Vinyl-group-containing fluorene compound

Abstract

A novel vinyl-group-containing fluorene compound and a method for producing the same, a polymerizable monomer and cross-linking agent including this compound, a leaving-group-containing fluorene compound, a monovinyl-group-containing fluorene compound, and methods for producing the same. This vinyl-group-containing fluorene compound is represented by formula (1). In the formula, W.sup.1 and W.sup.2 represent a group represented by formula (2), a group represented by formula (4), a hydroxyl group, or a (meth)acryloyloxy group, R.sup.3a and R.sup.3b represent a cyano group, a halogen atom, or a monovalent hydrocarbon, and n1 and n2 are integers of 0-4. In formulas (2) and (4), a ring (Z) is an aromatic hydrocarbon ring, X is a single bond or a group represented by S, R.sup.1 is a single bond or a C1-4 alkylene group, R.sup.2 is a specific substituent group such as a monovalent hydrocarbon, and m is an integer of 0 or greater. ##STR00001##

Claims

1. A vinyl-group-containing fluorene-based compound represented by the following formula (1): ##STR00056## wherein W.sup.1 and W.sup.2 each independently represent a group represented by the following formula (2), a group represented by the following formula (4), a hydroxyl group, or a (meth)acryloyloxy group, provided that W.sup.1 and W.sup.2 do not simultaneously represent a hydroxyl group or the group represented by the following formula (4), and at least one of W.sup.1 and W.sup.2 represents a group represented by the formula (2); R.sup.3a and R.sup.3b each independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group; and n1 and n2 each independently represent an integer of 0 to 4, ##STR00057## wherein a ring Z represents a fused aromatic hydrocarbon ring; X represents a single bond or S; R.sup.1 represents a single bond; R.sup.2 represents substituent group A or B, wherein substituent group A represents a monovalent hydrocarbon group, a hydroxyl group, a group represented by OR.sup.4a, a group represented by SR.sup.4b, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by NHR.sup.4c, a group represented by N(R.sup.4d).sub.2, a (meth)acryloyloxy group, or a sulfo group; and substituent group B represents a group formed by substituting at least a part of hydrogen atoms bonded to carbon atoms of the substituents contained in substituent group C below with a monovalent hydrocarbon group, a group represented by OR.sup.4a, a group represented by SR.sup.4b, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by NHR.sup.4c, a group represented by N(R.sup.4d).sub.2, a (meth)acryloyloxy group, a mesyloxy group, or a sulfo group, wherein substituent group C represents a monovalent hydrocarbon group, a group represented by OR.sup.4a, a group represented by SR.sup.4b, an acyl group, an alkoxycarbonyl group, a group represented by NHR.sup.4c or a group represented by N(R.sup.4d).sub.2; R.sup.4a to R.sup.4d each independently represent a monovalent hydrocarbon group; and m is an integer of 0 or more, and ##STR00058## wherein a ring Z, X, R.sup.1, R.sup.2, and m are as defined above.

2. The vinyl-group-containing fluorene-based compound according to claim 1, wherein the ring Z is a naphthalene ring.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described more specifically with examples, but the scope of the present invention is not limited to these examples.

(2) Compounds Represented by the Formula (1) and Comparative Compounds

(3) Compounds 1 to 3 represented by the following formulae were provided as the compounds represented by the general formula (1). Further, for comparison, Comparative Compounds 1 to 6 represented by the following formulae were provided.

(4) ##STR00041## ##STR00042##

(5) Synthesis methods for Compounds 1 to 3 will be described below (Synthesis Examples 1 to 3). Materials used in Synthesis Examples were as follows.

(6) [Inorganic Base]

(7) (1) Light Ash Sodium Carbonate

(8) Particle diameter distribution: 250 m or more; 3% by weight

(9) 150 m (inclusive) to 250 m (exclusive); 15% by weight

(10) 75 m (inclusive) to 150 m (exclusive); 50% by weight

(11) Less than 75 m; 32% by weight

(12) The particle diameter distribution was determined by sieving particles with sieves of 60 meshes (250 m), 100 meshes (150 m), and 200 meshes (75 m) and measuring the weight of oversize particles and undersize particles.

(13) [Transition Element Compound Catalyst]

(14) (1) di--chlorobis(1,5-cyclooctadiene)diiridium(I): [Ir(cod)Cl].sub.2
[Hydroxy Compound] (1) 9,9-Bis(6-hydroxy-2-naphthyl)fluorene (2) 9,9-Bis(4-hydroxyphenyl)fluorene
[Vinyl Ester Compound]

(15) (1) Vinyl propionate

[Synthesis Example 1] Synthesis of Compound 1

(16) A 1000-ml reaction vessel equipped with a cooling pipe and a decanter that conducts separation of a condensate and returns an organic layer to the reaction vessel and discharges a water layer to the outside of the system was charged with di--chlorobis(1,5-cyclooctadiene)diiridium(I) [Ir(cod)Cl].sub.2 (839 mg, 1.25 mmol), light ash sodium carbonate (12.7 g, 0.12 mol), 9,9-bis(6-hydroxy-2-naphthyl)fluorene (225 g, 0.5 mol), vinyl propionate (125 g, 1.25 mol), and toluene (300 ml). Thereafter, the temperature of the system was gradually raised while stirring with a stirring blade having a surface area of 10 cm.sup.2 at a rotation speed of 250 rpm, followed by reflux. A reaction was allowed to proceed for 5 hr under reflux while removing water produced as by-product with the decanter. The reaction solution was analyzed by gas chromatography. As a result, it was found that the conversion of 9,9-bis(6-hydroxy-2-naphthyl)fluorene was 100%, and 9,9-bis(6-vinyloxy-2-naphthyl)fluorene (Compound 1) and bis-6-naphthofluorene monovinyl ether were produced at yields of 81% and 4%, respectively, based on 9,9-bis(6-hydroxy-2-naphthyl)fluorene.

(17) .sup.1H-NMR (CDCl.sub.3): 4.47 (dd, 2H, J=1.5 Hz, 5.0 Hz), 4.81 (dd, 2H, J=3.5 Hz, 12.0 Hz), 6.71 (dd, 2H, J=6.0 Hz), 7.12-7.82 (m, 20H)

[Synthesis Example 2] Synthesis of Compound 2 (Isolation)

(18) The reaction product obtained in Synthesis Example 1 was subjected to separation and purification by column chromatography on silica gel to isolate bis-6-naphthofluorene monovinyl ether (Compound 2).

(19) .sup.1H-NMR (CDCl.sub.3): 4.55 (dd, 1H, J=6.0 Hz), 4.88 (dd, 1H, J=3.5 Hz), 6.79 (dd, 1H, J=6.0 Hz, 14.0 Hz), 7.20-7.89 (m, 20H)

[Synthesis Example 3] Synthesis of Compound 3

(20) A 1000-ml reaction vessel equipped with a cooling pipe and a decanter that conducts separation of a condensate and returns an organic layer to the reaction vessel and discharges a water layer to the outside of the system was charged with di--chlorobis(1,5-cyclooctadiene)diiridium(I) [Ir(cod)Cl].sub.2 (839 mg, 1.25 mmol), light ash sodium carbonate (12.7 g, 0.12 mol), 9,9-bis(4-hydroxyphenyl)fluorene (186 g, 0.5 mol), vinyl propionate (125 g, 1.25 mol), and toluene (300 ml). Thereafter, the temperature of the system was gradually raised while stirring with a stirring blade having a surface area of 10 cm.sup.2 at a rotation speed of 250 rpm, followed by reflux. A reaction was allowed to proceed for 5 hr under reflux while removing water produced as by-product with the decanter. The reaction solution was analyzed by gas chromatography. As a result, it was found that the conversion of 9,9-bis(4-hydroxyphenyl)fluorene was 100%, and 9,9-bis(4-vinyloxyphenyl)fluorene (Compound 3) and bis-4-phenolfluorene monovinyl ether were produced at yields of 72% and 9%, respectively, based on 9,9-bis(4-hydroxyphenyl)fluorene.

(21) .sup.1H-NMR (CDCl.sub.3): 4.47 (dd, 2H), 4.81 (dd, 2H), 6.71 (dd, 2H), 7.12-7.82 (m, 16H)

(22) Evaluation

(23) Compounds 1 and 3 and Comparative Compounds 1 to 6 were dissolved in propylene glycol monomethyl ether acetate to prepare solutions having a concentration of 20% by mass. The solutions were coated with a spin coater on a glass substrate, and the coatings were prebaked at 100 C. for 120 sec to form dried coatings (coating thickness 2.0 m). The dried coatings were postbaked at 230 C. for 20 min to obtain cured films (film thickness 1.7 m).

(24) In order to evaluate the reactivity of Compounds 1 and 3 and Comparative Compounds 1 to 6, for the cured films, the pencil hardness was measured according to JIS K 5400. The higher the pencil hardness, the higher the reactivity of the compound.

(25) For the cured films (for the dried coatings when the cured film was not obtained), a light transmittance at a wavelength of 633 nm and a refractive index were measured as optical parameters.

(26) Further, in order to evaluate the heat resistance of the cured films, the cured films were heated from room temperature (about 20 C.) at a temperature rise rate of 10 C. per min to conduct a thermogravimetric analysis in the air. In the thermogravimetric analysis, a temperature at which the mass was reduced by 5% based on the mass of the cured films at the start of the analysis, T.sub.d5%, was measured.

(27) The results of measurement are shown in Table 1.

(28) TABLE-US-00001 TABLE 1 Pencil Light Refractive T.sub.d5% hardness transmittance index ( C.) Compound 1 7 H 98% 1.74 357 Compound 3 6 H 98% 1.65 335 Comparative compound 1 Uncured 90% 1.72 Comparative compound 2 Uncured 94% 1.63 Comparative compound 3 5 H 97% 1.69 400 Comparative compound 4 4 H 97% 1.59 376 Comparative compound 5 2 H 88% 1.67 396 Comparative compound 6 3 H 92% 1.57 389

(29) As is apparent from Table 1, the cured films obtained from Compounds 1 and 3 had a high pencil hardness, and these compounds had a high reactivity. For the cured films obtained from Compounds 1 and 3, the light transmittance met a value of not less than 98% that is required of recent functional membranes, and the refractive index and the heat resistance were good.

(30) On the other hand, the cured films obtained from Comparative Compounds 1 to 6 had a lower pencil hardness than the cured films obtained form Compounds 1 and 3, and Comparative Compounds 1 to 6 had an inferior reactivity. Further, the cured films obtained from Comparative Compounds 1 to 6 were inferior in light transmittance to the cured films obtained from Compounds 1 and 3.

Synthesis Examples Through Leaving Group-Containing Fluorene-Based Compounds

Synthesis Example 4

(31) 6,6-(9-Fluorenylidene)-bis(2-naphthyloxyethanol) (598 g, 1.11 mol), pyridine (87.8 g, 1.11 mol), and dipropylene glycol dimethyl ether (1670 mL) were added to a 5-L reactor, the atmosphere of the system was replaced by nitrogen, and the temperature was raised to 60 C. Thionyl chloride (395.9 g, 3.33 mol) was added dropwise over a time period of 3 hr, followed by ripening for 2 hr. The reaction solution was cooled to 30 C., water was added to stop the reaction, and methanol was added dropwise at a temperature in the range of 15 to 20 C. to obtain a target compound with the hydroxyl group replaced by chlorine at a yield of 96% (compound represented by the following formula; the compound being referred to also as Compound 4).

(32) .sup.1H-NMR (CDCl.sub.3): 3.85 (t, 4H, J=6.0 Hz), 4.31 (t, 4H, J=6.0 Hz), 7.08-7.82 (m, 20H)

(33) ##STR00043##

Synthesis Example 5

(34) A solution of potassium-t-butoxide (327.5 g, 2.92 mol) in tetrahydrofuran (1260 mL) was added dropwise at a temperature in the range of 20 C. to 40 C. to a 5-L reactor that had been charged with Compound 4 (560 g, 0.97 mol) and tetrahydrofuran (1260 mL). The reaction solution was ripened at 60 C. for 2 hr. Water was added to stop the reaction. The organic layer was separated and concentrated in an evaporator to a weight that was twice larger than the charged amount of Compound 4. The concentrate was added dropwise to methanol to obtain 9,9-bis(6-vinyloxy-2-naphthyl)fluorene (compound represented by the following formula, that is, Compound 1) as a white or grayish white solid at a yield of 77%.

(35) .sup.1H-NMR (CDCl.sub.3): 4.48 (dd, 2H, J=1.5 Hz, 6.5 Hz), 4.81 (dd, 2H, J=1.5 Hz, 13.5 Hz), 6.73 (dd, 2H, J=6.5 Hz, 13.5 Hz), 7.13-7.83 (m, 20H)

(36) ##STR00044##

Synthesis Example 6

(37) Ethylene glycol (1.00 g, 0.0161 mol), triethylamine (3.42 g, 0.0338 mol), and tetrahydrofuran (3.38 mL) were added to a 25-mL reactor. The atmosphere of the reactor was replaced by nitrogen, and the system was cooled to 0 C. Methanesulfonyl chloride (3.88 g, 0.0338 mol) was added dropwise over a time period of 2 hr. The reaction solution was ripened for one hr, and water was added to stop the reaction. Ethyl acetate was added, the organic layer was separated, and the solvent was removed by evaporation in an evaporator to obtain a compound that was ethylene glycol at a yield of 80% with a methanesulfonyl group added thereto (compound represented by the following formula; hereinafter referred to also as EG-DMs)

(38) .sup.1H-NMR (CDCl.sub.3): 3.10 (s, 6H), 4.47 (s, 4H)

(39) ##STR00045##

Synthesis Example 7

(40) 6,6-(9-Fluorenylidene)-2,2-dinaphthol (compound represented by the following formula indicated on the left side; 1.00 g, 0.0022 mol; hereinafter referred to also as Compound 5), potassium carbonate (0.64 g, 0.0047 mol), and tetrahydrofuran (3.38 mL) were added to a 25-mL reactor. The atmosphere of the reactor was replaced by nitrogen. A solution of EG-DMs (1.02 g, 0.0047 mol) synthesized in Synthesis Example 6 in tetrahydrofuran (1.12 mL) was added at room temperature, the mixture was heated to 60 C., and the reaction solution was ripened for 15 hr. The reaction solution was analyzed by HPLC. As a result, it was found that Compound 6 (compound represented by the following formula indicated on the right side) was synthesized at a conversion of Compound 5 of 99% and a selectivity of 65%.

(41) (Compound 6) .sup.1H-NMR (CDCl.sub.3): 3.08 (s, 6H), 4.32 (t, 4H, J=4.4 Hz), 4.60 (t, 4H, J=4.4 Hz), 7.05-7.83 (m, 20H)

(42) ##STR00046##

Synthesis Example 8

(43) A solution of potassium-t-butoxide (1.45 g, 0.0130 mol) in tetrahydrofuran (2.25 mL) was added dropwise at a temperature in the range of 20 C. to 40 C. to a 25-mL reactor charged with Compound 6 (2.00 g, 0.00288 mol), dipropylene glycol dimethyl ether (2.25 mL). The reaction solution was ripened at 100 C. for 2 hr. The reaction solution was analyzed by HPLC. As a result, it was found that Compound 1 was synthesized at a conversion of Compound 6 of 99% and a selectivity of 58% and a monovinyl monomesyl compound (compound represented by the following formula; hereinafter referred to also as Compound 7) was synthesized at a selectivity of 32%.

(44) .sup.1H-NMR (CDCl.sub.3): 3.10 (s, 3H), 4.34 (t, 2H, J=3.6 Hz), 4.49 (dd, 1H, J=1.2 Hz, 5.2 Hz), 4.62 (t, 2H, J=3.6 Hz), 4.81 (dd, 1H, J=1.2 Hz, 11.2 Hz), 6.73 (dd, 1H, J=5.2 Hz, 11.2 Hz), 7.06-7.83 (m, 20H)

(45) ##STR00047##

Synthesis Example 9

(46) 2-Chloroethanol (3.00 g, 0.048 mol), triethylamine (5.87 g, 0.058 mol), and tetrahydrofuran (10.12 mL) were added to a 50-mL reactor. The atmosphere in the reactor was replaced by nitrogen. Thereafter, the reaction solution was cooled to 0 C. Methanesulfonyl chloride (6.09 g, 0.053 mol) was added dropwise over a time period of 2 hr. The reaction solution was ripened for one hr. Water was added to stop the reaction. Ethyl acetate was added, the organic layer was separated, and the solvent was removed by evaporation in an evaporator to obtain a compound that was 2-chloroethanol with a methanesulfonyl group added thereto (compound represented by the following formula; hereinafter referred to also as ClEMs) at a yield of 80%.

(47) .sup.1H-NMR (CDCl.sub.3): 3.09 (s, 3H), 3.77 (t, 2H, J=5.5 Hz), 4.45 (t, 2H, J=5.5 Hz)

(48) ##STR00048##

Synthesis Example 10

(49) Compound 5 (1.00 g, 0.0022 mol), potassium carbonate (0.64 g, 0.0047 mol), and dipropylene glycol dimethyl ether (2.23 mL) were added to a 25-mL reactor. The atmosphere in the reactor was replaced by nitrogen. A solution of ClEMs (1.06 g, 0.0067 mol) in dipropylene glycol dimethyl ether (1.12 mL) was added at room temperature. The mixture was heated to 60 C., and the reaction mixture was ripened for 15 hr. The reaction solution was analyzed by HPLC. As a result, it was found that Compound 4 was synthesized at a conversion of Compound 5 of 17% and a selectivity of 4% and Compound 8 (compound represented by the following formula) was synthesized at a selectivity of 12%.

(50) .sup.1H-NMR (CDCl.sub.3): 3.86 (t, 2H, J=6.0 Hz), 4.32 (t, 2H, J=6.0 Hz), 7.09-7.82 (m, 20H)

(51) ##STR00049##

Synthesis Example 11

(52) A solution of potassium-t-butoxide (0.58 g, 0.0052 mol) in tetrahydrofuran (6.8 mL) was added dropwise at a temperature in the range of 20 C. to 40 C. to a 25-mL reactor charged with Compound 4 (3.0 g, 0.0052 mol) and tetrahydrofuran (6.8 mL). The reaction solution was ripened at 60 C. for 2 hr. Water was then added to stop the reaction. The organic layer was analyzed by HPLC. As a result, it was found that Compound 1 was synthesized at a conversion of Compound 4 of 57% and a selectivity of 25% and a monovinyl monochloro compound (compound represented by the following formula; hereinafter referred to also as Compound 9) was synthesized at a selectivity of 75%.

(53) .sup.1H-NMR (CDCl.sub.3): 3.84 (t, 2H, J=6.0 Hz), 4.30 (t, 2H, J=6.0 Hz), 4.48 (dd, 1H, J=1.6 Hz, 6.0 Hz), 4.81 (dd, 1H, J=1.6 Hz, 13.6 Hz), 6.72 (dd, 1H, J=6.0 Hz, 13.6 Hz), 7.08-7.82 (m, 20H)

(54) ##STR00050##

Synthesis Example 12

(55) 9,9-Bis(4-(2-hydroxyethoxy)phenyl)fluorene (6.26 g, 0.0143 mol), pyridine (2.82 g, 0.0357 mol), dipropylene glycol dimethyl ether (33.4 mL), and tetrahydrofuran (33.7 mL) were added to a 200-mL reactor. The atmosphere in the reactor was replaced by nitrogen. The reaction solution was heated to 60 C. Thionyl chloride (6.79 g, 0.0571 mol) was added dropwise over a time period of 2 hr. The reaction solution was then ripened for 2 hr. After cooling to 30 C., water was added to stop the reaction, and methanol was added dropwise at a temperature in the range of 15 to 20 C. to obtain a target compound in which the hydroxyl group was replaced with chlorine (compound represented by the following formula; hereinafter referred to also as Compound 10) at a yield of 95%.

(56) .sup.1H-NMR (CDCl.sub.3): 3.75 (t, 4H, J=6.0 Hz), 4.14 (t, 4H, J=6.0 Hz), 6.73-7.75 (m, 16H)

(57) ##STR00051##

Synthesis Example 13

(58) A solution of potassium-t-butoxide (3.53 g, 0.0315 mol) in tetrahydrofuran (13.6 mL) was added dropwise at a temperature in the range of 20 C. to 40 C. to a 100-mL reactor charged with Compound 10 (5.0 g, 0.0105 mol) and tetrahydrofuran (11.5 mL). The reaction solution was ripened at 60 C. for 2 hr. Water was then added to stop the reaction. The organic layer was separated and concentrated in an evaporator to a weight that was twice larger than the charged amount of Compound 10. The concentrate was added dropwise to methanol to obtain 9,9-bis(4-vinyloxyphenyl)fluorene (compound represented by the following formula, that is, Compound 3), as a white or grayish white solid at a yield of 79%.

(59) .sup.1H-NMR (CDCl.sub.3): 4.47 (dd, 2H), 4.81 (dd, 2H), 6.71 (dd, 2H), 7.12-7.82 (m, 16H)

(60) ##STR00052##

Compounds Represented by General Formula (19)

Synthesis Example 14

(61) Compound 5 (3.00 g, 0.00666 mol), triethylamine (1.48 g, 0.0146 mol), phenothiazine (9.00 mg, 0.0000452 mol), and tetrahydrofuran (16.9 mL) were added to a 50-mL reactor. The atmosphere in the reactor was replaced by nitrogen. The reaction solution was cooled to 0 C. Acryloyl chloride (1.51 g, 0.0166 mol) was added dropwise over a time period of one hr, and the reaction solution was ripened for 2 hr. Water was added to stop the reaction, and the organic layer was separated. The solvent was removed by evaporation in an evaporator, and the residue was then purified by column chromatography on silica gel to obtain a target diacryl compound (compound represented by the following formula; hereinafter referred to also as Compound 11) as a white solid at a yield of 63%.

(62) .sup.1H-NMR (CDCl.sub.3): 6.03 (dd, 2H, J=1.5 Hz, 10.0 Hz), 6.36 (dd, 2H, J=10.0 Hz, 17.5 Hz), 6.63 (dd, 2H, J=1.5 Hz, 17.5 Hz), 7.19-7.84 (m, 20H)

(63) ##STR00053##

Synthesis Example 15

(64) Compound 5 (3.00 g, 0.00666 mol), triethylamine (1.48 g, 0.0146 mol), phenothiazine (9.00 mg, 0.0000452 mol), and tetrahydrofuran (16.9 mL) were added to a 50-mL reactor. The atmosphere in the reactor was replaced by nitrogen. The reaction solution was then cooled to 0 C. Methacryloyl chloride (1.74 g, 0.0166 mol) was added dropwise over a time period of one hr, and the reaction solution was then gradually heated to 40 C. and ripened for 2 hr. Water was added to stop the reaction, and the organic layer was separated. The solvent was removed by evaporation in an evaporator, and the residue was purified by column chromatography on silica gel to obtain a target dimethacryl compound (compound represented by the following formula; hereinafter referred to also as Compound 12) as a white solid at a yield of 73%.

(65) .sup.1H-NMR (CDCl.sub.3): 2.08 (s, 6H), 5.77 (s, 2H), 6.38 (s, 2H), 7.18-7.84 (m, 20H)

(66) ##STR00054##

Preparation of Negative-Type Photosensitive Resin Composition

Example 1

(67) The following ingredients were added to a mixed solvent of 3-methoxybutyl acetate (MA)/tetramethylurea (TMU)/propylene glycol monomethyl ether acetate (PM)=55/10/35 (mass ratio). The mixture was mixed with a stirrer for one hr and filtered through a 5-m membrane filter to prepare a negative-type photosensitive resin composition having a solid content of 15% by mass as a filtrate.

(68) An alkali-soluble resin

(69) Resin (R-1) (solid content 55%, solvent: 3-methoxybutyl acetate) . . . 60 parts by mass

(70) Photopolymerizable monomer

(71) Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) . . . 20 parts by mass

(72) Photopolymerization initiator

(73) OXE-02 (tradename: manufactured by BASF) . . . 10 parts by mass

(74) Compound represented by general formula (1)

(75) Compound 1 . . . 10 parts by mass

(76) Coloring Agent

(77) Carbon dispersion CF black (tradename: manufactured by Mikoku Color Ltd., solid content 25%, solvent: 3-methoxybutyl acetate) . . . 400 parts by mass

(78) The resin (R-1) was synthesized by the following method.

(79) At the outset, a 500-mL four-necked flask was charged with 235 g of a bisphenolfluorene epoxy resin (epoxy equivalent 235), 110 mg of tetramethyl ammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid. The contents were heat-dissolved at 90 to 100 C. while blowing air thereinto at a rate of 25 ml/min. Next, in such a state that the solution was cloudy, the solution was gradually heated to 120 C. for full dissolution. In this case, the solution gradually became transparent and viscous but was continued to be stirred. In this period, the acid value was measured, and heating with stirring was continued until the acid value reached less than 1.0 mg KOH/g. A time period of 12 hr was necessary until the acid value reached a target value. The solution was then cooled to room temperature to obtain a bisphenolfluorene epoxy acrylate that was colorless, transparent and solid and represented by the following formula (r-4)

(80) ##STR00055##

(81) Next, 600 g of 3-methoxybutyl acetate was added to and dissolved in 307.0 g of the bisphenolfluorene epoxy acrylate. 80.5 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed into the solution. The mixture was gradually heated, and a reaction was allowed to proceed at 110 to 115 C. for 4 hr. After the disappearance of an acid anhydride group, 38.0 g of 1,2,3,6-tetrahydro phthalic anhydride was mixed thereinto, and a reaction was allowed to proceed at 90 C. for 6 hr to obtain a resin (R-1). The disappearance of the acid anhydride group was confirmed by an IR spectrum.

(82) The resin (R-1) corresponds to a compound represented by the general formula (r-1).

Example 2 and Comparative Examples 1 to 6

(83) In Example 2 and Comparative Examples 2 to 6, negative-type photosensitive resin compositions were prepared in the same manner as in Example 1, except that Compound 3 and Comparative Compound 1 to 5 were used instead of Compound 1. Further, in Comparative Example 1, a negative-type photosensitive resin composition was prepared in the same manner as in Example 1, except that Compound 1 was not used.

(84) [Evaluation]

(85) Negative-type photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 to 6 were spin-coated on a glass substrate (100 mm100 mm), and the coatings were prebaked at 90 C. for 120 sec to form coatings having a thickness of 1.0 m. Next, the coatings were irradiated with ultraviolet light using a mirror projection aligner (product name: TME-150RTO, manufactured by Topcon Corp.) at an exposure gap of 50 m through a negative mask with a line pattern of 5, 10, 15, and 20 m formed therein. The exposure was 10 mJ/cm.sup.2. After exposure, the coating films were developed with a 0.04 mass % aqueous KOH solution of 26 C. for 40 sec and postbaked at 230 C. for 30 min to form line patterns.

(86) The line patterns thus formed were observed under an optical microscope to evaluate pattern adhesion. The pattern adhesion was evaluated as good when the line pattern was formed without separation from the substrate; and was evaluated as no adhesion when the line pattern was not formed due to separation from the substrate.

(87) The results are shown in Table 3 below.

(88) TABLE-US-00002 TABLE 2 Compound of formula (1) or comparative Adhesion of pattern compound 5 m 10 m 15 m 20 m Example 1 Compound 1 Good Good Good Good Example 2 Compound 3 Good Good Good Good Comparative None None None Good None Example 1 Comparative Comparative None None Good None Example 2 Example 1 Comparative Comparative None Good None None Example 3 Example 2 Comparative Comparative None Good None None Example 4 Example 3 Comparative Comparative None None Good None Example 5 Example 4 Comparative Comparative None None Good None Example 6 Example 5

(89) As is apparent from Table 3, when the negative-type photosensitive resin compositions of Examples 1 and 2 containing Compounds 1 and 3 represented by the general formula (1) were used, a 5-m line pattern was closely adhered to substrate even at a low exposure of 10 mJ/cm.sup.2.

(90) On the other hand, when the negative-type photosensitive resin composition of Comparative Example 1 free from the compound represented by the general formula (1), and the negative-type photosensitive resin compositions of Comparative Examples 2 to 6 that were free from the compound represented by the general formula (1) and contained Comparative Compounds 1 to 5 were used, as is apparent from Table 3, the pattern adhesion was inferior to that in Examples 1 and 2 and good micropatterning properties could not be obtained.