JP2004137262A - Fluorene derivative and optically active compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optically active compound having a high sensitivity toward a light source of a short wave length and useful for forming a pattern in a high resolution in a use for a resist. <P>SOLUTION: This optically active compound is used by combining with a photosensitive agent and constituted by an optically active compound (a fluorene derivative) expressed by formula (I) [wherein, J<SP>1</SP>, J<SP>2</SP>are each a linking group; X<SP>1</SP>-Pro<SP>1</SP>, X<SP>2</SP>-Pro<SP>2</SP>are each a hydrophilic group blocked by eliminative groups Pro<SP>1</SP>or Pro<SP>2</SP>; R<SP>1</SP>to R<SP>4</SP>are each an alkyl, an alkenyl, an alkoxy, a cycloalkyl, an aryl, a halogen atom or hydroxy; m1, m2 are each 0 or 1: n1 and n2 are each 0 or a 1-4 integer; and p1, p2, q1 and q2 are each a 0-4 integer, provided that at least one of n1 and n2 is 1-4, and (n1+p1) and (n2+p2) are each ≤5 integer]. <P>COPYRIGHT: (C)2004,JPO

Description

INDUSTRIAL APPLICABILITY The present invention is used in combination with a novel fluorene derivative, in particular, a photosensitizer, and is useful for forming a fine pattern such as a semiconductor integrated circuit using a light beam such as an ultraviolet ray or a far ultraviolet ray (including an excimer laser). It relates to a fluorene derivative.

In the field of semiconductor resists, with the development of VLSI, more advanced fine processing technology is required. In place of g-line (wavelength 436 nm) and i-line (wavelength 365 nm) of the conventional high-pressure mercury lamp, a shorter time is required. A light source having a wavelength, for example, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and an F ₂ excimer laser (wavelength 157 nm) are used.

(4) In addition to the increase in the degree of integration of semiconductor integrated circuits, there is also a demand for improvements in resolution of resists (pattern formation of sub-micron or quarter-micron or less) and improvement in etching resistance in a dry development process.

However, a conventional resist material using g-line or i-line, for example, a novolak resin / diazonaphthoquinone-type positive resist has a high sensitivity even when using a KrF excimer laser or an ArF excimer laser due to light absorption of the novolak resin. And the resolving power is greatly reduced.

As a resist applicable to an exposure source having a shorter wavelength, I. Sondi and E. Matijevic, Resist Technology and Processing XVII, Francis M. Houlihan, Editor, Proceedings of SPIE Vol. 3999 (2000) (Non-Patent Document 1) Pp. 627-637 disclose a film composed of a p-hydroxystyrene-t-butyl acrylate copolymer containing SiO ₂ nanoparticles (silica sol), and a resist containing such SiO ₂ nanoparticles is disclosed. It describes that high resolution is exhibited and that a resist system using transparent SiO ₂ nanoparticles is useful for wavelengths such as 157 nm. However, in such a method, the difference in dissolution rate between the exposed part and the unexposed part cannot be increased, and the resolution cannot be sufficiently improved.

Further, JP-A-6-51519 (Patent Document 1) discloses that an acid-decomposable group having at least two groups capable of decomposing with an acid together with a resin insoluble in water and soluble in an aqueous alkali solution and an acid generator is disclosed. A positive-type photosensitive composition containing a compound having 10 or more bonding atoms excluding an acid-decomposable group at the position where the distance between them is the longest is disclosed. JP-A-6-167811 (Patent Document 2) discloses a low molecular weight resin together with a resin in which part of an alkali-affinity functional group in an alkali-soluble resin is protected by an acid dissociable group and a radiation-sensitive acid generator. A radiation-sensitive resin composition containing a compound in which a hydrogen atom of a phenolic compound is substituted with an alkoxyalkyl group or a t-alkoxycarbonylalkyl group is disclosed. However, even with these compositions, sensitivity and resolution cannot be sufficiently improved.
I. Sondi and E. Matijevic, Resist Technology and Processing XVII, Francis M. Houlihan, Editor, Proceedings of SPIE Vol. 3999 (2000) (pp. 627-637) JP-A-6-51519 (Claim 1) JP-A-6-167811 (Claim 1)

Accordingly, an object of the present invention is to provide a novel photoactive compound, particularly a photoactive compound, a resist additive and a photosensitive resin composition useful for improving the sensitivity and resolution of a resist in combination with a photosensitizer. Is to do.

Another object of the present invention is to provide a photoactive compound, a resist additive, and a photosensitive resin composition which are highly sensitive to an exposure source having a short wavelength and are useful for forming a fine pattern with high resolution. Is to do.

Still another object of the present invention is to provide a photoactive compound, a resist additive and a photosensitive resin composition useful for increasing the difference in solubility in a developer between an exposed portion and an unexposed portion. .

Another object of the present invention is to provide a fluorene derivative useful for forming a fine pattern such as a semiconductor integrated circuit.

The present inventors have conducted intensive studies to achieve the above object, and as a result, when a novel fluorene derivative is used in combination with a photosensitizer, the sensitivity and resolution of the resist can be improved even with a shorter wavelength light source such as a KrF excimer laser. The inventors have found that it can be easily improved, and have completed the present invention.

That is, the fluorene derivative of the present invention is represented by the following formula (I).

(Wherein, J ¹ and J ² are a linking group, -X ¹ -Pro ¹ and -X ² -Pro ² are hydrophilic groups protected by a removable protecting group Pro ¹ or Pro ² , respectively, and R ¹ to R ⁴ represents an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, an aryl group, a halogen atom or a hydroxyl group, m1 and m2 are 0 or 1, n1 and n2 are 0 or an integer of 1 to 4, p1, p2 , Q1 and q2 represent an integer of 0 to 4, provided that at least one of n1 and n2 is 1 to 4, and n1 + p1 and n2 + p2 are integers of 5 or less.)
In the above formula (I), -X ¹ -Pro ¹ and -X ² -Pro ² may be a hydroxyl group or a carboxyl group protected by a protecting group. Pro ¹ and Pro ² may be an acetal-based protecting group or an alkyl ester-based protecting group, for example,-(J ¹ ) _m1 -X ¹ -Pro ¹ and-(J ² ) _m2 -X ² -Pro ² is —O—CH (R ^a ) —OR ^b or —OC (O) —OR ^c (where R ^{a to} R ^c are the same or different and represent an alkyl group) Good. _{^{Furthermore, - (J 1) m1 -X}} 1 -Pro 1 and _{^{- (J 2) m2 -X 2}} -Pro 2 ^{is, -C (R d) = C} (R e) -C (O) -OR f ( In the formula, R ^d and ^Re represent a hydrogen atom or an alkyl group, and R ^f represents an alkyl group. In the formula (I), usually, p1 and p2 is an integer of 0 to 2, is q1 and q2 are 0, R ¹ and R ² is an alkyl group.

The present invention also includes a photoactive compound used in combination with a photosensitizer, the photoactive compound being composed of the fluorene derivative. The protecting group Pro (the protecting groups Pro ¹ and Pro ² ) may be detachable in association with the photosensitizer by light irradiation.

The present invention also includes a photosensitive resin composition composed of a base resin, a photosensitive agent, and the photoactive compound. The photosensitive resin composition may be water- or alkali-developable, or may be a positive photosensitive resin composition. The base resin may be composed of a resin capable of generating a hydrophilic group by the action of an acid, and the photosensitizer may be composed of a photoacid generator. The base resin may be composed of, for example, a homopolymer or a copolymer of a monomer having a hydrophilic group selected from a hydroxyl group and a carboxyl group and having a protective group that can be removed by the action of an acid. Good.

The present invention further includes a resist additive composed of the fluorene derivative (I).

The fluorene derivative (I) of the present invention is a novel photoactive compound and can be hydrophilized by deprotection caused by light irradiation. And the like, and is useful for improving the sensitivity and resolution of a resist formed of a photosensitive resin composition containing the same. Further, the sensitivity to a short wavelength exposure source can be improved, and the resolution of a fine pattern can be improved. Further, the difference in solubility in the developing solution between the exposed and unexposed portions of the resist can be increased, and a fine pattern can be formed with high sensitivity and high resolution.

[Fluorene derivative]
In the fluorene derivative (I), the linking groups J ¹ and J ² are, for example, a direct bond, an alkylene group [methylene, ethylene, dimethylmethylene, di (trifluoromethyl) methylene, propylene, trimethylene, tetramethylene, t-butylene, etc. Linear or branched alkylene group (e.g., C _1-6 alkylene group)], alkenylene group [e.g., C _2-4 alkenylene group such as vinylene, isopropenylene, propenylene], alkynylene group [e.g., C _{2 -4} alkynylene group, etc.], cycloalkylene group [C _4-8 cycloalkylene group such as cyclohexylene group, etc.], and arylene group [C _6-10 arylene group such as phenylene group, etc.]. In addition, the repeating numbers m1 and m2 of the linking group are 0 or 1.

The linking groups J ¹ and J ² are usually a direct bond, an alkylene group [a linear or branched alkylene group (eg, a C _1-6 alkylene group)], an alkenylene group [a C _2-4 alkenylene group such as vinylene, etc.] , Alkynylene group [C _2-4 alkynylene group such as ethynylene group], cycloalkylene group [C _4-8 cycloalkylene group such as cyclohexylene group], arylene group [C _6-10 arylene group such as phenylene] And particularly, a direct bond, an alkenylene group, or an alkylene group.

Further, the hydrophilic groups corresponding to the groups X ¹ and X ² protected by the protecting groups Pro ¹ and Pro ² (hereinafter, the group X may be simply referred to as a hydrophilic group) include an amino group and an N-substituted amino group. Groups (such as N, N-diC _1-4 alkylamino groups), hydroxyl groups (including hydroxy (poly) alkoxy groups), carboxyl groups, and sulfur-containing derivative groups corresponding to these hydrophilic groups Examples thereof include hydrophilic groups such as a mercapto group, a thiocarboxyl group, a dithiocarboxyl group, and the like (a group that imparts water or alkali solubility to diphenylfluorene). Particularly, a hydroxyl group, a —O— (AO) _r —H group (where A represents a C _2-4 alkylene group, and r represents an integer of 1 or more) and a carboxyl group are preferred.

As the protecting group for these hydrophilic groups, conventional protecting groups (removable in connection with light irradiation or by an acid) can be used. For example, "PROTECTIVE GROUPS in ORGANIC SYNTHESIS, THIRD EDITION", Green Wuts, WILEY -Refer to INTERSCIENCE, published in 1999.

Examples of the protecting group for the hydroxyl group (including the —O— (AO) _r —H group) include, for example, methyl, ethyl, propyl, isopropyl, isobutyl, s-butyl, t-butyl, 2-cyclohexyl-2-propyl, A linear or branched C _1-12 alkyl group which may have a substituent such as a hexyl group (preferably a C _1-10 alkyl group, more preferably a C _1-6 alkyl group); an allyl group, etc. Linear or branched alkenyl group (preferably 2-C _3-10 alkenyl group, more preferably 2-C _3-6 alkenyl group); chloromethyl, fluoromethyl, trichloromethyl, trifluoromethyl, pentafluoro Halo C _1-6 alkyl group such as propyl group (preferably halo C _1-4 alkyl group, more preferably fluoro C _1-4 alkyl group); linear or branched such as methylthiomethyl group A chain alkylthioalkyl group (preferably a C _1-6 alkylthio C _1-6 alkyl group); a C _5-8 cycloalkyl group which may have a substituent such as a cyclohexyl group and a 1-methylcyclohexyl group (for example, A C _5-6 cycloalkyl group); an optionally substituted decalinyl group or hydrogenated naphthyl group (eg, 1-decalinyl, 2-decalinyl, 2-methyl-2-decalinyl group, etc.), An adamantyl group which may have (for example, 1-adamantyl, 2-adamantyl, 1-methyl-2-adamantyl, 2-methyl-2-adamantyl group, etc.), a norbornyl group which may have a substituent ( For example, 1-norbornyl, 2-norbornyl, 2-methyl-2-norbornyl group, etc., and optionally substituted boronyl group (for example, 2-bornyl group) And the like may have a substituent such as a 2- to 4-cyclic C _3-30 hydrocarbon ring group (a bridged cyclic alicyclic hydrocarbon group (for example, a bi-tetracycloalkyl group)); naphthyl Group (eg, 2-naphthyl group), hydrogenated naphthyl group (eg, 1,4-dihydro-2-naphthyl group), anthryl group (eg, 9- (9-phenyl-10-oxa) anthryl group, etc. ), An aryl group such as a 2,4-dinitrophenyl group (eg, a nitro-substituted phenyl group); benzyl, 2,6-dichlorobenzyl, 2-nitrobenzyl, triphenylmethyl Aralkyl groups such as α-naphthyldiphenylmethyl, p-methoxyphenyldiphenylmethyl (for example, an optionally substituted mono- to tri-C _6-10 aryl-C _1-4 alkyl group; Arylselenylalkyl groups such as 2- (phenylselenyl) ethyl group; oxacycloalkyl groups such as tetrahydrofuranyl, tetrahydropyranyl, and 4-methoxytetrahydropyranyl (for example, 5- to 8-membered oxacycloalkyl groups) Thiacycloalkyl groups such as tetrahydrothiafuranyl, tetrahydrothiapyranyl, and 4-methoxytetrahydrothiapyranyl groups (for example, a 5- to 8-membered thiacycloalkyl group); linear or branched alkoxyalkyl Groups (e.g., C _1-10 alkoxy-C _1-6 alkyl groups such as 1-methoxyethyl, 1-ethoxyethyl, 1-ethoxypropyl, 1-methoxy-isopropyl, 1-methyl-1-methoxyethyl groups, preferably the C _1-6 alkoxy -C _1-4 alkyl group, more preferably C _1-4 alkoxy Shi -C _1-4 alkyl group) or an alkoxyalkoxy group (e.g., 2-methoxyethoxy C _1-4 alkoxy -C _1-4 alkoxy -C _1-4 alkyl group such as methyl group), dialkoxy alkyl group [ For example, a bis (halogenated C _1-4 alkoxy) C _1-4 alkyl group such as a bis (2-chloroethoxy) methyl group] and the like; an acetal protecting group; a linear or branched alkylcarbonyl group (formyl , Acetyl, propionyl, isopropionyl, butyryl, t-butyryl, valeryl, isovaleryl and the like C _1-10 alkyl-carbonyl group, preferably C _1-8 alkyl-carbonyl group, more preferably C _1-6 alkyl-carbonyl group , in particular C _1-4 alkyl - carbonyl group), C _5-8 Shikuroa such cycloalkyl group (a cyclohexyl group Kill - carbonyl group, preferably a C _5-6 cycloalkyl - carbonyl group), arylcarbonyl groups (C _6-10 aryl, such as benzoyl group - acyl group such as carbonyl group); t-butoxycarbonyl (t-BOC) Linear or branched C _1-6 alkoxy-carbonyl group (eg, C _1-4 alkoxy-carbonyl group); aralkyloxycarbonyl group (eg, C _6-10 aryl) such as benzyloxycarbonyl group; -C _1-4 alkyloxy -, carbonyl groups); trimethylsilyl, isopropyl dimethylsilyl, t- butyl dimethyl silyl, linear or branched alkyl silyl group such as triisopropylsilyl group (e.g., C _1-6 alkylsilyl , especially tri C _1-4 alkylsilyl group), straight-chain or branched-chain alkyl aryl silyl group (e.g. If, like t- butyldiphenylsilyl group), an aralkyl silyl group (e.g., tribenzylsilyl group).

Examples of the carboxyl protecting group include, for example, methyl, ethyl, 2,2,2-trichloroethyl, 2-haloethyl, isopropyl, 2-cyclohexyl-2-propyl, butyl, s-butyl, t-butyl, A linear or branched C _1-12 alkyl group which may have a substituent such as a hexyl group (preferably a C _1-10 alkyl group, more preferably a C _1-6 alkyl group); methylthiomethyl, A straight-chain or branched-chain alkylthioalkyl group such as St-butyl group (preferably a C _1-6 alkylthio-C _1-6 alkyl group); a straight-chain or branched-chain alkoxyalkyl group (for example, a methoxymethyl group) aralkyloxy group (e.g., benzyloxymethyl group);; C _1-4 alkoxy -C _1-4 alkyl group), such as arylcarbonyl group (e.g., off Etc. Nasir group); cyclohexyl, optionally C _3-8 cycloalkyl group which may have a substituent such as a 1-methylcyclohexyl group; which may have a substituent decalinyl group (e.g., 1-decalinyl, 2 -Decalinyl, 2-methyl-2-decalinyl group and the like, and an optionally substituted adamantyl group (for example, 1-adamantyl, 2-adamantyl, 1-methyl-2-adamantyl, 2-methyl-2- Adamantyl group), optionally substituted norbornyl group (eg, 1-norbornyl, 2-norbornyl, 2-methyl-2-norbornyl group, etc.), optionally substituted boronyl group ( for example, 2-bornyl group) substituents optionally may 2-4 bicyclic C _3-30 be hydrocarbon Hajime Tamaki having a (crosslinked cyclic alicyclic hydrocarbon group, etc.); 2,4 Gini Aryl groups such as a lophenyl group (eg, a nitro-substituted phenyl group); benzyl, 2,6-dichlorobenzyl, 2-nitrobenzyl, triphenylmethyl, bis (o-nitrophenyl) methyl, 9-anthrylmethyl, Aralkyl groups such as 2- (9,10-dioxa) anthrylmethyl group (for example, mono- to tri-C _6-10 aryl-C _1-4 alkyl group which may have a substituent); phthalimidoalkyl group (E.g., N-phthalimidomethyl group); arylalkenyl group (e.g., cinnamyl group); arylsulfonylalkyl group [e.g., 2- (p-toluenesulfonyl) ethyl group]; Good tetrahydrofuranyl group (for example, tetrahydrofuran-3-yl group, 3-methyltetrahydrofuran-3- An optionally substituted tetrahydropyranyl group (eg, a tetrahydropyran-3-yl group, a 3-methyltetrahydropyran-3-yl group). An oxacycloalkyl group (e.g., a 5- to 8-membered oxacycloalkyl group); a γ-butyrolactone ring group optionally having a substituent (e.g., tetrahydro-2-furanone-4-yl, 4-methyl) A tetrahydro-2-furanone-4-yl group or the like, and an optionally substituted δ-valerolactone ring group (for example, tetrahydro-2-pyron-4-yl, 4-methyltetrahydro-2-pyrone- A lactone ring group which may have a substituent such as a 4-yl group); a carbamoyl group which may have a substituent (such as an alkyl group or an aryl group) [carbamoyl Groups; N-C _1-6 alkyl-carbamoyl groups (preferably N-C _1-4 alkyl-carbamoyl groups) such as N-methylcarbamoyl and N-ethylcarbamoyl groups; and C _6-10 arylcarbamoyl groups such as phenylcarbamoyl groups. A diC _1-4 alkyl phosphinothioyl group such as a dimethylphosphinothioyl group; a diC _6-10 arylphosphinothioyl group such as a diphenylphosphinothioyl group, and an alkylsilyl such as a trimethylsilyl group. Groups (eg, C _1-6 alkylsilyl, especially tri-C _1-4 alkylsilyl).

In particular, the protective group is preferably a hydrophobic protective group that imparts hydrophobicity to a hydrophilic group. For example, as the protecting group for the hydroxyl group, a linear or branched acyl group (particularly a C _1-6 alkyl-carbonyl group such as a t-butylcarbonyl group or a 2,2-dimethylpropionyl group), a linear or branched Branched alkoxycarbonyl group (C _1-6 alkoxycarbonyl group such as t-BOC group), 5- or 6-membered oxacycloalkyl group (tetrahydropyranyl group, etc.), bi- or tri- A cycloalkyl group (having a substituent such as a norbornyl group, 2-adamantyl, and 2-methyl-2-adamantyl group which may have a substituent such as 2-norbornyl and 2-methyl-2-normanyl); And a straight-chain or branched-chain alkoxyalkyl group (1-methoxyethyl, 1-ethoxyethyl, 1-ethoxypropyl, - methoxy - such as C _1-6 alkoxy -C _1-6 alkyl group such as isopropyl group (particularly C _1-4 alkoxy -C _1-4 alkyl group)), a linear or branched C _1-4 alkylsilyl And the like. Examples of the carboxyl-protecting group include a linear or branched alkyl group (a C _1-4 alkyl group such as a t-butyl group), an optionally substituted bis or tricycloalkyl group (a bridged ring). Formula alicyclic hydrocarbon group, for example, 2-norbornyl, norbornyl group which may have a substituent such as 2-methyl-2-norbornyl group, 2-adamantyl, 2-methyl-2-adamantyl group, etc. An adamantyl group which may have a substituent, a 5- or 6-membered oxacycloalkyl group which may have a substituent, a lactone ring group which may have a substituent, a carbamoyl group or N- A substituted carbamoyl group is preferred. Among these protective groups, an alkyl group or an alkoxy group is preferably a short-chain alkyl group having about 1 to 2 carbon atoms or a branched structure.

Incidentally, fluorene derivative (I) may have at least one protected hydrophilic _{^{group, - (J 1) m1 -X}} 1 -Pro 1 or ^{_{- (J 2) m2 -X 2}} -Pro Instead of ² , it may have a hydrophilic group (hydroxyl group, carboxyl group) having no protective group.

N1 or n2 is preferably 0 to 3, particularly preferably 1 to 2. The sum of n1 and n2 (n1 + n2) may be, for example, 1 to 8, preferably 1 to 6 (particularly, 1 to 4).

R ^{1 to} R ⁴ represent an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a halogen atom or a hydroxyl group, and p1, p2, q1 and q2 are integers of 0 to 4 (preferably 0 to 3, more preferably 0 to 3). Represents 0 to 2, especially 0 or 1). p1 and p2 are usually 0 to 2 (particularly 0 or 1), and q1 and q2 are usually 0. The types of the substituents R ^{1 to} R ⁴ may be different depending on the values of p1, p2, q1, and q2 indicating the number of the substituents.

Examples of the alkyl group include C _1-6 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl.

Examples of the alkenyl group include C _2-6 alkenyl groups such as vinyl, allyl, butenyl and pentenyl groups.

Examples of the alkoxy group include C _1-6 alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy and t-butoxy groups.

Examples of the cycloalkyl group include a C _4-8 cycloalkyl group (preferably a C _5-6 cycloalkyl group) such as a cyclopentyl and a cyclohexyl group.

Examples of the aryl group include C _1-4 alkylphenyl groups such as phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, and 3,5-dimethylphenyl groups, and a naphthyl group. Can be illustrated.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As R ¹ and R ² , an alkyl group (eg, a C _1-4 alkyl group, particularly a methyl group), an alkenyl group (eg, an allyl group), a cycloalkyl group (eg, a cyclohexyl group), an aryl group (eg, a phenyl group) Group), a halogen atom (eg, a fluorine atom), and particularly a C _1-3 alkyl group such as a methyl group. Furthermore, for example, if n1 is 0, it may be at least one of the hydroxyl groups of R ^1.

Substituents on the benzene ring _{^{- (J 1) m1 -X 1}} -Pro 1 or - and _{^{(J 2) m2 -X 2 -Pro}} 2, the substitution position of the substituents R ¹ or R ² is not particularly limited, For example, the substituent-(J ¹ ) _m1 -X ¹ -Pro ¹ may be any of the 2-, 3-, and 4-positions in the phenyl group, and is preferably the 4-position. Further, a plurality of _{^{- (J 1) m1 -X 1}} -Pro 1 or - (J ²⁾ The same applies to the case with _{m @ 2} -X ² -Pro ^2, for example, if n1 and / or n2 is 2, in the phenyl group, two groups _{^{- (J 1) m1 -X 1}} -Pro 1 ( or _{^{- (J 2) m2 -X 2}} -Pro 2) is 3,4-position, substitution such as 3,5-positions And one-(J ¹ ) _m1 -X ¹ -Pro ¹ or-(J ² ) _m2 -X ² -Pro ² may be usually substituted at the 4-position.

The substitution position of R ¹ (or R ²⁾ is in the phenyl group, 2-position, 3-position may be either of the 4-position, substitution positions of substituents R ¹ (or R ²⁾ is And the phenyl group includes 2,3-position, 2,4-position, 2,6-position, 3,4-position, 3,5-position and the like.

In the formula (I), examples of preferable combinations of coefficients include, for example, a combination in which m1 and m2 are 0 or 1, n1 and n2 are 1 to 3, p1 and p2 are 0 to 2, and q1 and q2 are 0. Is mentioned.

Further, a hydrophilic group corresponding to X ¹ and X ² is a hydroxyl group or a —O— (AO) _r —H group (where A is a C _2-4 alkylene group, and r is an integer of 1 or more) When R ¹ and R ² are each an alkyl group (for example, a C _1-4 alkyl group, particularly a methyl group), an alkenyl group, a cycloalkyl group, an aryl group, or a halogen atom ( Especially a C _1-4 alkyl group), the linking groups J ¹ and J ² are a direct bond, an alkenylene group (especially a vinylene group) or an alkylene group, and the protecting groups Pro ¹ and Pro ² are linear or branched. Acyl group, linear or branched alkoxycarbonyl group, 5- or 6-membered oxacycloalkyl group, bis or tricycloalkyl group which may have a substituent, linear or branched alkoxyalkyl group Or linear or branched Chain C _1-4 alkylsilyl group (of these, in particular, and C _1-6 alkoxycarbonyl groups, C _1-6 alkoxy -C _1-6 alkyl group), such as combinations thereof is.

Further, when the hydrophilic group corresponding to X ¹ and X ² is a carboxyl group, a preferable combination of substituents is that R ¹ and R ² are an alkyl group (for example, a C _1-4 alkyl group, particularly a methyl group ), An alkenyl group, a cycloalkyl group, an aryl group, or a halogen atom (particularly a C _1-4 alkyl group), wherein the linking groups J ¹ and J ² are a direct bond, an alkenylene group or an alkylene group, and the protecting group Pro ¹ and Pro ² are a linear or branched alkyl group, a bis or tricycloalkyl group optionally having a substituent, a 5- or 6-membered oxacycloalkyl group optionally having a substituent, Examples thereof include a combination of a lactone ring group which may have a substituent, a carbamoyl group, and an N-substituted carbamoyl group (particularly, a C _1-4 alkyl group).

In the formula (I), Pro ¹ and Pro ² may be an acetal-based protecting group or an alkyl ester-based protecting group, for example,-(J ¹ ) _m1 -X ¹ -Pro ¹ and-(J ² ) _m2 -X ² -Pro ² (hereinafter sometimes referred to as-(J) _m -X-Pro) is converted to -O-CH (R ^a ) -OR ^b or -OC (O) -OR ^c (formula Wherein R ^{a to} R ^c are the same or different and each represents an alkyl group). Further,-(J) _m -X-Pro is -A ¹ -C (O) -OR ^f (where A ¹ represents an alkylene group or an alkenylene group, and R ^f represents an alkyl group) Is also good.

A fluorene derivative in which the group — (J) _m —X—Pro is —O—CH (R ^a ) —OR ^b is a compound of the formula (I) in which m1 and m2 are 0, and X ¹ and X ² are oxygen. The compound in which the atoms, Pro ¹ and Pro ² are alkoxyalkyl groups may be used. The alkoxyalkyl group which is a protecting group is preferably an acetal type C _1-10 alkoxy-C _1-6 alkyl group, more preferably an acetal type C _1-6 alkoxy-C _1-4 alkyl group (particularly, acetal type C _{1 -4} alkoxyethyl group). Such a fluorene derivative can be represented, for example, by the following formula (Ia).

(In the formula, R ¹ , R ² , R ^{5 to} R ⁸ represent an alkyl group, n1 and n2 represent an integer of 1 to 3, and p1 and p2 represent an integer of 0 to 2).

In the formula (Ia), examples of the alkyl groups R ⁵ and R ⁷ include a C _1-6 alkyl group such as a methyl, ethyl, propyl, and t-butyl group, preferably a C _1-4 alkyl group. And a C _1-3 alkyl group such as a methyl group. Examples of the alkyl groups R ⁶ and R ⁸ include C _1-10 alkyl groups such as methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, pentyl, and hexyl groups, and preferably C _1-6 alkyl groups. And is usually a C _1-3 alkyl group such as a methyl group or an ethyl group. Desirable n1 or n2 is 1 or 2. As the substituents R ¹ and R ² on the benzene ring, a C _1-3 alkyl group such as a methyl group is preferable, and the substitution position is the same as described above. The number of substituents R ¹ and R ² is preferably 0 or 1.

Specific examples of the compound (Ia) include 9,9-bis (alkoxyalkoxyphenyl) fluorenes (compounds in which n1 = n2 = 1) and 9,9-bis {di (alkoxyalkoxy) phenyl} fluorenes (Compounds where n1 = n2 = 2), 9,9-bis {tri (alkoxyalkoxy) phenyl} fluorenes (compounds where n1 = n2 = 3) and the like.

Examples of 9,9-bis (alkoxyalkoxyphenyl) fluorenes include, for example, 9,9-bis {4-[(1-ethoxy) ethoxy] phenyl} fluorene and 9,9-bis {2-[(1-ethoxy) 9,9-bis [(1-C _1-10 alkoxy) C _1-6 alkoxyphenyl] fluorene such as ethoxy] phenyl} fluorene; 9,9-bis {4-[(1-ethoxy) ethoxy] -3 -Methyl-phenyl} fluorene, 9,9-bis {4-[(1-ethoxy) ethoxy] -2-methyl-phenyl} fluorene, 9,9-bis} 2-[(1-ethoxy) ethoxy] -5 -Methyl-phenyl {fluorene, 9,9-bis} 4-[(1-ethoxy) ethoxy] -3-isopropyl-phenyl} fluorene, 9,9-bis {4-[(1-ethoxy) ethoxy 3-isobutyl - phenyl} fluorene, 9,9-bis {4 - [(1-ethoxy) ethoxy] -3-t-butyl - phenyl} fluorene 9,9-bis [(1-C _1-10 Alkoxy) C _1-6 alkoxy-C _1-6 alkylphenyl] fluorene; 9,9-bis {4-[(1-ethoxy) ethoxy] -2,5-dimethyl-phenyl {fluorene, 9,9-bis} 9 such as 4-[(1-ethoxy) ethoxy] -3,5-dimethyl-phenyl} fluorene and 9,9-bis {4-[(1-ethoxy) ethoxy] -2,6-dimethyl-phenyl} fluorene; , 9-bis [(1-C _1-10 alkoxy) C _1-6 alkoxy-di C _1-6 alkylphenyl] fluorene.

As the 9,9-bis {di (alkoxyalkoxy) phenyl} fluorenes, fluorene derivatives corresponding to the above 9,9-bis (alkoxyalkoxyphenyl) fluorenes, for example, 9,9-bis {3,4-diene [(1-ethoxy) ethoxy] phenyl} fluorene, 9,9-bis {3,5-di [(1-ethoxy) ethoxy] phenyl} fluorene such as 9,9-bis {di [(1-C ₁ 9,9-bis {di [, such as ₁₀ alkoxy) C _1-6 alkoxy] phenyl} fluorene; 9,9-bis {3,4-di [(1-ethoxy) ethoxy] -5-methyl-phenyl} fluorene (1-C _1-10 alkoxy) C _1-6 alkoxy] -C _1-6 alkylphenyl {fluorene; 9,9-bis} 2,4-di [(1-ethoxy) ethoxy] -3,6-dimethyl -Phenyl Examples thereof include 9,9-bis {di [(1-C _1-10 alkoxy) C _1-6 alkoxy] -di C _1-6 alkylphenyl} fluorene such as fluorene.

As the 9,9-bis {tri (alkoxyalkoxy) phenyl} fluorenes, fluorene derivatives corresponding to the above 9,9-bis (alkoxyalkoxyphenyl) fluorenes, for example, 9,9-bis {3,4,5 9,9-bistri [(1 such as -tri [(1-ethoxy) ethoxy] phenyl} fluorene, 9,9-bis {2,4,5-tri [(1-ethoxy) ethoxy] phenyl} fluorene; —C _1-10 alkoxy) C _1-6 alkoxy] phenyl} fluorene.

In addition, among these compounds, a compound in which a part of the hydrophilic group is not protected (that is, a compound having an unprotected hydroxyl group) can also be used.

Among these fluorene derivatives, 9,9-bis [(1-C _1-6 alkoxy) C _1-4 alkoxyphenyl] such as 9,9-bis {4-[(1-ethoxy) ethoxy] phenyl} fluorene 9,9-bis [(1-C _1-6 alkoxy) C _1-4 alkoxy-C such as fluorene, 9,9-bis {4-[(1-ethoxy) ethoxy] -3-methyl-phenyl} fluorene _1-3 alkylphenyl] fluorene, 9,9-bis {3,4-di [(1-ethoxy) ethoxy] phenyl} fluorene such as 9,9-bis {di [(1-C _1-6 alkoxy) C 9,9-bis {di [(1-C) such as _1-4 alkoxy] phenyl} fluorene and 9,9-bis {3,4-di [(1-ethoxy) ethoxy] -5-methyl-phenyl} fluorene. _1-6 alkoxy) C _1-4 alkoxy] -C _1-3 a Rukirufeniru} fluorene, 9,9-bis {3,4,5-[(1-ethoxy) ethoxy] phenyl} fluorene such as 9,9-bis {tri [(1-C _1-10 alkoxy) C _{1 -6} alkoxy] phenyl} fluorene and the like are preferred.

Group - (J) _m -X-Pro is a fluorene derivative is a -O-C (O) -OR ^c, in formula (I), m1 and m2 are 0, X ¹ and X ² is an oxygen atom , Pro ¹ and Pro ² may be compounds having an alkoxycarbonyl group. The alkoxycarbonyl group is a protecting group, preferably a linear or branched C _1-6 alkoxy - carbonyl group, more preferably a straight-chain or branched-chain C _1-4 alkoxycarbonyl group (especially branched-chain C _{1 -4} alkoxycarbonyl group). Such a fluorene derivative can be represented, for example, by the following formula (Ib).

(In the formula, R ¹ , R ² , R ⁹ and R ¹⁰ are alkyl groups, n1 and n2 are integers of 1 to 3, and p1 and p2 are integers of 0 to 2).

In the formula (Ib), as the alkyl groups R ⁹ and R ¹⁰ , for example, a straight-chain or branched-chain C such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl group and the like _{A 1-10} alkyl group, preferably a straight-chain or branched C _1-6 alkyl group, etc., is usually a straight-chain C _1-3 alkyl group such as a methyl group or a branched chain such as a t-butyl group. It is a C _3-6 alkyl group (particularly a branched C _3-6 alkyl group). Desirable n1 or n2 is 1 or 2. The substituents R ¹ and R ² on the benzene ring are the same as described above. The number of substituents R ¹ and R ² is preferably 0 or 1.

As the compound (Ib), specifically, 9,9-bis (alkoxycarbonyloxyphenyl) fluorenes (compounds in which n1 = n2 = 1), 9,9-bis {di (alkoxycarbonyloxy) phenyl} Fluorenes (compounds where n1 = n2 = 2) and 9,9-bis {tri (alkoxycarbonyloxy) phenyl} fluorenes (compounds where n1 = n2 = 3) are included.

Examples of 9,9-bis (alkoxycarbonyloxyphenyl) fluorenes include 9,9-bis [4- (t-butoxycarbonyloxy) phenyl] fluorene and 9,9-bis [2- (t-butoxycarbonyloxy) 9,9-bis (C _1-10 alkoxycarbonyloxyphenyl) fluorene such as phenyl] fluorene; 9,9-bis [4- (t-butoxycarbonyloxy) -3-methyl-phenyl] fluorene, 9,9- Bis [4- (t-butoxycarbonyloxy) -2-methyl-phenyl] fluorene, 9,9-bis [2- (t-butoxycarbonyloxy) -5-methyl-phenyl] fluorene, 9,9-bis [ 4- (t-butoxycarbonyloxy) -3-isopropyl-phenyl] fluorene, 9,9-bis [4- (t-buty Shi carbonyloxy) -3-isobutyl - phenyl] fluorene, 9,9-bis [4-(t-butoxycarbonyl-oxy) -3-t-butyl - phenyl] fluorene such as 9,9-bis (C _1-10 Alkoxycarbonyloxy-C _1-6 alkylphenyl) fluorene; 9,9-bis [4- (t-butoxycarbonyloxy) -2,5-dimethyl-phenyl] fluorene, 9,9-bis [4- (t- 9,9-bis (C ₁ ) such as butoxycarbonyloxy) -3,5-dimethyl-phenyl] fluorene and 9,9-bis [4- (t-butoxycarbonyloxy) -2,6-dimethyl-phenyl] fluorene _-10 alkoxy-di C _1-6 alkylphenyl) fluorene.

As the 9,9-bis {di (alkoxycarbonyloxy) phenyl} fluorenes, fluorene derivatives corresponding to the above 9,9-bis (alkoxycarbonyloxyphenyl) fluorenes, for example, 9,9-bis [3,4 9,9-bis [di (C _1-10 alkoxycarbonyl) such as -di (t-butoxycarbonyloxy) phenyl] fluorene and 9,9-bis [3,5-di (t-butoxycarbonyloxy) phenyl] fluorene Oxy) phenyl] fluorene; 9,9-bis [di (C _1-10 alkoxycarbonyloxy)-such as 9,9-bis [3,4-di (t-butoxycarbonyloxy) -5-methylphenyl] fluorene; C _1-6 alkyl phenyl] fluorene; 9,9-bis [2,4-di (t-butoxycarbonyl-oxy) -3,6-dimethyl Butylphenyl] 9,9-bis [di (C _1-10 alkoxycarbonyloxy) of fluorene - and di C _1-6 alkyl phenyl] fluorene can be exemplified.

As the 9,9-bis (tri (alkoxycarbonyloxy) phenyl} fluorenes, fluorene derivatives corresponding to the above 9,9-bis (alkoxycarbonyloxyphenyl) fluorenes, for example, 9,9-bis [3,4 9,9-bis [tri (C ₁ ), such as 2,5-tri (t-butoxycarbonyloxy) phenyl] fluorene and 9,9-bis [2,4,5-tri (t-butoxycarbonyloxy) phenyl] fluorene. _-10 alkoxycarbonyloxy) phenyl] fluorene.

In addition, among these compounds, a compound in which a part of the hydrophilic group is not protected (that is, a compound having an unprotected hydroxyl group) can also be used.

Among these fluorene derivatives, 9,9-bis (C _1-6 alkoxycarbonyloxyphenyl) fluorene such as 9,9-bis [4- (t-butoxycarbonyloxy) phenyl] fluorene, and 9,9-bis [ 9,9-bis (C _1-6 alkoxycarbonyloxy-C _1-3 alkylphenyl) fluorene such as 4- (t-butoxycarbonyloxy) -3-methyl-phenyl] fluorene, 9,9-bis [3, 9,9-bis [di (C _1-6 alkoxycarbonyloxy) phenyl] fluorene such as 4-di (t-butoxycarbonyloxy) phenyl] fluorene, 9,9-bis [3,4-di (t-butoxy) 9,9-bis such carbonyloxy) -5-methylphenyl] fluorene [di (C _1-6 alkoxycarbonyloxy) -C _1-3 alkyl-phenylene ] Fluorene, etc. 9,9-bis [3,4,5-(t-butoxycarbonyl) phenyl] fluorene such as 9,9-bis [tri (C _1-10 alkoxycarbonyloxy) phenyl] fluorene are preferred .

Group - (J) _m -X-Pro is Furureon derivative is -A ¹ -C (O) -OR ^f, in formula (I), m1 and m2 are 1, J ¹ and J ² is alkenylene Or a compound in which X ¹ and X ² are oxycarbonyl groups, and Pro ¹ and Pro ² are alkyl groups. The alkyl group which is a protecting group for the carboxyl group is preferably a linear or branched C _1-6 alkyl group, and more preferably a linear or branched C _1-4 alkyl group. The alkenylene group or alkylene group as a linking group is preferably a C _2-4 alkenylene group such as a vinylene group. Such a fluorene derivative can be represented, for example, by the following formula (Ic).

(Wherein A ¹ and A ² are alkenylene groups, R ¹ , R ² , R ¹¹ and R ¹² are alkyl groups, n1 and n2 are integers from 1 to 3, and p1 and p2 are integers from 0 to 2) .

In the above formula (Ic), the alkyl groups R ¹¹ and R ¹² are linear or branched C _1-10 such as methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, pentyl and hexyl groups. alkyl group, preferably such as straight-chain or branched-chain C _1-6 alkyl group and the like, usually, branched C _3, such as linear C _1-3 alkyl group or a t- butyl group such as a methyl group _-6 alkyl group (particularly, a branched C _3-6 alkyl group). Examples of the alkenylene groups A ¹ and A ² include C _2-4 alkenylene groups such as vinylene, propenylene, and methylvinylene group, and are usually vinylene groups. That is, in the fluorene derivative (Ic), for example,-(J) _m -X-Pro is represented by -C (R ^d ) = C (R ^e ) -C (O) -OR ^f (where R ^d and R ^e represents a hydrogen atom or an alkyl group, and R ^f represents an alkyl group). Desirable n1 or n2 is 1 or 2. The substituents R ¹ and R ² on the benzene ring are the same as described above. The number of substituents R ¹ and R ² is preferably 0 or 1.

As the compound (Ic), specifically, 9,9-bis (alkoxycarbonylvinylphenyl) fluorenes (compounds in which n1 = n2 = 1), 9,9-bis {di (alkoxycarbonylvinyl) phenyl} Fluorenes (compounds where n1 = n2 = 2), 9,9-bis {tri (alkoxycarbonylvinyl) phenyl} fluorenes (compounds where n1 = n2 = 3) and the like are included.

Examples of 9,9-bis (alkoxycarbonylvinylphenyl) fluorenes include 9,9-bis [4- (2-t-butoxycarbonylvinyl) phenyl] fluorene and 9,9-bis [2- (2-t- 9,9-bis (C _1-10 alkoxycarbonylvinylphenyl) fluorene such as butoxycarbonylvinyl) phenyl] fluorene; 9,9-bis [4- (2-t-butoxycarbonylvinyl) -3-methylphenyl] fluorene , 9,9-bis [4- (2-t-butoxycarbonylvinyl) -2-methylphenyl] fluorene, 9,9-bis [2- (2-t-butoxycarbonylvinyl) -5-methylphenyl] fluorene , 9,9-bis [4- (2-t-butoxycarbonylvinyl) -3-isopropylphenyl] fluorene, 9,9-bis 9,9-bis such as 4- (2-t-butoxycarbonylvinyl) -3-isobutylphenyl] fluorene and 9,9-bis [4- (2-t-butoxycarbonylvinyl) -3-t-butylphenyl] fluorene -Bis (C _1-10 alkoxycarbonylvinyl-C _1-6 alkylphenyl) fluorene; 9,9-bis [4- (2-t-butoxycarbonylvinyl) -2,5-dimethylphenyl] fluorene, 9,9 -Bis [4- (2-t-butoxycarbonylvinyl) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-t-butoxycarbonylvinyl) -2,6-dimethylphenyl] fluorene And 9,9-bis (C _1-10 alkoxycarbonylvinyl-di C _1-6 alkylphenyl) fluorene.

As the 9,9-bis (di (alkoxycarbonylvinyl) phenyl) fluorenes, fluorene derivatives corresponding to the above 9,9-bis (alkoxycarbonylvinylphenyl) fluorenes, for example, 9,9-bis [3,4 9,9-bis [di (C _1-10 alkoxycarbonyl) such as -di (t-butoxycarbonylvinyl) phenyl] fluorene and 9,9-bis [3,5-di (t-butoxycarbonylvinyl) phenyl] fluorene Vinyl) phenyl] fluorene; 9,9-bis [di (C _1-10 alkoxycarbonylvinyl)-such as 9,9-bis [3,4-di (t-butoxycarbonylvinyl) -5-methylphenyl] fluorene C _1-6 alkyl phenyl] fluorene; 9,9-bis [2,4-di (t-butoxycarbonyl-vinyl) -3,6-dimethyl Butylphenyl] 9,9-bis [di (C _1-10 alkoxycarbonyl vinyl) such as fluorene - and di C _1-6 alkyl phenyl] fluorene can be exemplified.

As the 9,9-bis {tri (alkoxycarbonylvinyl) phenyl} fluorenes, fluorene derivatives corresponding to the above 9,9-bis (alkoxycarbonylvinylphenyl) fluorenes, for example, 9,9-bis [3,4 9,9-bis [tri (C ₁ ) such as 2,5-tri (t-butoxycarbonylvinyl) phenyl] fluorene and 9,9-bis [2,4,5-tri (t-butoxycarbonylvinyl) phenyl] fluorene _-10 alkoxycarbonylvinyl) phenyl] fluorene.

In addition, among these compounds, a compound in which a part of the hydrophilic group is not protected (that is, a compound having an unprotected hydroxyl group) can also be used.

Among these fluorene derivatives, 9,9-bis (C _1-6 alkoxycarbonylvinylphenyl) fluorene such as 9,9-bis [4- (2-t-butoxycarbonylvinyl) phenyl] fluorene, 9,9-bis 9,9-bis (C _1-6 alkoxycarbonylvinyl-C _1-3 alkylphenyl) fluorene such as bis [4- (2-t-butoxycarbonylvinyl) -3-methylphenyl] fluorene, 9,9-bis 9,9-bis [di (C _1-6 alkoxycarbonylvinyl) phenyl] fluorene such as [3,4-di (t-butoxycarbonylvinyl) phenyl] fluorene, and 9,9-bis [3,4-di ( t- butoxycarbonyl vinyl) -5-methyl phenyl] fluorene such as 9,9-bis [di (C _1-6 alkoxycarbonyl vinyl) -C _1-3 alkyl Eniru] fluorene, etc. 9,9-bis [3,4,5-(t-butoxycarbonyl) phenyl] 9,9-bis fluorene [tri (C _1-10 alkoxycarbonyl) phenyl] fluorene preferable.

The fluorene derivative (I) can be produced by a conventional method. For example, it is produced by reacting a fluorene represented by the following formula (II) with a reactant corresponding to the protecting group Pro ¹ or Pro ² or a reactant corresponding to-(J) _m -X-Pro. May be.

Wherein Z ¹ and Z ² are hydroxyl groups or —O— (AO) _r H groups (where A is a C _2-4 alkylene group such as ethylene or propylene, and r is 1 or more, preferably 1 to 10 R ¹ , R ² , R ³ , R ⁴ , or a leaving group (such as a halogen atom or a trifluoroalkylsulfonyl group). , N1, n2, p1, p2, q1 and q2 are the same as described above].

In the formula (II), when Z ¹ and Z ² are a hydroxyl group or a —O— (AO) _r H group, the fluorenes (II) are protected with a reactant corresponding to the protecting group Pro ¹ or Pro ^2. The fluorene derivative can be obtained by the above method. For example, a reaction with a reactant or a protecting agent [eg, dialkyl dicarbonate (such as di-t-butyl dicarbonate), 2-t-butoxycarbonyloxyimino-2-phenylacetonitrile (Boc-ON), etc.], olefins ( It can be easily protected by an addition reaction with an alkyl vinyl ether (such as ethyl vinyl ether) or an esterification reaction with a carboxylic acid (such as isobutyric acid). Examples of the method for protecting fluorenes include the method described in "PROTECTIVE GROUPS in ORGANIC SYNTHESIS, THIRD EDITION", Green Wuts, WILEY-INTERSCIENCE, published in 1999, and the like.

In the above formula (II), when Z ¹ and Z ² are a leaving group, it is obtained by an elimination reaction between the fluorenes (II) and a reactant corresponding to-(J) _m -X-Pro. Can be. Specifically, the fluorenes (II) having a leaving group (particularly, fluorenes having a halogen atom such as a bromine or iodine atom) and a carboxylic acid ester (particularly, a C _1-4 alkyl acrylate) Can be easily introduced by a coupling reaction (such as Heck reaction). Furthermore, in the coupling reaction, after using an unsaturated compound as the carboxylic acid ester, the unsaturated bond introduced into the fluorene (II) may be hydrogenated. The fluorenes (II) in which Z ¹ and Z ² are leaving groups can be derived, for example, from the fluorenes in which Z ¹ and Z ² are hydroxyl groups (bisphenolfluorenes).

The above-mentioned fluorene derivative (I) may be produced by a method in which an acyl halide group is formed from fluorenes with thionyl chloride and esterified with an alcohol (such as t-butanol) corresponding to the protecting group.

Examples of the fluorenes (II) (compounds in which Z ¹ and Z ² are hydroxyl groups) include (a) 9,9-bis (hydroxyphenyl) fluorenes and (b) 9,9-bis (dihydroxyphenyl) ) Fluorenes and (c) 9,9-bis (trihydroxyphenyl) fluorenes.

(A) Examples of 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (hydroxy-alkylphenyl) fluorene, and 9,9-bis (hydroxy) -Dialkylphenyl) fluorene, 9,9-bis (hydroxy-alkenylphenyl) fluorene and 9,9-bis (hydroxy-halophenyl) fluorene.

9,9-bis (hydroxyphenyl) fluorene includes, for example, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (2-hydroxyphenyl) fluorene, and the like.

9,9-bis (hydroxy-alkylphenyl) fluorene includes, for example, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene , 9,9-bis (2-hydroxy-5-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-isopropylphenyl) fluorene, 9,9-bis (4-hydroxy-3-isobutylphenyl) Fluorene and 9,9-bis (hydroxy-C _1-4 alkylphenyl) fluorene such as 9,9-bis (4-hydroxy-3-t-butylphenyl) fluorene are included.

9,9-bis (hydroxy-dialkylphenyl) fluorene includes, for example, 9,9-bis (4-hydroxy-2,5-dimethylphenyl) fluorene and 9,9-bis (4-hydroxy-3,5- 9,9-bis (hydroxy-diC _1-4 alkylphenyl) fluorene such as dimethylphenyl) fluorene and 9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene.

9,9-bis - The (hydroxy alkenyl phenyl) fluorene, e.g., 9,9-bis (4-hydroxy-3-allyl phenyl) fluorene such as 9,9-bis (hydroxy -C _2-4 alkenyl-phenyl) Fluorene and the like are included.

9,9-bis (hydroxy-halophenyl) fluorene includes, for example, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene.

(B) As the 9,9-bis (dihydroxyphenyl) fluorenes, fluorenes corresponding to the above fluorenes (a), for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9-bis (3,3) 4-dihydroxyphenyl) fluorene (biscatecholfluorene (BCAF)), 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9-bis (2,5-dihydroxyphenyl) fluorene, etc.], 9,9 9, such as -bis (dihydroxy-alkylphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene and 9,9-bis (3,4-dihydroxy-6-methylphenyl) fluorene; , 9-bis (dihydroxy -C _1-4 alkylphenyl) fluorene], 9,9-bis (dihydroxy Etc. - dialkyl phenyl) fluorene [di C _1-4 alkyl phenyl) fluorene 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) fluorene such as 9,9-bis (dihydroxy] .

(C) As 9,9-bis (trihydroxyphenyl) fluorenes, fluorenes corresponding to the above fluorenes (a), for example, 9,9-bis (2,4,6-trihydroxyphenyl) fluorene, 9,9-bis (trihydroxyphenyl) fluorene such as 9,9-bis (2,4,5-trihydroxyphenyl) fluorene and 9,9-bis (3,4,5-trihydroxyphenyl) fluorene; included.

The fluorenes (b) and (c) are novel compounds, and the production method thereof is not particularly limited, but can be usually produced by the following method.

(Method for producing fluorenes (b) and (c))
The fluorenes (b) and (c) are obtained by reacting a fluorenone represented by the following formula (1) with a polyhydric phenol represented by the following formula (2) in the presence of an acid catalyst. be able to.

(In the formula, R represents an alkyl group, p represents an integer of 0 to 2, and n represents 2 or 3. R ³ , R ⁴ , q1, and q2 are the same as described above.)
In the formula (2), R corresponds to R ¹ or R ² , n corresponds to n 1 or n 2, p corresponds to p 1 or p 2, and a preferred embodiment Etc. are as described above. A typical fluorenone represented by the formula (1) is 9-fluorenone (q1 = q2 = 0).

Examples of the polyhydric phenols represented by the formula (2) (hereinafter sometimes simply referred to as polyhydric phenol) include, for example, dihydroxybenzene (catechol, resorcinol, hydroquinone), alkyl-dihydroxybenzene [dihydroxytoluene (3, Mono- or di-C _1-6 alkyl-dihydroxybenzene, such as 5-dihydroxytoluene, 3-methylcatechol, 4-methylcatechol), 4-t-butylcatechol, 2,6-dihydroxy-p-xylene. And dihydroxybenzenes, and corresponding trihydroxybenzenes [trihydroxybenzene (pyrogallol, hydroxyhydroquinone, phloroglucinol) and the like]. Polyhydric phenols may be reacted with fluorenones alone or in combination of two or more.

The amount of the polyhydric phenol used may be, for example, about 2 to 20 mol, preferably about 2.5 to 10 mol, and more preferably about 3 to 5 mol, per 1 mol of the fluorenone.

反 応 The reaction (condensation reaction) between the polyhydric phenol and the fluorenone is not particularly limited, but can be usually performed in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids [sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid and the like], organic acids [sulfonic acid (alkanesulfonic acid such as methanesulfonic acid and the like) and the like]. The sulfuric acid includes dilute sulfuric acid, concentrated sulfuric acid, fuming sulfuric acid and the like, and sulfur trioxide may be used as a sulfuric acid precursor as long as it can be converted into sulfuric acid in the reaction system. The acid catalysts may be used alone or in combination of two or more. Preferred acid catalysts are hydrochloric acid or sulfuric acid.

The amount of the acid catalyst to be used can be selected according to the type of the acid catalyst. It may be about 0.01 to 50 parts by weight. In particular, the amount of sulfuric acid (in terms of H ₂ SO ₄ ) used may be a very small amount, and is usually 0.001 to 0.5 parts by weight (for example, 0.005 to 0.5 parts by weight) per 1 part by weight of fluorenone. 5 parts by weight), preferably about 0.01 to 0.5 parts by weight, more preferably about 0.05 to 0.5 parts by weight (for example, about 0.1 to 0.3 parts by weight). The amount of hydrochloric acid used is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably about 10 to 30 parts by weight, based on 100 parts by weight of fluorenone in terms of hydrogen chloride.

The condensation reaction may be carried out using thiols as a co-catalyst in addition to the acid catalyst. By combining with thiols, the condensation reaction can proceed effectively and the yield can often be improved. Examples of the thiols include conventional thiols that function as cocatalysts, for example, mercaptocarboxylic acids (thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid) Alkyl mercaptans (e.g., methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, etc., _C1-16 alkyl mercaptan (especially _C1-4 alkyl mercaptan), etc.), aralkyl mercaptan (benzyl mercaptan, etc.) or These salts are exemplified. Examples of the salt include an alkali metal salt (such as a sodium salt). Among these thiols, mercapto C _2-6 carboxylic acid (for example, β-mercaptopropionic acid) is preferable. The thiols can be used alone or in combination of two or more.

The amount of thiols used can be selected from the range of about 0 to 0.2 parts by weight, for example, 0.001 to 0.1 parts by weight, preferably 0.003 to 0.03 parts by weight per 1 part by weight of fluorenone. Parts by weight, more preferably about 0.005 to 0.015 parts by weight.

The amount of thiols used can be selected from a range of about 0 to 10 parts by weight, preferably 1 to 10 parts by weight, more preferably 0.01 to 10 parts by weight, based on 1 part by weight of the acid catalyst. May be about 0.01 to 2 parts by weight. In particular, the thiols may be 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, more preferably about 0.01 to 0.3 part by weight with respect to 1 part by weight of sulfuric acid. . The thiols are used in an amount of 0.1 to 3 parts by weight, preferably 0.3 to 1 part by weight, and more preferably about 0.5 to 1.5 parts by weight, based on 1 part by weight of hydrochloric acid (in terms of hydrogen chloride). May be.

The condensation reaction may be performed in the absence of a solvent, or may be performed in a solvent. Representative solvents (organic solvents) include ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), halogen solvents (halogenated hydrocarbons such as methylene chloride), and aromatic solvents. Group-based solvents (such as aromatic hydrocarbons such as toluene and anisole). Further, an excess of polyhydric phenols may be used as a solvent. Among these solvents, cyclic ethers (such as tetrahydrofuran and 1,4-dioxane) are preferred. The solvents may be used alone or in combination of two or more.

The amount of the solvent to be used can be selected from a range of about 0 to 20 parts by weight, for example, 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 2 to 2 parts by weight based on 1 part by weight of the fluorenone. It may be about 5 parts by weight.

The condensation reaction varies depending on the type of polyhydric phenols, acid catalyst, thiols, etc. used, but is usually 10 to 150 ° C., preferably 20 to 120 ° C., and more preferably 30 to 100 ° C. There are many. The reaction time can be adjusted according to the type of the raw material, the reaction temperature, the concentration in the solvent, and the like, and is, for example, 30 minutes to 48 hours, usually 1 to 24 hours, and preferably about 1 to 10 hours. The reaction may be performed with stirring, in air or in an inert atmosphere (nitrogen, rare gas, or the like), or at normal pressure or under pressure.

The reaction mixture after completion of the reaction can be separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, and column chromatography, or a separation means combining these. For example, after removing an acid catalyst (and thiols) by a conventional method, a crystallization solvent may be added and the mixture may be cooled to cause crystallization, and then purified by filtration and separation.

For the method for producing the fluorenes (b) and (c), reference may be made to the following literature relating to the method for producing bis (hydroxylphenyl) fluorenes. For example, (a) Documents [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087 and JP-A-8-217713 (hydrochloric acid gas and mercaptocarboxylic acid) A method of reacting a fluorenone with a phenol in the presence), (b) JP-A-2000-26349 [a method of reacting 9-fluorenone with an alkylphenol in the presence of an acid catalyst (and an alkyl mercaptan)], (C) JP-A-2002-47227 (method of reacting fluorenones with phenols in the presence of hydrochloric acid and thiols), (d) JP-A-2003-221352 (in the presence of sulfuric acid and thiols, A method in which a fluorenone is reacted with a phenol to form a crystallization with a crystallization solvent composed of a hydrocarbon and a polar solvent).

That is, in the methods of these documents, the polyhydric phenols (the compound represented by the formula (2)) are used instead of the phenols, and the synthesis method (the purification method, the addition ratio of the components, and the like) is referred to. Thus, polyhydric alcohols [9,9-bis (polyhydroxyphenyl) fluorenes] may be produced. Of these methods, in particular, when a method using hydrochloric acid or sulfuric acid (the above methods (c) and (d)) is applied, a product with higher yield and higher purity is often obtained.

The fluorenes (II) are compounds corresponding to the fluorenes [fluorenes (a) to (c)], wherein the hydroxyl group of the fluorenes is a —O— (AO) _r H group or a hydroxyl group. A compound which is a leaving group can also be exemplified.

Such compounds can be prepared by using conventional reactions, for example, by adding C _2-4 alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) to fluorenes (a) to (c) depending on the number of additions r. Or C _2-4 alkylene carbonate (ethylene carbonate, propylene carbonate, butylene carbonate, etc.) can be easily obtained. The reaction with the alkylene oxide or alkylene carbonate may be carried out in the absence of a catalyst, or may be carried out in the presence of a catalyst. Usually, a base catalyst [metal hydroxide, metal carbonate, tertiary amine (Eg, trialkylamines such as triethylamine, aromatic tertiary amines such as N, N-dimethylaniline, and heterocyclic tertiary amines such as 1-methylimidazole). Can be. In addition, the reaction may be performed in a solvent or under heating. In particular, when an alkylene carbonate is used, the reaction is often performed at, for example, about 70 to 150 ° C, preferably about 80 to 120 ° C in order to efficiently perform the decarboxylation reaction. The reaction may be carried out with stirring, in air or in an inert atmosphere, or at normal pressure or under pressure. Further, the reaction may be performed while removing a gas (such as carbon dioxide) generated as necessary. Furthermore, an alkylene oxide adduct of a polyhydric alcohol may be obtained by purifying the reaction mixture after completion of the reaction using a conventional purification method (extraction, crystallization, etc.).

Among these fluorenes (II), 9,9-bis (hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-3-methylphenyl) 9,9-bis (hydroxy-C _1-4 alkylphenyl) fluorene such as fluorene, 9,9-bis (dihydroxyphenyl) fluorene such as 9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9 9,9-bis (dihydroxy-C _1-4 alkylphenyl) fluorene such as -bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) 9,9-Bis (trihydroxyphenyl) fluorene such as fluorene is preferred.

Specifically, the fluorene derivative (Ia) includes, for example, fluorenes (II) in which Z ¹ and Z ² are hydroxyl groups or —O— (AO) _r H groups, and alkyl ethers (for example, ethyl vinyl ether and the like). With alkyl vinyl ethers and halogenated alkyl ethers) to produce an acetal. The proportion of the alkyl ethers is, depending on the number of n1 and n2, 1 mol or more, preferably 2 mol or more (for example, 2 to 50 mol), more preferably 3 to 1 mol, per 1 mol of the fluorenes (II). It is about 30 mol, usually about 5 to 20 mol.

The reaction may be performed in the presence of a catalyst. As the catalyst, an acidic catalyst is preferable, and specific examples include inorganic acids (hydrogen chloride, hydrochloric acid, hydrochloric acid / ether solution, sulfuric acid, phosphorus pentoxide, etc.) and organic acids (p-toluenesulfonic acid, methanesulfonic acid, etc.). Can be The ratio of the catalyst is about 0.0001 to 1 mol, preferably about 0.001 to 0.1 mol, per 1 mol of the fluorene (II).

溶媒 A solvent may be used for the reaction. The solvent can be used widely as long as it does not react with the acidic catalyst and dissolves the fluorenes (II). Specifically, a linear or cyclic ether solvent such as diethyl ether, tetrahydrofuran or dioxane, methylene chloride, Halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; aliphatic ester solvents such as ethyl acetate; aromatic hydrocarbon solvents such as benzene, toluene, xylene and anisole; and aliphatic ketone solvents such as acetone. No. Of these, tetrahydrofuran and halogenated hydrocarbon solvents are preferred.

The reaction can be carried out by putting fluorenes (II), alkyl ether compounds, catalysts and solvents into a reactor and stirring. The reaction temperature varies depending on the starting materials to be used, but it can usually be carried out within the range of 20 ° C to the boiling point of the solvent, for example, about 30 to 80 ° C. The reaction time varies depending on the type of the raw material and the reaction temperature, but is usually about 1 to 48 hours.

After the completion of the reaction, the mixture is neutralized by adding an aqueous alkali solution such as an aqueous sodium hydrogen carbonate solution, and then, if necessary, by adding an organic solvent such as an aromatic hydrocarbon (such as toluene) to extract the fluorene derivative (Ia). Can be isolated. Further, it can be purified by recrystallization and column chromatography.

The fluorene derivative (Ib) can be produced, for example, by reacting the fluorenes (II) with a dialkyl dicarbonate (for example, a di-C _1-10 alkyl dicarbonate such as di-t-butyl dicarbonate). The ratio of the dialkyl dicarbonate depends on the number of n1 and n2, but is 1 mol or more, preferably 1.5 mol or more (for example, 1.5 to 30 mol) per 1 mol of the fluorenes (II), More preferably, it is about 2 to 20 mol, and usually about 2 to 10 mol.

The reaction may be performed in the presence of a catalyst. As the catalyst, a basic catalyst is preferable. Specifically, organic bases (aliphatic, alicyclic, aromatic or heterocyclic amines and the like), for example, aliphatic amines such as trimethylamine and triethylamine, cyclopentylamine And alicyclic amines such as cyclohexylamine, aromatic amines such as aniline and diethylaniline, and heterocyclic amines such as 4-dimethylaminopyridine. The ratio of the catalyst is about 0.0001 to 1 mol, preferably about 0.001 to 0.1 mol, per 1 mol of the fluorene (II).

溶媒 A solvent may be used for the reaction. The solvent is inert to the reaction and can be used widely as long as it dissolves the fluorenes (II). Specifically, a linear or cyclic ether solvent such as diethyl ether, tetrahydrofuran or dioxane, methylene chloride, Halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; aliphatic ester solvents such as ethyl acetate; aromatic hydrocarbon solvents such as benzene, toluene, xylene and anisole; aliphatic ketone solvents such as acetone and methyl ethyl ketone And the like.

The reaction can be carried out by putting fluorenes (II), dialkyl dicarbonate, catalyst and solvent into a reactor and stirring. The reaction temperature varies depending on the starting materials to be used, but it can usually be carried out within the range of 20 ° C to the boiling point of the solvent, for example, about 30 to 80 ° C. The reaction time varies depending on the type of the raw material and the reaction temperature, but is usually about 1 to 48 hours.

終了 After the reaction is completed, the fluorene derivative (Ib) can be isolated by adding an alkali such as potassium hydroxide to make the compound alkaline and precipitate the target compound. Further, it can be purified by recrystallization using an organic solvent such as an aromatic hydrocarbon (such as toluene).

The fluorene derivative (Ic) is obtained, for example, by reacting the fluorenes (II) with a trihaloalkanesulfonic acid (for example, trifluoromethanesulfonic acid or the like), and then forming an alkyl (meth) acrylate (for example, t-butyl acrylate). (C _1-10 alkyl acrylate).

溶媒 A solvent may be used for the reaction between the fluorenes (II) and the trihaloalkanesulfonic acid. A wide range of solvents can be used as long as the fluorenes (II) can be dissolved therein. Specific examples thereof include basic solvents such as pyridine, triethylamine and aniline, and chain or cyclic ethers such as diethyl ether, tetrahydrofuran and dioxane. Solvents, halogenated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, etc .; aliphatic ester solvents such as ethyl acetate; aromatic hydrocarbon solvents such as benzene, toluene, xylene and anisole; acetone, methyl ethyl ketone etc. Examples thereof include aliphatic ketone solvents.

The reaction can be carried out by putting fluorenes (II), trihaloalkanesulfonic acid, and a basic solvent into the reactor. The reaction temperature varies depending on the starting materials used, but can be carried out within a range of about -30 to 30 ° C, and is usually about -20 to 20 ° C (for example, ice temperature). The reaction time varies depending on the type of the raw material and the reaction temperature, but is usually about 1 to 48 hours.

終了 After the completion of the reaction, the fluorene derivative (Ic) can be isolated by adding an acidic solution such as hydrochloric acid or sulfuric acid to make it acidic and precipitate. Further, for example, purification can be performed by recrystallization using a mixed solvent of an aliphatic hydrocarbon-based solvent (such as hexane) and an aliphatic ester-based solvent (such as ethyl acetate).

反 応 The reaction between the obtained reactant and the alkyl (meth) acrylate may be performed in the presence of a catalyst. As the catalyst, for example, an aromatic phosphorus-based catalyst such as triphenylphosphine or tolylphosphine may be combined with a Group VIII metal compound such as palladium acetate. The ratio of the catalyst is about 0.0001 to 1 mol, preferably about 0.001 to 0.1 mol, per 1 mol of the fluorene (II).

溶媒 A solvent may be used for the reaction. The solvent can be widely used as long as it does not react with the acidic catalyst and dissolves the fluorenes (II). Specific examples include basic solvents such as pyridine, triethylamine and aniline, acetonitrile, propionitrile, butyronitrile, Aliphatic or aromatic nitrile solvents such as benzonitrile, chain or cyclic ether solvents such as diethyl ether, tetrahydrofuran, dioxane, methylene chloride, chloroform, halogenated hydrocarbon solvents such as carbon tetrachloride, ethyl acetate and the like Examples thereof include aliphatic ester solvents, aromatic hydrocarbon solvents such as benzene, toluene, xylene, and anisole, and aliphatic ketone solvents such as acetone. Among these, a mixed solvent of a basic solvent such as triethylamine and a nitrile solvent such as acetonitrile is preferable. The proportion of the solvent may be such that the fluorenes (II) can be dissolved, but is usually about 0.5 to 50 parts by weight, preferably about 1 to 10 parts by weight, per 1 part by weight of the fluorenes (II).

The reaction is carried out by placing the fluorenes (II), the reactants, the catalyst and the solvent in a reactor and stirring. The reaction temperature varies depending on the raw materials used, but can be carried out within the range of 50 to 200 ° C to the boiling point of the solvent used, and is usually about 60 to 150 ° C, preferably about 80 to 130 ° C. The reaction time varies depending on the type of the raw material and the reaction temperature, but is usually about 1 to 48 hours.

後 After completion of the reaction, the fluorene derivative (Ic) can be isolated by adding an acidic aqueous solution such as hydrochloric acid or sulfuric acid to precipitate the target compound. Further, it can be purified by recrystallization and column chromatography using an organic solvent such as an aromatic hydrocarbon (such as toluene).

[Photoactive compound]
The fluorene derivative (I) is useful as a photoactive compound (photosensitive compound) and is used in combination with a photosensitizer. In particular, when the fluorene derivative (I) is used in resist applications, it is easy to control the affinity of the resist with the base resin and the solubility in the developer. Therefore, the protecting group Pro can be removed in association with the photosensitizer by light irradiation.

用途 The use of such a photoactive compound is not particularly limited, but it is particularly suitable for resist applications. That is, the photoactive compound is hydrophobic (or can be made hydrophobic by interaction with an alkali), but when used in combination with a photosensitizer (such as a photoacid generator), the protective group is exposed to light. (Particularly in connection with the photosensitizer by light irradiation), thereby generating a hydrophilic group and being able to be hydrophilized. Therefore, when applied to a resist (especially a positive resist), a hydrophilic domain is formed in an exposed portion, and dissolution of the resist film is promoted. In an unexposed portion, the affinity with the base resin is increased by the action of a protecting group. The dissolution can be suppressed by increasing the dissolution rate, and the difference in dissolution rate between the exposed portion and the unexposed portion can be increased. In particular, by using a hydrophobic group as the protecting group, the solubility in the unexposed area can be significantly suppressed, the swelling of the resist due to development can be suppressed, and the resolution can be improved. is there. The elimination of the protecting group often occurs in relation to the photosensitizer, particularly by the catalytic action of an acid. As such an acid, it is advantageous to use an acid generated upon irradiation with light (particularly an acid generated from a photoacid generator constituting the photosensitive resin composition).

As the photosensitizer to be combined with the photoactive compound, a conventional photosensitizer or photosensitizer used for a positive resist, for example, diazonium salts (diazonium salts, tetrazonium salts, polyazonium salts, etc.), quinonediazides (diazobenzoquinone derivatives, diazonium salts) A naphthoquinone derivative), a photoacid generator, a dissolution inhibitor, and the like.

Examples of the photoacid generator include the following compounds. For reference, the product name manufactured by Midori Kagaku Co., Ltd. is described in parentheses. Sulfonium salt derivatives [sulfonic acid esters, for example, arylalkanesulfonates such as 1,2,3-tri (methylsulfonyloxy) benzene (especially C _6-10 aryl C _1-2 alkanesulfonates); 2,6-dinitrobenzyltoluene Arylbenzenesulfonates such as sulfonates and benzoin tosylate (particularly C _{6-10 aryltoluenesulfonate optionally} having a benzoyl group); aralkylbenzenesulfonates such as 2-benzoyl-2-hydroxy-2-phenylethyltoluenesulfonate (especially optionally having benzoyl C _6-10 aryl -C _1-4 alkyl toluenesulfonate); disulfonic such as diphenyl sulfone; Lewis acid salt (triphenylsulfonium hexafluorophosphate (TPS-1 2), triphenylsulfonium hexafluoroantimony (TPS-103), 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimony (DTS-103), 4-methoxyphenyldiphenylsulfonium hexafluoroantimony (MDS-103), triphenylsulfonium Methanesulfonyl, triphenylsulfonium trifluoromethanesulfonyl (TPS-105), triphenylsulfonium nonafluorobutanesulfonyl (TPS-109) and other triarylsulfonium salts (especially triphenylsulfonium salts), etc.), phosphonium salt derivatives, diaryl Halonium salt derivative [diaryliodonium salt (diphenyliodonium hexafluorophosphate, 4,4′-di (t -Butylphenyl) iodonium hexafluorophosphate (BBI-102), 4,4'-di (t-butylphenyl) iodonium hexafluoroantimonate (BBI-103), 4,4'-di (t-butylphenyl) iodonium Tetrafluoroborate (BBI-101), 4,4'-di (t-butylphenyl) iodonium trifluoromethanesulfonate (BBI-105), 4,4'-di (t-butylphenyl) iodonium camphorsulfonate (BBI-106) ), Lewis acid salts such as diphenyliodonium trifluoromethanesulfonate (DPI-105), 4-methoxyphenylphenyliodonium trifluoromethanesulfonate (DPI-105), etc.), diazonium salt derivatives (p-nitro Lewis acid salts such as enyldiazonium hexafluorophosphate), diazomethane derivatives, triazine derivatives [1-methoxy-4- (3,5-di (trichloromethyl) triazinyl) benzene (TAZ-104), 1-methoxy-4- Haloalkyltriazinylaryl such as (3,5-di (trichloromethyl) triazinyl) naphthalene (TAZ-106), 1-methoxy-4- [2- (3,5-ditrichloromethyltriazinyl) ethenyl] benzene (TAZ-110), 1,2-dimethoxy-4- [2- (3,5-ditrichloromethyltriazinyl) ethenyl] benzene (TAZ-113), 1-methoxy-2- [2- (3 5-ditrichloromethyltriazinyl) ethenyl] haloalkyl such as benzene (TAZ-118) Ridinylalkenylaryl, etc.), imidylsulfonate derivatives [succinimidyl camphorsulfonate (SI-106), succinimidyl phenylsulfonate (SI-100), succinimidyl toluylsulfonate (SI-101), succinimidyl trifluoromethylsulfonate (SI-105), Phthalimidyl trifluorosulfonate (PI-105), naphthalimidyl camphorsulfonate (NAI-106), naphthalimidyl methanesulfonate (NAI-100), naphthalimidyl trifluoromethanesulfonate (NAI-105), naphthalimidyl toluylsulfonate (NAI-101), norbornaneimidyl Trifluoromethanesulfonate (NDI-105) etc.] It can be shown. Further, a sulfone derivative [for example, a compound having a —SO ₂ —C (＝ N) — unit such as “DAM-101”, “DAM-102”, “DAM-105”, “DAM-201”; “DSM-301” -CH ₂ -SO _2, such as "- compounds having the unit;" = N-O-SO _2, such as PAI-101 "- compounds having a unit etc.] are also included. In particular, Lewis acid salts (Lewis acid salts such as phosphonium salts) are preferred.

In particular, the photoacid generator, the photoactive compound which is deprotected by an acid generated by light irradiation from the acid generator to generate a hydrophilic group, and a base resin (particularly, the protective group is removed by the acid. A photosensitive resin composition in combination with a base resin which becomes alkali-soluble when separated is useful as a chemically amplified resist.

[Photosensitive resin composition]
In the present invention, a photosensitive resin composition (or a resist composition) can be constituted by the fluorene derivative (I), which is a photoactive compound, the photosensitive agent, and a base resin (oligomer or polymer). The photosensitive resin composition may be developable with an organic solvent (such as alcohols), but is generally preferably developable with water or an alkali.

(Base resin)
Examples of the base resin include a hydroxyl group-containing polymer [polyvinyl acetal, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, a hydroxyl group-containing cellulose derivative (such as hydroxyethyl cellulose), a polyvinylphenol-based resin, and a novolak resin (phenol novolak resin). ], A carboxyl group-containing polymer [a homopolymer or copolymer containing a polymerizable unsaturated carboxylic acid ((meth) acrylic acid, maleic anhydride, itaconic acid, etc.), a carboxyl group-containing cellulose derivative (such as carboxymethyl cellulose or a salt thereof), etc. ] Or an ester group-containing polymer [monomeric or copolymer (polyvinyl acetate) of monomers such as vinyl carboxylate (eg, vinyl acetate) and (meth) acrylate (eg, methyl methacrylate). Ethylene-vinyl acetate copolymer, (meth) acrylic resin, etc.), polyester, cellulose esters, etc.], polymer having an ether group [polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether-based resin, silicon resin, cellulose ether And the like], a carbonate-containing polymer, a polymer having an amide group or a substituted amide group [polyvinylpyrrolidone, polyurethane-based polymer, polyurea, nylon or polyamide-based polymer (polyamide using lactam component, dicarboxylic acid component or diamine component) Poly (meth) acrylamide-based polymers; polyamino acids; polymers having burette bonds; polymers having allohanate bonds; proteins such as gelatin; etc.), and polymers having nitrile groups (acrylonitrile Polymer, glycidyl group-containing polymer (epoxy resin, glycidyl (meth) acrylate homo- or copolymer, etc.), halogen-containing polymer (polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinylidene chloride polymer) , Chlorinated polypropylene, etc.), polymers having a non-aromatic ring group (for example, polymers having a C _5-8 cycloalkyl group such as cyclohexyl (meth) acrylate; norbornyl (meth) acrylate, (meth) acrylic acid A polymer having a crosslinked cyclic _C7-20 hydrocarbon ring group such as adamantyl), a polymerizable oligomer or polymer (an oligomer or polymer having a polymerizable group such as a (meth) acryloyl group, an allyl group, a vinyl group, a cinnamoyl group) Etc.) can be exemplified. These base resins may be used alone or in combination of two or more. As the base resin, a base resin constituting a negative photosensitive resin composition may be used, but a base resin constituting a positive photosensitive resin composition (positive resist) is preferable.

Typical base resins that constitute a positive resist include novolak resins (phenol novolak resins, cresol novolak resins, etc.) and hydrophilic groups (hydroxyl groups and / or carboxyl groups, etc.) that are protected by removable protecting groups. Resin and the like. The base resins may be used alone or in combination of two or more.

As the novolak resin, an alkali-soluble novolak resin is usually used. When the novolak resin is used as a resist for semiconductor production, a conventional novolak resin used in the resist field can be used. The novolak resin can be obtained by condensing a phenol having at least one phenolic hydroxyl group in the molecule and an aldehyde in the presence of an acid catalyst. Examples of phenols include phenol, o-, m- or p-cresol, 2,5-, 3,5- or 3,4-xylenol, 2,3,5-trimethylphenol, ethylphenol, propylphenol, Examples thereof include C _1-4 alkylphenols of butylphenol and 2-t-butyl-5-methylphenol, dihydroxybenzene, and naphthols. Aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde and glyoxal, and aromatic aldehydes such as benzaldehyde and salicylaldehyde.

Phenols can be used alone or in combination of two or more, and aldehydes can be used alone or in combination of two or more. Examples of the acid catalyst include inorganic acids (eg, hydrochloric acid, sulfuric acid, phosphoric acid), organic acids (eg, oxalic acid, acetic acid, p-toluenesulfonic acid), and organic acid salts (eg, divalent metal salts such as zinc acetate). Can be The condensation reaction can be carried out in a conventional manner, for example, at a temperature of about 60 to 120 ° C. for about 2 to 30 hours. The reaction may be performed in bulk or in a suitable solvent.

The base resin is preferably composed of a resin capable of generating a hydrophilic group by the action of an acid. Such a base resin is a simple group having a hydrophilic group (particularly a hydrophilic group selected from a hydroxyl group and a carboxyl group) and having a hydrophilic group that can be protected by a protective group that can be removed by the action of an acid. It can be composed of a homo- or copolymer of a monomer. Examples of the resin in which the hydrophilic group (such as a hydroxyl group and / or a carboxyl group) is protected by a removable protective group (or a resin that can be protected by a protective group) include, for example, a phenolic hydroxyl group capable of being released. Polyvinylphenol-based resin protected with a protecting group (e.g., a homopolymer of vinylphenol or a copolymer with a copolymerizable monomer), a hydroxyl group and / or carboxyl group-containing (meth) acrylic resin [for example, (Meth) acrylate homopolymer or copolymer, or (meth) acrylate and copolymerizable monomer copolymer, etc.), hydroxyl group and / or carboxyl group-containing norbornene resin (hydroxyl group and / or carboxyl group) And a copolymer of a norbornene derivative and a copolymerizable monomer. When a resin having high transparency to an exposure wavelength (a non-aromatic resin such as a (meth) acrylic resin or a norbornene resin) is used as the base resin, the sensitivity to exposure light having a short wavelength is increased. Can be. When a non-aromatic photosensitive resin composition is used, a shorter wavelength exposure source can be used and a finer pattern can be formed.

The resin in which the hydrophilic group is protected by a removable protecting group may be obtained by polymerizing a monomer in which the hydrophilic group is protected in advance by a protecting group (such as the protecting group exemplified in the section of the fluorene derivative). Or by polymerizing a monomer having a hydrophilic group, and protecting the hydrophilic group of the obtained resin with the protective group.

Among the monomers having a hydrophilic group, monomers having a hydroxyl group include vinylphenol monomers (such as vinylphenol); allyl alcohol; hydroxyalkyl (meth) acrylate (hydroxyethyl (meth) acrylate , hydroxypropyl (meth) acrylate, and 2-hydroxy-C _2-6 (meth) acrylates such as hydroxybutyl (meth) acrylate); diethylene glycol mono (meth) acrylate such as (poly) oxyalkylene glycol mono (meth) acrylate; hydroxy cycloalkyl (meth) acrylate (hydroxy C _3-8 cycloalkyl (meth) acrylates such as hydroxy cyclohexyl (meth) acrylate), a single ring, such as hydroxyalkyl oxacycloalkyl (meth) acrylate (Meth) acrylates having an alicyclic group; cross-linked alicyclic rings such as hydroxydecalinyl (meth) acrylate, hydroxybornyl (meth) acrylate, hydroxynorbornyl (meth) acrylate, and hydroxyadamantyl (meth) acrylate (Meth) acrylates having an aromatic group (e.g., hydroxy to tetra C _3-8 cycloalkyl (meth) acrylate); hydroxy norbornene, hydroxyalkyl-norbornene (hydroxy C _1-4 such as hydroxymethyl-norbornene, hydroxyethyl-norbornene, etc.) Norbornene derivatives having a hydroxyl group such as alkyl-norbornene). Examples of the monomer having a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, and vinylbenzoic acid; carboxy C _5-8 cycloalkyl (meth) such as carboxycyclohexyl (meth) acrylate Acrylate; (meth) acrylate having a carboxyl group-containing crosslinked cyclic alicyclic hydrocarbon group (for example, carboxydecalinyl (meth) acrylate, carboxynorbornyl (meth) acrylate, carboxymethyl-norbornyl (meth) acrylate, Carboxybiyl such as carboxybornyl (meth) acrylate and carboxyadamantyl (meth) acrylate to tetra C _3-8 cycloalkyl (meth) acrylate, and the like. These monomers having a hydrophilic group can be used alone or in combination of two or more.

Examples of the copolymerizable monomer include a conventional copolymerizable monomer, for example, a (meth) acrylic monomer [for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like. Alkyl (meth) acrylate (C _1-10 alkyl (meth) acrylate); cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate (cyclo C _3-8 alkyl (meth) acrylate); oxacycloalkyl (meth) A) a (meth) acrylate having a monocyclic heterocyclic group such as an acrylate; (Meth) acrylate (bi to tetracyclo C _3-8 alkyl (meth) Acrylate); hydroxy C _2-6 alkyl (meth) acrylate such as hydroxyethyl (meth) acrylate; epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate; (meth) acrylonitrile, etc.); imide monomer body [e.g., maleimide, N- methyl maleimide, N- ethyl-N-C _1-4 alkyl maleimides such as maleimide, etc. N-C _6-10 aryl maleimides such as N- phenyl maleimide]; unsaturated carboxylic acids [e.g., Crotonic acid, maleic anhydride, itaconic acid, etc.], styrene, α-methylstyrene, pt-butylstyrene, vinyltoluene and other aromatic vinyl monomers (styrene monomers); vinyl methyl ether, vinyl Vinyl ether monomers such as ethyl ether; vinyl acetate, propion Fatty acid vinyl S-based monomers such as vinyl acid are exemplified.

These copolymerizable monomers can be used alone or in combination of two or more. In the copolymer with the copolymerizable monomer, the proportion of the monomer having a hydrophilic group is from 10 to 100% by weight, preferably from 25 to 80% by weight, based on the total amount of the monomer. Preferably, it is about 30 to 70% by weight.

In the resin that forms a hydrophilic group by the deprotection, as the protecting group for the hydrophilic group, the protecting group exemplified in the section of the fluorene derivative, for example, an alkoxyalkyl group, an alkoxycarbonyl group, a cycloalkyl group, an oxacycloalkyl A protecting group for a hydroxyl group such as a group, a bridged cyclic alicyclic group or an alkylsilyl group; a protecting group for a carboxyl group such as an alkyl group.

As a typical resin, for example, a polyalicyclic alcohol-based resin (hydroxycycloalkyl (meth) acrylate) in which a hydroxyl group is protected by a protecting group such as an alkoxyalkyl group or an alkoxycarbonyl group (such as a t-BOC group) A hydroxyl group-containing alicyclic (meth) acrylate such as a homo- or copolymer) or a hydroxyl group also includes a cycloalkyl group (oxacycloalkyl group; norbornyl group, adamantyl group, and other bi- or tricycloalkyl group) ) And the like. (Meth) acrylic resin protected with an alicyclic group (e.g., a hydroxyalkyl (meth) acrylate homopolymer or copolymer) and a carboxyl group having a protective group such as an alkyl group (e.g., a t-butyl group) (Meth) acrylic resin (homo- or copolymer of (meth) acrylic acid) Etc.), and the like.

(4) The weight average molecular weight of the base resin is about 6,000 to 50,000, preferably about 7,000 to 30,000, and more preferably about 7,000 to 20,000.

Preferred positive resists include a combination of a resin that produces a hydrophilic group by deprotection (particularly deprotection by the catalytic action of an acid generated from an acid generator) and a photosensitive agent (photoacid generator).

(Ratio of each component)
The ratio (weight ratio) of the fluorene derivative (I) and the photosensitizer can be selected from a wide range of about 0.01 / 1 to 100/1, usually 0.1 / 1 to 75/1. And preferably about 1/1 to 50/1.

In the positive photosensitive resin composition (positive resist), the amount of the photosensitive agent used is, for example, 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the base resin. Can be selected from the range of about 1 to 20 parts by weight (particularly, 1 to 10 parts by weight).

In the photosensitive resin composition, the proportion of the fluorene derivative (I) is 50% by weight or less (for example, about 1 to 50% by weight), and preferably 3 to 40% by weight, based on the whole solid content of the resist. %, More preferably about 5 to 30% by weight. The ratio of the fluorene derivative (I) is 1 to 1000 parts by weight (for example, 5 to 1000 parts by weight), preferably 10 to 500 parts by weight, and more preferably 100 to 100 parts by weight of the solid resin. It is preferably about 10 to 300 parts by weight, particularly about 10 to 100 parts by weight.

(4) The photosensitive resin composition may optionally contain various additives such as a stabilizer such as an antioxidant, a plasticizer, a surfactant, a dissolution promoter, and a coloring agent such as a dye or a pigment. Further, in order to improve workability such as applicability, the photosensitive resin composition contains solvents [hydrocarbons, halogenated hydrocarbons, alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, cyclohexanone, etc.)] ), Esters (eg, ethyl acetate, ethyl lactate), ethers, cellosolves (eg, methyl cellosolve, ethyl cellosolve, butyl cellosolve), carbitols, glycol ether esters (eg, cellosolve acetate, propylene glycol monomethyl ether acetate (eg, PGMEA)) (Poly) oxyalkylene glycol alkyl ether acetate).

The photosensitive resin composition can be prepared by a conventional method, for example, by mixing a photosensitive resin [a photosensitive resin composition composed of a base resin (polymer or oligomer) and a photosensitive agent] and a photoactive compound. . The photosensitive resin composition usually contains a solvent [eg, lactate ester such as ethyl lactate; (poly) oxyalkylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate (eg, PGMEA)]. The amount of the solvent used is not particularly limited, and is, for example, about 0.1 to 50 parts by weight, preferably about 1 to 40 parts by weight, and more preferably about 5 to 30 parts by weight, based on 1 part by weight of the photosensitive resin. .

[Photosensitive layer]
A photosensitive layer can be formed by applying (coating or coating) the photosensitive resin composition to a substrate. The substrate (substrate) can be appropriately selected from metal (aluminum), glass, ceramics (alumina, copper-doped alumina, tungsten silicate, etc.), plastic, etc., depending on the characteristics and use of the pattern, and a semiconductor substrate such as a silicon wafer. It may be.

The substrate may be subjected to a surface treatment in advance in order to improve the adhesion to the photosensitive layer depending on the application. Examples of the surface treatment include a surface treatment with the silane coupling agent (such as a hydrolyzable polymerizable silane coupling agent having a polymerizable group) and an anchor coat agent or a base material (polyvinyl acetal, acrylic resin, vinyl acetate). Resin, epoxy resin, urethane resin, etc.), or a coating treatment with a mixture of these base materials and inorganic fine particles.

After applying the photosensitive resin composition to the substrate, the solvent may be evaporated by drying. The solvent may be removed by soft baking (pre-baking) using a heating means such as a hot plate, for example.

感光 The photosensitive layer of the photosensitive resin composition of the present invention may be formed on at least the surface of the resist layer. The structure of the photosensitive layer can be selected according to a pattern forming process, a circuit structure, and the like, and may be a single layer structure or a multilayer structure (or a laminated or composite structure).

The thickness of the photosensitive layer is not particularly limited and can be selected, for example, from a range of about 0.01 to 10 μm, preferably about 0.05 to 5 μm, and preferably about 0.08 to 2 μm, and is usually 0.05 to 1 μm (for example, , 0.1 to 0.7 μm).

The photosensitive layer can be formed by a conventional coating method, for example, a spin coating method, a dipping method, a casting method or the like, and if necessary, can be dried to remove a solvent to form a photosensitive layer.

[Pattern forming method]
The pattern (especially a fine pattern) can be formed by using a conventional lithography technique which combines exposure, development, etching and the like.

For example, a pattern can be formed by applying the photosensitive resin composition to a substrate to form a photosensitive layer, exposing, and developing. In particular, when a chemically amplified photosensitive resin is used, it is preferable to perform a heat treatment (post-exposure bake (post-exposure bake, PEB)) after the exposure in order to efficiently diffuse the acid generated by the exposure. After patterning by development, etching may be performed by plasma processing (eg, oxygen plasma).

Exposure to the photosensitive layer can be performed by a conventional method, for example, by irradiating or irradiating a light beam with a pattern through a predetermined mask. Various light rays (active light rays) depending on the photosensitive characteristics of the photosensitive resin composition, the fineness of the pattern, the type of the base resin, and the like, for example, light rays such as a halogen lamp, a high-pressure mercury lamp, and a UV lamp; (436 nm), i-line (365 nm), excimer laser [eg, XeCl (308 nm), KrF (248 nm), KrCl (222 nm), ArF (193 nm), ArCl (172 nm), F ₂ (157 nm), etc.], electron beam , EB rays, EUV rays (13 nm), X-rays, and the like, and may be a single wavelength or a composite wavelength. In particular, excimer lasers such as KrF (248 nm), ArF (193 nm), and F ₂ (157 nm), and light beams having wavelengths of about 10 to 300 nm such as X-rays, EB rays, and EUV rays (13 nm) can be advantageously used.

In addition, by using a resist composed of a non-aromatic base resin, transparency to short-wavelength light can be improved, and sensitivity can be improved. For example, when a KrF excimer laser (248 nm) is used as an exposure source, a chemically amplified photosensitive resin composition, for example, a resin that generates a hydrophilic group by deprotection [a hydroxyl group is protected by a protecting group] Positive-type photosensitive resin compositions comprising a polyvinylphenol-based resin, a non-aromatic resin in which a hydroxyl group or a carboxyl group is protected by a protective group, and a photosensitive agent (acid generator) can be used. Examples of the non-aromatic resin in which a hydroxyl group or a carboxyl group is protected by a protecting group include, for example, a (meth) acrylic resin in which a carboxyl group is protected by a protecting group; a carboxyl group or a hydroxyl group protected by a protecting group. [For example, in a copolymer of an alicyclic monomer (for example, a norbornene derivative such as carboxynorbornene, hydroxynorbornene, or hydroxyethylnorbornene) and a copolymerizable monomer such as maleic anhydride; Such as a resin in which a hydroxyl group or a carboxyl group is protected by a protecting group].

When an ArF excimer laser (193 nm) is used as an exposure source, for example, a non-aromatic resin in which the hydroxyl group or carboxyl group is protected by a protective group can be used.

The exposure energy can be selected according to the photosensitive properties (solubility, etc.) of the photosensitive resin composition and the like, and the exposure time is usually about 0.005 seconds to 10 minutes, preferably about 0.01 seconds to 1 minute. You can choose from a range.

The temperature of heating (prebaking and PEB) is 50 to 150 ° C., preferably 60 to 150 ° C., more preferably about 70 to 150 ° C., and the heating time is 30 seconds to 5 minutes, preferably 1 to 2 minutes. It is about.

パ タ ー ン After the pattern exposure, a high-resolution pattern can be formed by developing with a conventional method. Various developers (water, aqueous alkaline solution, etc.) can be used for development depending on the type of the photosensitive resin composition. A preferred developer is water or an alkaline developer, and if necessary, a small amount of an organic solvent (eg, alcohols such as methanol, ethanol, isopropanol, ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves). , A hydrophilic or water-soluble solvent such as cellosolve acetate) or a surfactant. The development method is not particularly limited, and for example, a paddle (meniscus) method, a dip method, a spray method, and the like can be employed.

In addition, the coating film (photosensitive layer) may be heated or cured at an appropriate temperature in an appropriate step of the steps from application to development of the photosensitive resin composition, not limited to the prebaking and PEB. For example, a heat treatment may be performed after development, if necessary.

Since the fluorene derivative (I) of the present invention can be hydrophilized by deprotection caused by light irradiation, when used in combination with a photosensitive agent (photosensitive agent and base resin), a resist (formed of the photosensitive resin composition) is used. For example, when a photosensitive layer is formed, a difference in solubility between an exposed portion and an unexposed portion can be caused. In particular, in the unexposed area, the photosensitive layer is protected (particularly hydrophobized) and the surface becomes hydrophobic, and in the exposed area, the hydrophilized portion forms a hydrophilic domain. Dissolution is promoted. Therefore, the difference in dissolution rate between the unexposed portion and the exposed portion can be increased.

Therefore, the photoactive compound of the present invention is useful for application to a resist composition and the like, and the photosensitive resin composition composed of the photoactive compound can be used for various purposes, for example, a circuit forming material (semiconductor manufacturing). Resists, printed wiring boards, etc.), image forming materials (printing plate materials, relief images, etc.). In particular, since it is possible to obtain high sensitivity and resolution, it can be advantageously used for a resist for semiconductor production.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
In 50 ml of tetrahydrofuran, 27.7 g (0.079 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 40 g (0.56 mol) of ethyl vinyl ether, and 5 ml of a hydrochloric acid-ether solution (1 mol / l) were added. And stirred for about 5 hours. After the completion of the reaction, the mixture was washed with an aqueous sodium hydrogen carbonate solution, washed with water, and the solvent was distilled off. Purification by silica gel column chromatography (eluent: hexane) yielded 35.7 g of 9,9-bis {4-[(1-ethoxy) ethoxy] phenyl} fluorene (86% yield).

_{^{1 H-NMR (CDCl 3)}} ppm: 1.19 (t, 6H, terminal _{CH 3), 1.47 (d,} 6H, branched _{CH 3), 3.42~3.59 (m,} 2H, OCH 2 ), 3.70~3.84 (m, 2H, OCH 2), 5.30 (q, 2H, branched OCH), 6.82 (d, 4H , C 6 H 4), 7.09 (d, _{4H, C 6 H 4),} 7.21~7.41 (m, 6H, C 13 H 8), 7.75 (d, 2H, C 13 H 8).

Example 2
Example 9 was repeated in the same manner as in Example 1 except that 30 g (0.079 mol) of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene was used instead of 9,9-bis (4-hydroxyphenyl) fluorene. There were obtained 39.8 g (91% yield) of 9,9-bis {3-methyl-4-[(1-ethoxy) ethoxy] phenyl} fluorene.

_{^{1 H-NMR (CDCl 3)}} ppm: 1.19 (t, 6H, terminal _{CH 3), 1.48 (d,} 6H, branched _{CH 3), 2.13 (s,} 6H, cresol CH _3), 3 .46 to 3.60 (m, 2H, OCH ₂ ), 3.70 to 3.84 (m, 2H, OCH ₂ ), 5.30 (q, 2H, branched OCH), 6.78 (d, 2H) _{, C 6 H 4), 6.95} (d, 4H, C 6 H 4), 7.25~7.44 (m, 6H, C 13 H 8), 7.75 (d, 2H, C 13 H ₈ ).

Example 3
To 50 ml of dehydrated ethyl acetate were added 12.9 g (36.7 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene and 1.7 ml of a hydrochloric acid / ether solution (1 mol / l), and the mixture was set at 40 ° C. . Into this, 7.9 g (109.6 mmol) of ethyl vinyl ether was added dropwise and stirred overnight. After completion of the reaction, the resultant was washed with an aqueous solution of sodium hydrogencarbonate and then washed with water to remove the solvent. Purification by silica gel column chromatography (eluent: toluene) gave 14.1 g of 9,9-bis {4-[(1-ethoxy) ethoxy] phenyl} fluorene (yield 78%).

_{^{1 H-NMR (CDCl 3)}} ppm: 1.19 (t, 6H, terminal _{CH 3), 1.47 (d,} 6H, branched _{CH 3), 3.42~3.59 (m,} 2H, OCH 2 ), 3.70~3.84 (m, 2H, OCH 2), 5.30 (q, 2H, branched OCH), 6.82 (d, 4H , C 6 H 4), 7.09 (d, _{4H, C 6 H 4),} 7.21~7.41 (m, 6H, C 13 H 8), 7.75 (d, 2H, C 13 H 8).

Example 4
In 50 ml of dehydrated acetone, 12.9 g (36.7 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene and 4.5 mg of 4-dimethylaminopyridine [(CH ₃ ) ₂ NC ₅ H ₄ N] (3. 7 × 10 ^-2 mmol) were added, after heating to 40 ° C., was added dropwise di -tert- butyl dicarbonate 8 g (36.7 mmol) and stirred for 24 hours. After completion of the reaction, the reaction solution was poured into ice water, adjusted to be alkaline with a minimum amount of potassium hydroxide, and the resulting solid was filtered, dried and recrystallized from toluene to give 9,9-bis [4- (tert-butoxy). Carbonyloxy) phenyl] fluorene (18.2 g, yield 90%) was obtained.

¹ H-NMR (CDCl ₃ ) ppm: 1.55 (s, 18 H, tert-Bu), 7.03 (d, 4 H, C ₆ H ₄ ), 7.27 (d, 4 H, C ₆ H ₄ ) , 7.15~7.41 (m, 6H, C 13 H 8), 7.76 (d, 2H, C 13 H 8).

Example 5
In 50 ml of dehydrated acetone, 12.9 g (36.7 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene and 4.5 mg of 4-dimethylaminopyridine [(CH ₃ ) ₂ NC ₅ H ₄ N] (3. 7 × 10 ^-2 mmol) were added, after heating to 40 ° C., it was added dropwise di -tert- butyl dicarbonate 4g (18.4 mmol) and stirred for 24 hours. After completion of the reaction, the reaction solution is put in ice water, adjusted to be alkaline with a minimum amount of potassium hydroxide, and the resulting solid is filtered and dried, and then purified by a silica gel column (eluent: hexane / ethyl acetate = 7/3). Thereby, 12.1 g (yield 73%) of 9- [4- (tert-butoxycarbonyloxy) phenyl] 9- [4-hydroxyphenyl] fluorene was obtained.

¹ H-NMR (CDCl ₃ ) ppm: 1.55 (s, 9 H, tert-Bu), 6.67 (d, 2 H, C ₆ H ₄ ), 7.00 (d, 2 H, C ₆ H ₄ ) , 7.06 (d, 2H, C 6 H 4), 7.19 (d, 2H, C 6 H 4), 7.22~7.39 (m, 6H, C 13 H 8), 7.75 _{(d, 2H, C 13 H} 8).

Example 6
(I) 9,9-bis [4- (trifluoromethylsulfonyloxy) phenyl] Synthesis of fluorene 9,9-bis (4-hydroxyphenyl) fluorene 5.2 g (14.9 mmol) in dry pyridine (C ₅ was dissolved in H ₅ N) 50 ml, further triflic anhydride 8.8g of (31.2 mmol) was reacted at room temperature for 24 hours under ice-cooling. After pouring the reaction solution into ice water, hydrochloric acid was added to make the inside of the system acidic. The resulting solid was filtered, washed with water, dried and then recrystallized with a mixed solvent of hexane / ethyl acetate to give 6.51 g (10.6 mmol) of 9,9-bis [4- (trifluoromethylsulfonyloxy) phenyl] fluorene. Got.

(Ii) Synthesis of 9,9-bis [4- (2-tert-butoxycarbonylvinyl) phenyl] fluorene 9,9-bis [4- (trifluoromethylsulfonyloxy) phenyl] fluorene synthesized in step (i) To 7.4 g (21.2 mmol), 2.85 g (22.2 mmol) of tert-butyl acrylate, 10 ml of triethylamine, 30 ml of acetonitrile, 50 mg of palladium acetate [Pd (OAc) ₂ ] (2.22 × 10 ⁻¹⁾ Mmol) and 134 mg (4.42 × 10 ^-1 mmol) of tri-o-tolylphosphine were added, and the reaction system was purged with argon and reacted under heating and reflux for 24 hours. The reaction solution was poured into 500 ml of ice water, hydrochloric acid was added with stirring, and the resulting solid was filtered, washed with water, dried, and purified by silica gel column chromatography (eluent: toluene) to give 9 8.34 g (69% yield) of 9,9-bis [4- (2-tert-butoxycarbonylvinyl) phenyl] fluorene was obtained.

_{^{1 H-NMR (CDCl 3)}} ppm: 1.53 (s, 18H, tert-Bu), 6.29 (d, 2H, CH = CH), 7.08~7.45 (m, 14H, C 6 H ₄ and _{C 13 H 8), 7.51 (} d, 2H, CH = CH), 7.78 (d, 2H, C 13 H 8).

Example 7
36 g (about 0.2 mol) of 9-fluorenone, 88 g (about 0.8 mol) of catechol, 0.7 ml of β-mercaptopropionic acid, and 60 g of 1,4-dioxane were placed in a reactor and heated at 80 ° C. 5 ml of 98% sulfuric acid was added dropwise. After completion of the reaction, 200 ml of MIBK (methyl isobutyl ketone) and 100 ml of water were added for extraction. By performing the same operation three times, excess sulfuric acid was removed. After concentration of the solvent, MIBK (100 ml) and toluene (200 ml) were added, and the mixture was cooled to 10 ° C. to obtain biscatecholfluorene [9,9-bis (3,4-dihydroxyphenyl) fluorene] (65 g). The ¹ H-NMR spectrum data of the obtained biscatechol fluorene is shown below.

¹ H-NMR: 6.35 ppm (d, 2H), 6.58 ppm (m, 4H), 7.33 ppm (m, 6H), 7.89 ppm (d, 2H), 8.75 ppm (s, 2H), 8.80 ppm (s, 2H).

19.1 g (50 mmol) of the obtained biscatechol fluorene [9,9-bis (3,4-dihydroxyphenyl) fluorene], 100 mL of acetone, and 0.1 g of 2,4-dimethylaminopyridine were put into a reactor, Reaction was carried out by slowly dropping 48.0 g (0.22 mol) of t-butyl dicarbonate at 40 ° C. After completion of the reaction, 200 mL of hexane was added to precipitate crystals, followed by washing with a mixed solvent of hexane / acetone (volume ratio) = 1/1 to obtain 9,9-bis [3,4-di (t -Butoxycarbonyloxy) phenyl] fluorene was obtained in an amount of 37.5 g (yield: 96%).

¹ H-NMR (CDCl ₃ ) ppm: 1.43 (s, 18H), 1.48 (s, 18H), 7.05 to 7.11 (m, 6H), 7.22 to 7.39 (m , 4H), 7.48 (d, 2H), 7.80 (d, 2H).

感光 The photosensitive resin compositions containing the fluorene derivatives obtained in Examples 1, 3 and 4 were evaluated as follows.

(1) Preparation of Photosensitive Resin To 0.5 part by weight of a polyvinylphenol resin having a weight average molecular weight of 9,000 in which 35 mol% of hydroxyl groups was protected with 1-ethoxyethoxy group, 37 mol% of hydroxyl groups were added to t. 0.5 parts by weight of a polyvinylphenol resin having a weight average molecular weight of 8,500 substituted with a -BOC (tert-butoxycarbonyloxy) group was added, and 0.02 parts by weight of a photoacid generator represented by the following formula (A) was added. The mixture was added and 6 parts by weight of propylene glycol monomethyl ether acetate as a solvent was mixed to prepare a positive photoresist.

(2) Preparation of photosensitive resin composition The fluorene derivative obtained in Example 1 or 3 was added to the photosensitive resin solution obtained in the step (1), and the fluororesin (polytetrafluoroethylene) (0 .2 μm) to obtain a photosensitive resin composition. The ratio shown in Table 1 is a ratio to the solid content excluding the solvent in the photosensitive resin solution.

(3) Performance (sensitivity, resolution) evaluation After treating the washed silicon wafer with hexamethyldisilazane, the photosensitive resin composition obtained in the step (2) is dried with a spin coater to obtain a film thickness. Was applied to be 0.4 μm, and heated on a hot plate at 100 ° C. for 1 minute. Next, using a reduction projection exposure machine (FPA-3000EX5, manufactured by Canon Inc., NA = 0.63) having an exposure wavelength of 248 nm (KrF excimer laser), a test mask having line and space patterns having different line widths. , The exposure was changed stepwise. The wafer was heated on a hot plate at 100 ° C. for 1 minute, and then paddle-developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute to obtain a positive pattern.

Each characteristic of the positive pattern was evaluated as follows.
(i) Sensitivity: The exposure amount was such that the line: space = 1: 1 with a line width of 0.25 μm was equal to the mask size (the smaller the value, the higher the sensitivity and the better).
(ii) Resolution: Displayed with a minimum dimension at which lines are separated at an exposure amount where the line: space = 1: 1 with a line width of 0.25 μm conforms to the mask dimension (the smaller the value, the higher the resolution and the better).

The results are shown in Table 1. Table 1 also shows, as a comparative example, the sensitivity and resolution of the photosensitive resin composition containing no photoactive compound.

明 ら か As is clear from the results in Table 1, the photosensitive resin compositions using the fluorene derivatives of Examples have high sensitivity and high resolution.

Claims (14)

A fluorene derivative represented by the following formula (I).

(Wherein, J ¹ and J ² are a linking group, -X ¹ -Pro ¹ and -X ² -Pro ² are hydrophilic groups protected by a removable protecting group Pro ¹ or Pro ² , respectively, and R ¹ to R ⁴ represents an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, an aryl group, a halogen atom or a hydroxyl group, m1 and m2 are 0 or 1, n1 and n2 are 0 or an integer of 1 to 4, p1, p2 , Q1 and q2 represent an integer of 0 to 4, provided that at least one of n1 and n2 is 1 to 4, and n1 + p1 and n2 + p2 are integers of 5 or less.) The fluorene derivative according to claim 1, wherein in formula (I), -X ¹ -Pro ¹ and -X ² -Pro ² are a hydroxyl group or a carboxyl group protected with a protecting group. The fluorene derivative according to claim ^1, wherein in the formula (I), Pro ¹ and Pro ² are acetal-based protecting groups or alkyl ester-based protecting groups. In the formula ^{(I), - (J 1} ) m1 -X 1 -Pro 1 and _{^{- (J 2) m2 -X 2}} -Pro 2 ^{is, -O-C (R a)} -OR b or -O-CH ( O) -OR ^c (wherein, R ^a to R ^c are the same or different, fluorene derivative according to claim 1, wherein a represents an alkyl group). In the formula ^{(I), - (J 1} ) m1 -X 1 -Pro 1 and _{^{- (J 2) m2 -X 2}} -Pro 2 ^{is, -C (R d) = C} (R e) -C (O) -OR ^f (wherein, R ^d and R ^e are a hydrogen atom or an alkyl group, and R ^f represents an alkyl group) fluorene derivative according to claim 1, wherein a. In the formula (I), an integer of p1 and p2 is 0 to 2, q1 and q2 are 0, fluorene derivative according to claim 1, wherein R ¹ and R ² is an alkyl group. (4) A photoactive compound used in combination with a photosensitizer, wherein the photoactive compound comprises the fluorene derivative according to claim 1. (8) The photoactive compound according to (7), wherein the protecting group Pro is detachable in association with the photosensitizer by light irradiation. (8) A photosensitive resin composition comprising a base resin, a photosensitive agent, and the photoactive compound according to claim 7. 10. The photosensitive resin composition according to claim 9, which can be developed with water or alkali. 10. The photosensitive resin composition according to claim 9, which is a positive photosensitive resin composition. 10. The photosensitive resin composition according to claim 9, wherein the base resin is composed of a resin capable of generating a hydrophilic group by the action of an acid, and the photosensitive agent is composed of a photoacid generator. 10. The base resin is selected from a hydroxyl group and a carboxyl group, and is composed of a homo- or copolymer of a monomer having a hydrophilic group which can be protected by a protecting group which can be removed by the action of an acid. The photosensitive resin composition as described in the above. A resist additive comprising the fluorene derivative according to claim 1.