monomers 9 and 10 are more reactive, it is confirmed that the acid dissociation reaction is reactive due to the bonding position of the spiro ring. Further, with the difference in reactivity which is slightly observed in the results of Comparative Example 2-2 and Comparative Example 2-3, it is considered that the spiro ring bond is located at the position where the acid dissociation reaction point is separated from the six-membered ring by a single carbon 10 The 1,3-diaxial interaction of the acid dissociation reaction is therefore considered to be slightly higher reactivity than monomer 9.

Evaluation of photoresist materials 2 Comparison of pattern resolution [Examples 3-1 to 35, Comparative Examples 3-1 to 11]

The photoresist material (R-01-35) of the present invention and the photoresist material for comparison (R-36-46) are applied by spin coating to an antireflection film (manufactured by Nissan Chemical Industries Co., Ltd.). ARC29A, 90 nm) was heat-treated at 100 ° C for 60 seconds to form a photoresist film having a thickness of 100 nm. A photoresist film material (manufactured by Shin-Etsu Chemical Co., Ltd., SIOC-3, 50 nm) was spin-coated on the photoresist film, and heat-treated (90 ° C, 60 seconds), using ArF liquid immersion molecular laser step The feeder (manufactured by Nikon), NA=1.30), the transfer exposure is depicted as a 6% semi-transmissive phase retardation mask, and after heat treatment (PEB) for 60 seconds, 2.38 mass% of hydroxide is used. The methylammonium aqueous solution was subjected to scouring for 30 seconds to form a line and space pattern. In PEB, the optimum temperature is used for each photoresist material. The above-mentioned empty SEM (scanning electron microscope) was used to observe the wafer of the formed pattern, and the line width in the 40 nm 1:1 line and the space transfer pattern was measured, and the dependence of the line width on the exposure amount was investigated. The exposure amount at which the 40 nm line was formed was taken as the optimum exposure amount (mJ/cm ² ). Next, the exposure amount is determined to be within 40 nm ± 10% of the line width, and the exposure amount is divided by the percentage of the optimum exposure amount as the exposure margin. The larger the value, the smaller the dimensional change due to the change in exposure amount, and the exposure margin is good. Moreover, in order to obtain the scale of the faith of the mask, in the optimum exposure amount, the line width formed on the photoresist is plotted against the line width of the mask, and the slope of the approximate line is calculated, and the value is used as the mask error enhancement factor. (MEEF). The smaller the MEEF value is, the higher the faith of the mask is, and it is good because it can suppress the influence of the error of the mask pattern modification. In addition, in order to compare the roughness, the line width length was measured at a time interval of 100 μm in a range of 2 μm from the line of 40 nm 1:1 line and space. Next, the 3σ value of the measured values is calculated as the line width roughness (LWR). The smaller the LWR value, the smaller the roughness and the better.

The evaluation results of the respective photoresist materials are shown in Table 3.

From the results described in Table 3, it was confirmed that the photoresist material of the present invention has excellent resolution properties 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, and Example 3-4 Comparing with Examples 3-5 and Examples 3-6, it was confirmed that the difference in the resolution performance due to the presence or absence of the spiro structure or the difference in the spiro bond position in the acid dissociable monomer, and the present invention The acid generator combination can further improve the resolution.

Evaluation of photoresist materials 3 PEB temperature dependence [Examples 4-1 to 3, Comparative Examples 4-1 to 3]

Based on the 1:1 line and space pattern evaluation conditions of 40 nm of the above Examples 3-1 to 35 and Comparative Examples 3-1 to 11, the PEB temperature dependence of the line width of the optimum exposure amount was investigated.

In the photoresist materials (R-01 to 35) obtained in Example 1 and the photoresist materials (R-36 to 46) used in the comparative examples, the photoresist materials described in Table 4 were selected for each photoresist. In the range of ±B °C of the optimum PEB temperature shown in Table 4, change the PEB temperature on the scale of 2 °C, plot the line width to the PEB temperature, and insert the least square method of the linear approximation to compare the slope (nm/°C). ). The smaller the slope is, the smaller the PEB temperature dependency is, and the dimensional change due to the difference in thermal history on the wafer surface is suppressed.

The evaluation results are shown in Table 4.

From the results described in Table 4, it was confirmed that the photoresist of the present invention has a small PEB temperature dependency.

Claims (5)

An acid-dissociable ester type monomer having a spiro ring structure represented by the following general formula (2) or (3), (wherein X represents a divalent group of a substituted or unsubstituted cyclopentane ring, a cyclohexane ring or an original norbornane ring together with a carbon atom to which it is bonded, and R ¹ represents a hydrogen atom, a fluorine atom, Methyl or trifluoromethyl, R ² represents 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 a linear chain having a carbon number of 1 to 10. a branched or cyclic monovalent hydrocarbon group, or R ³ and R ⁴ represent a bond between each other and a carbon atom to which they are bonded to form a substituted or unsubstituted cyclopentane ring or a divalent group of a cyclohexane ring R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, and p represents 0 or 1). A polymer compound comprising a repeating unit obtained from an acid-dissociable ester type monomer having a spiro ring structure represented by the following general formula (1a) to (3a); (wherein, Za represents a trivalent group derived from a valence group Z having a polymerizable double bond and produced by polymerization, and X represents a substituted or unsubstituted cyclopentane together with a carbon atom to which it is bonded a divalent group of a ring, a cyclohexane ring or an ornidyl ring, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and R ² represents a linear, branched or cyclic carbon number of 1 to 10. a 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 bond to each other and the like. The carbon atoms together form a divalent group of a substituted or unsubstituted cyclopentane ring or a cyclohexane ring, R ⁵ represents a hydrogen atom or a methyl group, n represents 1 or 2, and p represents 0 or 1). A photoresist material characterized by containing the polymer compound of the second aspect of the patent application as a base resin and a compound which induces an acid upon irradiation with active light or radiation. A photoresist material according to item 3 of the patent application, wherein the compound which generates an acid by active light or radiation is an onium salt compound represented by the following formula (4): (wherein R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom, and a carbon number of 1 to 10; The alkoxy group or a halogen atom, and R ⁹ represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, and R ¹⁰ represents a hydrogen atom or a trifluoromethyl group. A pattern forming method, comprising the steps of coating a photoresist material of claim 3 or 4 on a substrate, heating the film through a mask with a high energy line or an electron beam, and optionally After the heat treatment, the step of developing the developing liquid is used.