PHOTOCHROMIC COMPOUND, NAPHTHOL DERIVATIVE, CURABLE COMPOSITION, OPTICAL ARTICLE, LENS, AND EYEGLASSES

Abstract

The purpose of the present invention is to provide: a photochromic compound having an excellent color fading rate and excellent durability; a naphthol derivative that can become an intermediate for the photochromic compound; and a curable composition, an optical article, a lens and eyeglasses each containing the photochromic compound. According to embodiments, a photochromic compound having a backbone represented by formula (1) is provided. In formula (1), M represents C, Si or Ge; R.sup.1 represents a haloalkyl group having 1 to 20 carbon atoms inclusive; R.sup.2 represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms inclusive or a substituted or unsubstituted haloalkyl group having 1 to 20 carbon atoms inclusive.

Claims

1. A photochromic compound having a backbone represented by Formula (1) below: ##STR00091## wherein M is C, Si, or Ge; R.sup.1 is a haloalkyl group having 1 or more and 20 or less carbon atoms; R.sup.2 is a substituted or unsubstituted alkyl group having 1 or more and 20 or less carbon atoms or a substituted or unsubstituted haloalkyl group having 1 or more and 20 or less carbon atoms; Ring A is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to any of the above-mentioned rings, or Ring A may not be present; and Ring B is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to any of the above-mentioned rings.

2. The photochromic compound according to claim 1, having a backbone represented by Formula (2) below: ##STR00092## wherein R.sup.1, R.sup.2, and M are each the same as in Formula (1).

3. The photochromic compound according to claim 1, represented by Formula (3) below: ##STR00093## wherein R.sup.1, R.sup.2, and M are each the same as in Formula (1); R.sup.3 and R.sup.4 are each independently a hydroxyl group, an optionally substituted alkyl group, an optionally substituted haloalkyl group, an optionally substituted cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, an optionally substituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, an optionally substituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an optionally substituted aralkyl group, an optionally substituted aralkoxy group, an optionally substituted aryloxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or an optionally substituted cycloalkylthio group, an optionally substituted silyl group, an optionally substituted oxysilyl group, a group represented by Formula (X) below, or a group represented by Formula (Y) below; c is an integer from 0 to 4; when c is 2 to 4, a plurality of R.sup.3s may be the same as or different from each other; when c is 2 to 4 and adjacent R.sup.3s are present, two adjacent R.sup.3s may be taken together with a carbon atom to which R.sup.3s are attached to form a ring optionally comprising an oxygen atom, a carbon atom, a sulfur atom, or a nitrogen atom, and the ring is optionally substituted; d is an integer from 0 to 4; when d is 2 to 4, a plurality of R.sup.4s may be the same as or different from each other; when d is 2 to 4 and adjacent R.sup.4s are present, two adjacent R.sup.4s may be taken together with a carbon atom to which R.sup.4s are attached to form a ring optionally comprising at least one atom selected from the group consisting of an oxygen atom, a carbon atom, a sulfur atom, and a nitrogen atom and the ring is optionally substituted; and R.sup.5 and R.sup.6 are each independently an optionally substituted aryl group or an optionally substituted heteroaryl group; ##STR00094## in formula (X), E is an oxygen atom or NR.sup.101 in which R.sup.101 is a hydrogen atom or an alkyl group; F is an oxygen atom or a sulfur atom; G is an oxygen atom, a sulfur atom, or NR.sup.202 in which R.sup.202 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; g is 0 or 1; R.sup.201 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; and when G is an oxygen atom or a sulfur atom, R.sup.201 is a group other than a hydrogen atom; in L.sup.1-R.sup.400, R.sup.400 is a hydrogen atom, an alkyl group, an aryl group, a polymerizable group, a photochromic group, or a silyl group with an alkyl group, an alkoxyl group, or an aryl group as a substituent; and L.sup.1 is a group represented by Formula (X2) below; ##STR00095## in Formula (X2), J is a divalent group, each independently being directly attached, a substituted methylene group, an oxygen atom, a sulfur atom, or NR.sup.301 in which R.sup.301 is a hydrogen atom or an alkyl group; L is an oxygen atom or a sulfur atom; R.sup.300 is an alkylene group, or a silylene group having an alkyl group or an aryl group as a substituent; R.sup.302, R.sup.303, and R.sup.304 are each independently an alkylene group; h, j, k, and l are an integer of 0 or 1; i is an integer from 1 to 200, and values of a plurality of units i may be the same as or different from each other; and a dashed line represents a bond to R.sup.400;
-Q.sup.1-(X.sup.1Q.sup.2)a-X.sup.2Q.sup.3(Y) in Formula (Y) Q.sup.1 is an alkylene group optionally comprising a halogen atom as a substituent; Q.sup.2 is an alkylene group optionally comprising a halogen atom as a substituent; Q.sup.3 is an alkyl group optionally comprising a halogen atom as a substituent; X.sup.1 and X.sup.2 are each independently O, S, NR.sup.700, PR.sup.701, or P(O); R.sup.700 is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group; R.sup.701 is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group; and a is 0, or 1 or more and 10 or less.

4. The photochromic compound according to claim 1, wherein R.sup.1 is a haloalkyl group having 2 or more and 10 or less carbon atoms.

5. The photochromic compound according to claim 1, wherein R.sup.2 is a haloalkyl group having 1 or more and 20 or less carbon atoms.

6. The photochromic compound according to claim 1, wherein R.sup.1 is a group represented by Formula (1a) below:
(CH.sub.X.sup.11.sub.).sub.CH.sub.X.sup.12.sub.(1a) wherein x.sup.11 and X.sup.12 are each independently a halogen atom; and are independently 0 or 1 or 2; +=2; is 0 or 1 or 2; is 1 or more and 3 or less; +=3; and is 0, or 1 or more and 10 or less.

7. The photochromic compound according to claim 3, represented by Formula (4) below: ##STR00096## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, c, and d are each independently the same as in Formula (3); R.sup.7 and R.sup.8 are each independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, an optionally substituted arylthio group having 6 to 10 carbon atoms, or the group represented by L.sup.1-R.sup.400; e is an integer of 0 to 5; when e is 2 to 5, R.sup.7s may be the same as or different from each other; when adjacent R.sup.7s are present, two adjacent R.sup.7s may be taken together with a carbon atom to which R.sup.7s are attached to form a ring optionally comprising at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom and the ring is optionally substituted; f is an integer of 0 to 5; when f is 2 to 5, R.sup.8s may be the same as or different from each other; and when adjacent R.sup.8s are present, two adjacent R.sup.8s may be taken together with a carbon atom to which R.sup.8s are attached to form a ring optionally comprising at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom and the ring is optionally substituted.

8. The photochromic compound according to claim 3, wherein R.sup.1 and R.sup.2 are the same substituent as each other.

9. A curable composition comprising: the photochromic compound according to claim 1; and at least one selected from the group consisting of a radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerization reactive group, and a (thio)urethane(urea)polymer.

10. An optical article comprising a cured product of the curable composition according to claim 9.

11. A lens comprising a cured product of the curable composition according to claim 9.

12. Eyeglasses comprising the lens according to claim 11.

13. A naphthol derivative having a backbone represented by Formula (5) below: ##STR00097## wherein M is C, Si, or Ge; R.sup.1 is a haloalkyl group having 1 or more and 20 or less carbon atoms; and R.sup.2 is a substituted or unsubstituted alkyl group having 1 or more and 20 or less carbon atoms or a substituted or unsubstituted haloalkyl group having 1 or more and 20 or less carbon atoms.

Description

EXAMPLES

Example 1

First Step

[0230] Three hundred milliliters of toluene was added to 20.0 g (20.0 mmol) of an iodine compound represented by Formula (22) below, and azeotropic dehydration was performed until a water content in the toluene was 100 ppm or less. After the azeotropic dehydration, the resultant was slowly cooled to 20 C., and 15 mL of n-BuLi (1.6 mol/L hexane solution) was slowly added dropwise while maintaining 15 to 20 C. After consumption of the raw materials, 6.6 g (30.0 mmol) of 1,1,1,7,7,7-hexafluoro-4-heptanone was slowly added dropwise thereto. After the addition, the resultant was stirred at 15 to 20 C. for 1 hour and then slowly warmed to room temperature. After stirring for 1 hour, the resultant was partitioned by adding 300 ml of water thereto. This operation was repeated three times, and a solvent was removed from the resulting organic layer, followed by purification by chromatography on silica gel to obtain a compound represented by Formula (23) below at a yield of 72%.

##STR00034##

Second Step

[0231] After dissolving 8.1 g (14.4 mmol) of the compound of Formula (23) in 165 mL of tetrahydrofuran (THE), 2.0 g of 5% Pd/C (50% water content) was added thereto, and the resultant was reacted under a pressure with hydrogen gas at 0.05 to 0.1 Mpa. After consumption of the raw materials was confirmed, the Pd/C was filtered off, and a solvent was removed from the resulting organic layer to obtain a compound represented by Formula (24) below at a yield of 100%.

##STR00035##

Third Step

[0232] First, 350 mL of toluene was added to 14.2 g (75.0 mmol) of p-toluenesulfonic acid monohydrate, and azeotropic dehydration was performed until a water content in the toluene was 300 ppm or less. Then, a toluene solution in which 6.8 g (14.4 mmol) of the Formula (24) was dissolved in 100 mL of toluene was added slowly while maintaining 85 to 100 C., and after the addition, the resultant was refluxed. After consumption of the raw materials was confirmed, the resultant was cooled to room temperature and partitioned by adding 500 mL of water thereto. This operation was repeated three times, and a solvent was removed from the resulting organic layer, followed by purification by chromatography on silica gel to obtain a naphthol derivative represented by Formula (25) below at a yield of 87%.

##STR00036##

Fourth Step

[0233] First, 1.04 g (2.3 mmol) of the naphthol compound of Formula (25) and 0.88 g (3.5 mmol) of propargyl alcohol represented by Formula (26) below were dissolved in 30 mL toluene, and 0.5 g (0.2 mmol) of pyridinium p-toluenesulfonate was added thereto and stirred at 85 C. for 1 hour. After the above reaction, a solvent was removed, followed by purification by chromatography on silica gel to obtain a photochromic compound represented by Formula (27) below at a yield of 79%.

##STR00037##

[0234] Elemental analysis values for the photochromic compound represented by Formula (27) were determined to be C, 73.42%; H, 5.25%, which are in good agreement with the calculated values for C.sub.42H.sub.36F.sub.6O.sub.2 of C, 73.46%; H, 5.28%.

[0235] Proton nuclear magnetic resonance spectra were measured and showed a 17H peak based on a methyl group and a trifluoropropyl group around : 0.5 to 3.0 ppm, a 3H peak based on a methoxy group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0236] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 60 ppm.

Example 2

First Step

[0237] A naphthol derivative represented by Formula (29) below was obtained at a yield of 80% in the same manner as in First to Third steps in Example 1, except that a compound represented by Formula (28) below, which was synthesized with reference to the method described in Patent Document 6, was used instead of the compound of Formula (22).

##STR00038##

Second Step

[0238] A photochromic compound represented by Formula (31) below was obtained at a yield of 76% in the same manner, except that the naphthol derivative of Formula (29) was used instead of the naphthol derivative of Formula (25) and propargyl alcohol represented by Formula (30) below was used instead of the propargyl alcohol of Formula (26) in Fourth step in Example 1.

##STR00039##

[0239] Elemental analysis values for the photochromic compound represented by Formula (31) were determined to be C, 68.49%; H, 4.47%, which are in good agreement with the calculated values for C.sub.41H.sub.32F.sub.6O.sub.5 of C, 68.52%, H: 4.49%.

[0240] Proton nuclear magnetic resonance spectra were measured and showed an 8H peak based on a trifluoropropyl group around : 0.5 to 3.0 ppm, an 8H peak based on a methoxy group and methylenedioxy around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0241] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 60 ppm.

Example 3

First Step

[0242] A naphthol derivative represented by Formula (33) below was obtained at a yield of 79% in the same manner, except that a compound represented by Formula (32) below was used instead of the compound of Formula (22) and 1,1,1,9,9,9-hexafluoro-5-nonanone was used instead of 1,1,1,7,7,7-hexafluoro-4-heptanone in First to Third steps in Example 1.

##STR00040##

Second Step

[0243] A photochromic compound represented by Formula (35) below was obtained at a yield of 76% in the same manner, except that the naphthol derivative of Formula (33) was used instead of the naphthol derivative of Formula (25) and propargyl alcohol represented by Formula (34) below was used instead of the propargyl alcohol of Formula (26) in Fourth step in Example 1.

##STR00041##

[0244] Elemental analysis values for the photochromic compound represented by Formula (35) were determined to be C, 69.68%; H, 5.28%; N, 1.54%; S, 3.59%, which are in good agreement with the calculated values for C.sub.52H.sub.47F.sub.6NO.sub.4S of C, 69.71%; H, 5.29%; N, 1.56%; S, 3.58%.

[0245] Proton nuclear magnetic resonance spectra were measured and showed a 12H peak based on a trifluorobutyl group around : 0.5 to 3.0 ppm, a 14H peak based on a methoxy group and a morpholino group around : 3.0 to 5.0 ppm, and a 21H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0246] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 4

First Step

[0247] First, 26.7 g (62.4 mmol) of a compound represented by Formula (36) below, which was synthesized from 4-methoxy-4-bromobenzophenone with reference to the method described in Patent Document 7, was dispersed in 100 mL of methanol. Then, 125 mL of an aqueous solution of 12.5 g (312 mmol) of sodium hydroxide was added to this solution and the resultant was refluxed for 3 hours. After the above reaction, the resultant was washed with concentrated hydrochloric acid and then water, a solvent was removed therefrom, and the resultant was purified by reslurrying with 300 mL of toluene to obtain a carboxylic acid compound represented by Formula (37) below at a yield of 90%.

##STR00042##

Second Step

[0248] First, 20.9 g (56.1 mmol) of the compound represented by Formula (37) and 15.7 g (123.6 mmol) of benzyl chloride were dissolved in 120 mL of DMF. Then, 19.4 g (140.6 mmol) of potassium carbonate was added to this solution, and the resultant was warmed to 80 C. and stirred for 3 hours. After the above reaction, a solvent was removed by washing with water. Then, 200 mL of isopropyl alcohol was added thereto, 220 mL of an aqueous solution of 22.4 g (561.0 mmol) of sodium hydroxide was added thereto, and the resultant was refluxed for 4 hours. After the above reaction, the resultant was cooled to 0 to 5 C. and partitioned by adding concentrated hydrochloric acid thereto to pH 1. A solvent was removed by washing with 500 mL of water twice. The resultant was purified by reslurrying with 300 mL of toluene to obtain a carboxylic acid compound represented by Formula (38) below at a yield of 89%.

##STR00043##

Third Step

[0249] First, 10.3 g (54.3 mmol) of p-trifluoromethylphenylboronic acid, 11.5 g (108.7 mmol) of sodium carbonate, 103.5 mL of water, 121.5 mL of 1,2-dimethoxyethane, and 12.2 mL of ethanol were added to 23.1 g (49.9 mmol) of the carboxylic acid compound represented by Formula (38) and the resultant was stirred while bubbling with nitrogen. The nitrogen bubbling was continued for about 20 minutes, and then 142.7 mg (0.1 mmol) of Pd(PPh.sub.3).sub.4 was added thereto and the resultant was reacted at 75 C. for 2 hours. After the above reaction, the resultant was cooled to room temperature, 650 mL of THE was added thereto, and the resultant was cooled to 0 to 5 C. and partitioned by adding concentrated hydrochloric acid thereto to pH 1. A solvent was removed by washing with 500 ml of water twice. The resultant was purified by reslurrying with 300 mL of methanol to obtain a carboxylic acid compound represented by Formula (39) below at a yield of 99%.

##STR00044##

Fourth Step

[0250] First, 26.1 g (49.4 mmol) of the carboxylic acid compound represented by Formula (39) was dispersed in 400 mL of toluene. Next, 24.9 g (247.0 mmol) of triethylamine and 17.7 g (64.6 mmol) of diphenylphosphoryl azide were added to this solution and the resultant was stirred at room temperature for 2 hours. Then, 20.0 g (435.3 mmol) of ethanol was added to this solution and the resultant was reacted at 70 C. for 2 hours. Five hundred milliliters of ethanol and then 30.0 g (535.7 mmol) of potassium hydroxide were added to this solution and the resultant was refluxed for 4 hours. After the above reaction, ethanol was distilled off at normal pressure, 300 mL of tetrahydrofuran was added thereto, and a solvent was removed by washing with 150 ml of water three times. Six hundred milliliters of acetonitrile and 150.0 g (247.0 mmol) of 6% hydrochloric acid aqueous solution were added thereto and the resultant was cooled to 0 C. to 5 C. Then, 15.3 g (74.1 mmol) of 33% sodium nitrite aqueous solution was added to this solution and the resultant was stirred for 30 minutes. Next, 41.2 g (247.0 mmol) of 50% potassium iodide aqueous solution was added to this solution and the resultant was stirred at room temperature for 4 hours. After the above reaction, 500 mL of toluene was added thereto and the resultant was washed with 300 ml of water three times. A solvent was removed from the resulting organic layer, followed by purification by chromatography on silica gel to obtain a compound represented by Formula (40) below at a yield of 70%.

##STR00045##

Fifth Step

[0251] A naphthol derivative represented by Formula (41) below was obtained at a yield of 76% in the same manner as in First to Third steps in Example 1, except that the compound represented by Formula (40) was used.

##STR00046##

Sixth Step

[0252] A photochromic compound represented by Formula (42) below was obtained at a yield of 75% in the same manner, except that the naphthol derivative of Formula (41) was used instead of the naphthol derivative of Formula (33) in Second step in Example 2.

##STR00047##

[0253] Elemental analysis values for the photochromic compound represented by Formula (42) were determined to be C, 67.87%; H, 4.43%, which are in good agreement with the calculated values for C.sub.48H.sub.37F.sub.9O.sub.4 of C, 67.92%, H: 4.39%.

[0254] Proton nuclear magnetic resonance spectra were measured and showed an 8H peak based on a trifluoropropyl group around : 0.5 to 3.0 ppm, a 9H peak based on a methoxy group around : 3.0 to 5.0 ppm, and a 20H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm. Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 60 ppm.

Example 5

First Step

[0255] First, 20.1 g (43.1 mmol) of an iodine compound represented by Formula (43) below, 1.0 g (4.3 mmol) of palladium acetate, 42.3 g (431.0 mmol) of potassium acetate, 38.8 g (387.9 mmol) of potassium bicarbonate, 74.9 g (431.0 mmol) of dibromomethane, 260 mL of N, N-dimethylformamide (DMF), 86 mL of N, N-dimethylacetamide (DMAc), 4.2 mL of isopropyl alcohol (IPA), and 43 mL of water were added, heated to 80 C., and then reacted. After consumption of the iodine compound was confirmed, the resultant was allowed to cool to room temperature and then partitioned between 100 ml of water and 300 mL of ethyl acetate. A solvent was removed from the resulting organic layer, followed by purification by chromatography on silica gel to obtain a compound represented by Formula (44) below at a yield of 58%.

##STR00048##

Second Step

[0256] First, 1.0 g (2.9 mmol) of the compound represented by Formula (44), 1.0 g (8.6 mmol) of potassium tertiary butoxide (tBuOK), and 50 mL of THE were added and cooled to 0 to 5 C. Then, 1.5 g (8.6 mmol) of 3-bromo-1,1,1-trifluoropropane diluted with 20 mL of THE was added dropwise thereto over 15 minutes. After completion of the addition, the resultant was stirred at room temperature. After consumption of the raw materials was confirmed, the resultant was cooled on ice and partitioned by adding 10 mL of 2% hydrochloric acid and 50 mL of ethyl acetate thereto. Twenty milliliters of water was added to the organic layer for washing with water. This operation was repeated until a pH of an aqueous layer reached 6 to 7. After a solvent was removed from the resulting organic layer, 20 mL of THE and 0.3 g of 5% Pd/C (50% water content) were added thereto, followed by reacting under a pressure with hydrogen gas at 0.05 to 0.1 Mpa. After consumption of the raw materials was confirmed, the Pd/C was filtered off, and a solvent was removed from the resulting organic layer, followed by purification by chromatography on silica gel to obtain a naphthol derivative represented by Formula (45) below at a yield of 74%.

##STR00049##

Third Step

[0257] A photochromic compound represented by Formula (46) below was obtained at a yield of 72% in the same manner, except that the naphthol derivative of Formula (45) was used instead of the naphthol derivative of Formula (33) in Second step in Example 3.

##STR00050##

[0258] Elemental analysis values for the photochromic compound represented by Formula (46) were determined to be C, 69.52%; H, 5.21%; N, 1.81%, which are in good agreement with the calculated values for C.sub.44H.sub.39F.sub.6NO.sub.4 of C, 69.56%; H, 5.17%; N, 1.84%.

[0259] Proton nuclear magnetic resonance spectra were measured and showed an 8H peak based on a trifluoropropyl group around : 0.5 to 3.0 ppm, a 14H peak based on a methoxy group and a morpholino group around : 3.0 to 5.0 ppm, and a 17H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0260] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 6

First Step

[0261] A naphthol derivative represented by Formula (47) below was obtained at a yield of 79% in the same manner, except that 3-bromo-4-methoxybenzophenone was used instead of 3,4-dimethoxy-4-bromobenzophenone and 4-diphenylaminophenylboronic acid was used instead of 4-trifluorophenylboronic acid in Example 4.

##STR00051##

Second Step

[0262] A photochromic compound represented by Formula (48) below was obtained at a yield of 77% in the same manner in Example 2, except that the naphthol derivative of Formula (47) was used for the reaction instead of the naphthol derivative of Formula (29).

##STR00052##

[0263] Elemental analysis values for the photochromic compound represented by Formula (48) were determined to be C, 74.70%; H, 5.03%; N, 1.47%, which are in good agreement with the calculated values for C.sub.59H.sub.47F.sub.6NO.sub.4 of C, 74.75%; H, 5.00%; N, 1.48%.

[0264] Proton nuclear magnetic resonance spectra were measured and showed an 8H peak based on a trifluoropropyl group around : 0.5 to 3.0 ppm, a 9H peak based on a methoxy group around : 3.0 to 5.0 ppm, and a 30H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0265] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 7

First Step

[0266] A naphthol derivative represented by Formula (50) below was obtained at a yield of 67% in the same manner, except that a compound of Formula (49) below was used instead of the compound of Formula (22) and 1,1,1-trifluoro-4-heptanone was used instead of 1,1,1,7,7,7-hexafluoro-4-heptanone in First step in Example 1.

##STR00053##

Second Step

[0267] A photochromic compound represented by Formula (51) below was obtained at a yield of 70 in the same manner as in Example 2, except that the naphthol derivative of Formula (50) was used instead of the naphthol derivative of Formula (29).

##STR00054##

[0268] Elemental analysis values for the photochromic compound represented by Formula (51) were determined to be C, 74.08%; H, 5.79%; N, 1.47%, which are in good agreement with the calculated values for C.sub.42H.sub.39F.sub.3O.sub.5 of C, 74.10%, H: 5.77%.

[0269] Proton nuclear magnetic resonance spectra were measured and showed an 11H peak based on a trifluoropropyl group and a propyl group around : 0.5 to 3.0 ppm, a 12H peak based on a methoxy group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0270] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 8

First Step

[0271] A naphthol derivative represented by Formula (52) below was obtained in the same manner, except that 1,1,1,5,5,5-hexafluoro-2-pentanone was used instead of 1,1,1,7,7,7-hexafluoro-4-heptanone in Example 1. Then, this naphthol derivative was reacted with propargyl alcohol in the same manner to obtain a photochromic compound represented by Formula (53) below at a yield of 65%.

##STR00055## ##STR00056##

[0272] Elemental analysis values for the photochromic compound represented by Formula (53) were determined to be C, 72.90%; H, 4.88%, which are in good agreement with the calculated values for C.sub.40H.sub.32F.sub.6O.sub.2 of C, 72.94%; H, 4.90%.

[0273] Proton nuclear magnetic resonance spectra were measured and showed a 13H peak based on a trifluoromethyl group and a methyl group around : 0.5 to 3.0 ppm, a 3H peak based on a methoxy group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0274] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

(Analytical Result for Naphthol Derivative)

[0275] Table 1 summarizes analytical results of the naphthol derivatives used in Examples 1 to 8.

TABLE-US-00001 TABLE 1 Compound Calculated value Determined value Example No. C H N S C H N S 1H-NMR 1 Formula 66.37 4.90 66.35 4.89 0.5-5.0 ppm 14H (25) 5.0-9.0 ppm 8H 2 Formula 61.54 3.87 61.51 3.90 0.5-5.0 ppm 10H (29) 5.0-9.0 ppm 8H 3 Formula 65.08 4.78 5.43 65.10 4.75 5.44 0.5-5.0 ppm 15H (33) 5.0-9.0 ppm 13H 4 Formula 62.21 3.87 62.17 3.93 0.5-5.0 ppm 11H (41) 5.0-9.0 ppm 12H 5 Formula 63.44 4.44 63.41 4.45 0.5-5.0 ppm 11H (45) 5.0-9.0 ppm 9H 6 Formula 72.30 4.77 2.01 72.28 4.79 2.04 0.5-5.0 ppm 11H (47) 5.0-9.0 ppm 22H 7 Formula 69.76 5.85 69.73 5.87 0.5-5.0 ppm 17H (50) 5.0-9.0 ppm 8H 8 Formula 65.09 4.28 65.06 4.29 0.5-5.0 ppm 10H (52) 5.0-9.0 ppm 8H

(Evaluation of Photochromic Plastic Lens Made by Coating Method for Physical Property)

Example 9

(Preparation of Curable Composition)

[0276] First, the photochromic compound obtained in Example 1, a photoinitiator, and a polymerizable compound were mixed to obtain a curable composition.

[0277] The polymerizable compound was a combination of the following radical polymerizable monomers:

[0278] Polyethylene glycol dimethacrylate (average molecular weight: 736): 42 parts by mass Polyethylene glycol dimethacrylate (average molecular weight: 536): 12 parts by mass Trimethylolpropane methacrylate: 38 parts by mass Y-Methacryloyloxypropyltrimethoxysilane: 2 parts by mass Glycidyl methacrylate: 1 part by mass.

[0279] Note that, in the curable composition, the photochromic compound was added in an amount of 0.27 mmol taking a total amount of the radical polymerizable monomers as 100 g.

[0280] The following additives were used:

[0281] Phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide (photoinitiator: Omnirad 819): 0.3 parts by mass Ethylene bis(oxyethylene) bis [3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate] (stabilizer, Irganox 245): 1 part by mass Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate: 3 parts by mass

[0282] Leveling agent (L7001) manufactured by DuPont Toray Specialty Materials K.K.: 0.1 parts by mass.

[0283] Note that, the above-mentioned additives are described with blended ratios taking a total of the radical polymerizable monomers as 100 parts by mass.

(Production of Optical Article)

[0284] Using this curable composition, a photochromic laminate was obtained by a lamination method including polymerization as follows.

[0285] First, a thiourethane plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. Note that, the thiourethane plastic lens had been alkaline-etched in a 10% sodium hydroxide aqueous solution at 50 C. for 5 minutes in advance, and then thoroughly washed with distilled water.

[0286] A spin coater (1H-DX2, manufactured by MIKASA CO., LTD) was used to coat a surface of the above-mentioned plastic lens with a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) at a rotation speed of 70 rpm for 15 seconds, followed by at 1000 rpm for 10 seconds. Then, about 2 g of the photochromic curable composition obtained as above was spin-coated at a rotation speed of 60 rpm for 40 seconds, followed by at 600 rpm for 10 to 20 seconds so as to achieve a photochromic coating layer with a film thickness of 40 m.

[0287] The lens of which surface had been coated with the photochromic curable composition (photochromic coating layer) was irradiated with light for 90 seconds in a nitrogen gas atmosphere using a metal halide lamp with an output of 200 mW/cm.sup.2 to cure the coating. The resultant was then further heated at 110 C. for 1 hour to produce a photochromic laminate with a photochromic layer.

Examples 10 to 16

[0288] Photochromic laminates were produced using the photochromic compounds obtained in Examples 2 to 8 (compounds according to Formula (31), Formula (35), Formula (42), Formula (46), Formula (48), Formula (51), and Formula (53)) in the same manner as in Example 9.

Comparative Examples 1 to 3

[0289] Photochromic laminates were obtained in the same manner as in Example 9 using photochromic compounds represented by Formulae (A) to (C) below.

##STR00057## ##STR00058## ##STR00059##

<Evaluation Method>

[0290] The resulting photochromic laminates were evaluated by the below-mentioned methods.

(1) Photochromic Property

[1] Maximum Absorption Wavelength (max):

[0291] This is the maximum absorption wavelength after color development determined by a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. (instantaneous multichannel photo detector MCPD3000) and was used as an index of a color tone upon color development.

[2] Color Developing Density at 23 C. (A.SUB.23.):

[0292] This is a difference between an absorbance {(240)} after irradiation with light at 23 C. for 240 seconds and an absorbance (0) when not irradiated with light at the above-mentioned maximum absorption wavelength and was used as an index of a color developing density. The higher this value is, the better photochromic property is.

[3] Color Fading Half-Life at 23 C. [1/2 (Sec).)]:

[0293] This is a period of time taken by an absorbance at the above-mentioned maximum absorption wavelength of a sample to decrease to of {(240)(0)} when irradiation is stopped after irradiation with light at 23 C. for 240 seconds, and was used as an index of a color fading rate. The shorter this period of time is, the faster the color fading rate is.

[0294] [4] Residual ratio (A.sub.50/A.sub.0100): The resulting photochromic plastic lens was subjected to accelerated degradation for 50 hours using a xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. Color developing densities were then evaluated as described above before and after a test, and a color developing density before the test (A.sub.0) and a color developing density after the test (A.sub.50) were measured. A ratio (A.sub.50/A.sub.0) was determined as a residual ratio and was used as an index of color development durability. The higher the residual ratio is, the more durable the color development is.

[0295] The results of Examples 9 to 16 are summarized in Table 2. The results of Comparative examples 1 to 3 are summarized in Table 3.

TABLE-US-00002 TABLE 2 Color devel- Color Maximum opment fading Resid- absorption density at half-life ual Compound wavelength 23 C. at 23 C. ratio No. (nm) () (sec) (%) Example Formula 434 0.48 46 83 9 (27) 551 0.89 46 83 Example Formula 454 0.57 16 84 10 (31) 566 0.39 16 84 Example Formula 484 0.57 19 82 11 (35) 597 0.62 19 82 Example Formula 440 0.59 21 83 12 (42) 576 0.77 21 83 Example Formula 458 0.35 16 81 13 (46) 589 0.66 16 81 Example Formula 471 0.80 30 87 14 (48) 565 0.68 30 87 Example Formula 424 0.69 78 82 15 (51) 592 1.05 78 82 Example Formula 432 0.55 79 82 16 (53) 552 0.98 79 82

TABLE-US-00003 TABLE 3 Color devel- Color Maximum opment fading Resid- Com- absorption density at half-life ual pound wavelength 23 C. at 23 C. ratio No. (nm) () (sec) (%) Comparative Formula 435 0.60 162 79 Example 1 (A) 557 1.06 162 79 Comparative Formula 438 0.53 95 62 Example 2 (B) 561 0.99 95 62 Comparative Formula 436 0.43 47 50 Example 3 (C) 560 0.78 47 50

[0296] The only difference between the compounds of Examples 9 and 16 and the compound of Comparative Examples 1 to 3 is a substituent attached to a carbon atom at position 13 of indenonaphthopyran. As can be clearly seen from Tables 2 and 3, the photochromic compounds according to the embodiment are photochromic compounds with superior color fading rate and durability to those of conventional photochromic compounds.

Example 17

First Step

[0297] First, 1.70 g (70.0 mmol) of magnesium was placed in a 300 mL 4-necked flask and dried well by heating under reduced pressure, and then 150 mL of dehydrated THE was added thereto and stirred. Then, 1-bromo-4-fluorobutane was slowly added dropwise thereto. After the addition, an internal temperature was slowly heated to reflux until the raw materials were completely consumed to prepare 4-fluorobutylmagnesium bromide.

Second Step

[0298] First, 2.95 g (10.0 mmol) of a benzyl-protected compound represented by Formula (54) below, which was synthesized with reference to the method described in Patent Document 6, 2.97 g (70.0 mmol) of lithium chloride, and 17.2 g (70.0 mmol) of anhydrous lanthanum chloride were added to a 500 mL four-necked flask and dried by heating under reduced pressure, and 100 mL of dehydrated THE was added thereto. After stirring, the resultant was cooled to 76 C. A THE solution of 4-fluorobutylmagnesium bromide prepared in First step was added slowly thereto.

##STR00060##

[0299] After completion of the addition, an internal temperature was slowly increased to room temperature and the resultant was stirred for 12 hours. After disappearance of the raw materials was confirmed, 300 mL of toluene was added, and 10% hydrochloric acid was added until a pH of an aqueous layer was 1. Then, the resultant was partitioned by adding 300 mL of water thereto and then this operation was repeated until a pH of an aqueous layer was around 7. The resulting organic layer was concentrated and purified by silica gel column chromatography to obtain a compound represented by Formula (55) below at a yield of 85%.

##STR00061##

Third Step

[0300] A compound represented by Formula (56) below was obtained at a yield of 100% in the same manner, except that the compound of Formula (55) was used for the reaction instead of the compound of Formula (23) in Second step in Example 1.

##STR00062##

Fourth Step

[0301] A naphthol compound represented by Formula (57) below was obtained at a yield of 85% in the same manner, except that the compound of Formula (56) was used instead of the compound of Formula (24) in Third step in Example 1.

##STR00063##

Fifth Step

[0302] A photochromic compound represented by Formula (58) below was obtained at a yield of 76% in the same manner, except that the naphthol compound of Formula (57) was used instead of the naphthol compound of Formula (33) in Second step in Example 3.

##STR00064##

[0303] Elemental analysis values for the photochromic compound represented by Formula (58) were determined to be C, 74.04%; H, 6.09%; N, 1.89%; S, 4.33%, which are in good agreement with the calculated values for C.sub.46H.sub.45F.sub.2NO.sub.4S of C, 74.07%; H, 6.08%; N, 1.88%; S, 4.30%.

[0304] Proton nuclear magnetic resonance spectra were measured and showed a 16H peak based on a fluorobutyl group around : 0.5 to 3.0 ppm, a 13H peak based on a methoxy group, a morpholino group, and a methylene group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0305] Furthermore, 13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 18

First Step

[0306] A carboxylic acid compound represented by Formula (59) below was synthesized from 4,4-dimethylbenzophenone with reference to the method described in Patent Document 7.

##STR00065##

[0307] Then, 95.4 g (500.0 mmol) of p-toluenesulfonic acid monohydrate and 1000 mL of toluene were added to 29.2 g (100.0 mmol) of the resulting carboxylic acid, followed by reacting while azeotropic dehydration was performed. After consumption of the raw materials was confirmed, the resultant was cooled to room temperature and the resulting solid was filtered to obtain a carbonyl compound represented by Formula (60) below at a yield of 87%.

##STR00066##

Second Step

[0308] The carbonyl compound represented by Formula (60) was reacted to obtain a naphthol derivative represented by Formula (61) below at a yield of 80% with reference to the method described in Patent Document 8.

##STR00067##

Third Step

[0309] A compound represented by Formula (63) below was obtained at a yield of 79% in the same manner, except that the compound of Formula (61) was used instead of the compound of Formula (25) and propargyl alcohol of Formula (62) below was used instead of the propargyl alcohol of Formula (26) in Fourth step in Example 1.

##STR00068##

Fourth Step

[0310] Thirty milliliters of dehydrated THE was added to 1.7 g (3.0 mmol) of the compound represented by Formula (63) and 2.1 g (15.0 mmol) of 1-bromo-3-fluoropropane and stirred. After dissolving, an internal temperature was cooled to 3 C., and 10 mL of a solution in which 1.0 g (9.0 mmol) of potassium tertiary butoxide is dispersed in THE was slowly added dropwise. After the addition, the resulting reaction liquid was warmed to slowly to room temperature. After disappearance of the raw materials, 10% hydrochloric acid was added until a pH of an aqueous layer was 1, and the resultant was partitioned by adding 30 mL of toluene thereto. The resultant was partitioned by adding 20 ml of water thereto. The resultant was repeatedly partitioned until a pH of the aqueous layer was 6 to 7, and a solvent was removed from the resulting organic layer, followed by purification by chromatography on silica gel to obtain a photochromic compound represented by Formula (64) below at a yield of 81%.

##STR00069##

[0311] Elemental analysis values for the photochromic compound represented by Formula (64) were determined to be C, 80.41%; H, 7.08%, which are in good agreement with the calculated values for C.sub.46H.sub.48F.sub.2O.sub.3 of C, 80.44%; H, 7.04%.

[0312] Proton nuclear magnetic resonance spectra were measured and showed a 28H peak based on a flulropropyl group, a propyloxy group, and a methyl group around : 0.5 to 3.0 ppm, a 4H peak based on a propyloxy group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0313] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 19

First Step

[0314] A naphthol compound represented by Formula (65) below was synthesized in the same manner, except that 3-bromo-4-methoxymethoxybenzophenone was used for the reaction instead of 4,4-dimethylbenzophenone in First step in Example 18.

##STR00070##

Second Step

[0315] A photochromic compound represented by Formula (67) below was obtained at a yield of 86% in the same manner, except that the compound of Formula (65) was used instead of the compound of Formula (25) and propargyl alcohol of Formula (66) below was used instead of the propargyl alcohol of Formula (26) in Fourth step in Example 1.

##STR00071##

Third Step

[0316] A photochromic compound represented by Formula (68) below was obtained at a yield of 87 in the same manner, except that the compound of Formula (67) was used instead of the compound of Formula (63) and 3-bromo-1,1,1-trifluoropropane was used instead of 1-bromo-3-fluoropropane in Fourth step in Example 18.

##STR00072##

Fourth Step

[0317] First, 60 mL of toluene was added to 2.8 g (3.0 mmol) of the compound of Formula (68), 0.4 g (4.2 mmol) of morpholine, and 1.1 g (12.0 mmol) of sodium tertiary butoxide and the resultant was subject to nitrogen bubbling for 20 minutes. Then, 0.05 g (0.06 mmol) of tris (dibenzylideneacetone) dipalladium (0) and 0.1 g (0.24 mmol) of 2-dicyclohexylphosphino-triisopropylbiphenyl was added thereto and the resultant was reacted at 80 C. for 4 hours. After consumption of the raw materials was confirmed, the resultant was cooled at 0 to 5 C. and partitioned by adding 10% hydrochloric acid thereto to pH 6 to 7. The resultant was partitioned by adding 100 mL of water thereto. An aqueous layer was repeatedly washed with water until a pH of the aqueous layer was 6 to 7, and a solvent was removed from the resulting organic layer, followed by purification by chromatography on silica gel to obtain a photochromic compound represented by Formula (69) below at a yield of 72%.

##STR00073##

[0318] Elemental analysis values for the photochromic compound represented by Formula (69) were determined to be C, 71.07%; H, 6.64%; N, 1.48%, which are in good agreement with the calculated values for C.sub.5H.sub.61F.sub.6NO.sub.5 of C, 71.03%; H, 6.61%; N, 1.51%.

[0319] Proton nuclear magnetic resonance spectra were measured and showed a 34H peak based on a trifluoromethyl group, a hexyloxy group, and a morpholino group around : 0.5 to 3.0 ppm, an 11H peak based on a methoxy group, a hexyloxy group, and a morpholino group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0320] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 20

[0321] A photochromic compound represented by Formula (70) below was obtained at a yield of 72% in the same manner, except that 2,4-dimethoxyphenylboronic acid was used instead of 4-trifluorphenylboronic acid in Example 4.

##STR00074##

[0322] Elemental analysis values for the photochromic compound represented by Formula (70) were determined to be C, 72.26%; H, 6.34%, which are in good agreement with the calculated values for C.sub.59H.sub.62F.sub.6O.sub.6 of C, 72.23%, H: 6.37%.

[0323] Proton nuclear magnetic resonance spectra were measured and showed a 30H peak based on a trifluoromethyl group and a hexyloxy group around : 0.5 to 3.0 ppm, a 13H peak based on a methoxy group and a hexyloxy group around : 3.0 to 5.0 ppm, and a 19H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0324] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 21

First Step

[0325] A naphthol compound represented by Formula (71) below was synthesized in the same manner, except that 4-bromo-3,4-dimethoxymethoxybenzophenone was used for the reaction instead of 4,4-dimethylbenzophenone in First step in Example 18.

##STR00075##

Second Step

[0326] A photochromic compound represented by Formula (72) below was synthesized at a yield of 81% in the same manner, except that the naphthol compound of Formula (71) was used instead of the naphthol compound of Formula (29) in Second step in Example 2.

##STR00076##

Third Step

[0327] A photochromic compound represented by Formula (73) below was synthesized at a yield of 83% in the same manner, except that the compound of Formula (72) was used instead of the compound of Formula (63) and 4-bromo-1,1,1-trifluorobutane was used instead of 1-bromo-3-fluoropropane in Fourth step in Example 18.

##STR00077##

Fourth Step

[0328] A photochromic compound represented by Formula (74) below was obtained at a yield of 88% in the same manner, except that 4-methylphenylboronic acid was used for the reaction instead of 4-trifluorphenylboronic acid in Example 4.

##STR00078##

Fifth Step

[0329] A photochromic compound represented by Formula (75) below was obtained at a yield of 48% using the compound of Formula (74) with reference to the method described in Patent Document 9.

##STR00079##

[0330] Elemental analysis values for the photochromic compound represented by Formula (75) were determined to be C, 72.88%; H, 5.87%; N, 1.58%, which are in good agreement with the calculated values for C.sub.55H.sub.53F.sub.6NO.sub.4 of C, 72.91%; H, 5.90%; N, 1.55%.

[0331] Proton nuclear magnetic resonance spectra were measured and showed a 21H peak based on a trifluoropropyl group, a piperidino group, and a methyl group around : 0.5 to 3.0 ppm, a 13H peak based on a methoxy group and a piperidino group around : 3.0 to 5.0 ppm, and a 19H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0332] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 22

[0333] A photochromic compound represented by Formula (76) below was obtained at a yield of 85% in the same manner, except that 1-bromo-5-fluoropentane was used for the reaction instead of 1-bromo-3-fluoropropane in Fourth step in Example 18.

##STR00080##

[0334] Elemental analysis values for the photochromic compound represented by Formula (76) were determined to be C, 80.80%; H, 7.62%, which are in good agreement with the calculated values for C.sub.50H.sub.56F.sub.2O.sub.3 of C, 80.83%; H, 7.60%.

[0335] Proton nuclear magnetic resonance spectra were measured and showed a 36H peak based on a flulropentyl group, a methyl group, and a propoxy group around : 0.5 to 3.0 ppm, a 4H peak based on a propoxy group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0336] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 23

[0337] A photochromic compound represented by Formula (77) below was obtained at a yield of 81% in the same manner, except that 4-bromo-1,1,1-trifluorobutane was used instead of 1-bromo-3-fluoropropane in Fourth step in Example 18.

##STR00081##

[0338] Elemental analysis values for the photochromic compound represented by Formula (77) were determined to be C, 73.24%; H, 6.17%, which are in good agreement with the calculated values for C.sub.48H.sub.48F.sub.6O.sub.3 of C, 73.27%, H: 6.15%.

[0339] Proton nuclear magnetic resonance spectra were measured and showed a 28H peak based on a triflulrobutyl group, a methyl group, and a propoxy group around : 0.5 to 3.0 ppm, a 4H peak based on a propoxy group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0340] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around: 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 24

[0341] A photochromic compound represented by Formula (78) below was obtained at a yield of 82% in the same manner, except that 1-bromo-4-fluorobutane was used instead of 1-bromo-3-fluoropropane in Fourth step in Example 18.

##STR00082##

[0342] Elemental analysis values for the photochromic compound represented by Formula (78) were determined to be C, 80.40%;

[0343] H, 7.02%, which are in good agreement with the calculated values for C.sub.46H.sub.48F.sub.2O.sub.3 of C, 80.44%, H: 7.04%.

[0344] Proton nuclear magnetic resonance spectra were measured and showed a 28H peak based on a flulrobutyl group, a methyl group, and a propoxy group around : 0.5 to 3.0 ppm, a 4H peak based on a propoxy group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0345] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Example 25

[0346] A photochromic compound represented by Formula (79) below was obtained at a yield of 80% in the same manner, except that 3-bromo-1,1,1-trifluoropropane was used for the reaction instead of 1-bromo-3-fluoropropane in Fourth step in Example 18.

##STR00083##

[0347] Elemental analysis values for the photochromic compound represented by Formula (79) were determined to be C, 72.78%; H, 5.82%, which are in good agreement with the calculated values for C.sub.46H.sub.4F.sub.6O.sub.3 of C, 72.81%, H: 5.84%.

[0348] Proton nuclear magnetic resonance spectra were measured and showed a 24H peak based on a triflulropropyl group, a methyl group, and a propoxy group around : 0.5 to 3.0 ppm, a 4H peak based on a propoxy group around : 3.0 to 5.0 ppm, and a 16H peak based on an aromatic proton and an alkene proton around : 5.0 to 9.0 ppm.

[0349] Furthermore, .sup.13C-nuclear magnetic resonance spectra were measured and showed a peak based on a carbon atom in an aromatic ring around : 110 to 160 ppm, a peak based on a carbon atom in an alkene around : 80 to 140 ppm, and a peak based on a carbon atom in an alkyl between : 20 to 70 ppm.

Examples 26 to 34

[0350] Photochromic laminates were produced using the compounds obtained in Examples 17 to 25 in the same manner as in Example 9. The results of Examples 26 to 34 are summarized in Table 4.

TABLE-US-00004 TABLE 4 Color devel- Color Maximum opment fading Resid- absorption density at half-life ual Compound wavelength 23 C. at 23 C. ratio No. (nm) () (sec) (%) Example Formula 480 0.65 37 79 26 (58) 592 0.62 38 79 Example Formula 434 0.47 37 86 27 (64) 557 0.78 37 86 Example Formula 467 1.12 43 80 28 (69) 560 0.56 43 80 Example Formula 454 0.66 32 82 29 (70) 568 0.60 32 82 Example Formula 477 1.75 100 77 30 (75) 565 0.84 100 79 Example Formula 434 0.64 77 84 31 (76) 558 1.02 77 83 Example Formula 437 0.59 63 86 32 (77) 560 0.99 63 86 Example Formula 438 0.59 70 84 33 (78) 561 0.97 70 84 Example Formula 438 0.42 28 83 34 (79) 556 0.77 28 84

(Use of Resin Composition for Forming Photochromic Layer)

Example 35

(Production of Photochromic Layer (Photochromic Adhesive Layer))

[0351] A photochromic layer was prepared as follows.

(Production of Terminal Non-Reactive Urethane Urea Resin for Photochromic Layer Forming Composition)

[0352] First, 252 parts by mass of polycarbonate diol with a number average molecular weight of 800, 100 parts by mass of isophorone diisocyanate, and 72 parts by mass of toluene were charged into a 2L 4-necked flask equipped with a stirring blade, a condense tube, a thermometer, and a nitrogen gas inlet tube and reacted under a nitrogen atmosphere at 100 C. for 7 hours. Thus, a urethane prepolymer with a terminal isocyanate group was synthesized. After the reaction of the above-mentioned urethane prepolymer was completed, the resulting reaction liquid was cooled to about 0 C. and dissolved into 205 parts by mass of isopropyl alcohol and 382 parts by mass of diethyl ketone, and then a temperature of the resulting liquid was kept at 0 C. Next, a mixed solution of 23 parts by mass of bis-(4-aminocyclohexyl) methane serving as a chain extender and 20 parts by mass of diethyl ketone was added dropwise thereto within 30 minutes and reacted at 0 C. for 1 hour. Then, 5.7 parts by mass of 1,2,2,6,6-pentamethyl-4-aminopiperidine was added dropwise thereto and reacted at 0 C. for 1 hour to obtain a solution of a terminal non-reactive urethane urea resin in diethylketone.

[0353] One hundred parts by mass of the resulting solution of a terminal non-reactive urethane urea resin, the photochromic compound of Formula (27) (0.27 mmol), 4 parts by mass of an isomer mixture of 4,4-methylenebis(cyclohexylisocyanate) (polyisocyanate compound), and 0.4 parts by mass of ethylenebis (oxyethylene) bis [3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate] serving as an antioxidant and 0.06 parts by mass of DOW CORNING TORAY L-7001 serving as a surfactant were added and stirred and mixed at room temperature to obtain a photochromic layer forming composition.

(Synthesis of Adhesive for Adhesive Layer and Terminal Non-Reactive Urethane Urea Resin)

[0354] A 5 L separable flask (4-necked) equipped with a stirring blade, a condense tube, a thermometer, and a nitrogen gas inlet tube was prepared and 400 parts by mass of polycarbonate diol with a number average molecular weight of 1000, 175 parts by mass of isophorone diisocyanate, and 120 parts by mass of toluene were charged into the flask and reacted under a nitrogen atmosphere at 110 C. for 7 hours. Thus, a urethane prepolymer with a terminal isocyanate group was synthesized. After the reaction of the urethane prepolymer is completed, the resulting reaction liquid is cooled to about 20 C. and dissolved into 2500 parts by mass of propylene glycol monomethyl ether, and then a temperature of the resulting liquid was kept at 20 C. Next, 60 parts by mass of isophoronediamine serving as a chain extender was added dropwise thereto and reacted at 20 C. for 1 hour. Then, 3 parts by mass of n-butylamine was added dropwise thereto and reacted at 20 C. for 1 hour to obtain a solution of a terminal non-reactive urethane urea resin in propylene glycol-monomethyl ether.

[0355] Then, 0.2 parts by mass of DOW CORNING TORAY L-7001 serving as a surfactant was added to 500 parts by mass of the resulting solution of a terminal non-reactive urethane urea resin and the resultant was stirred and mixed at room temperature to obtain an adhesive for an adhesive layer.

(Production of Photochromic Layer)

[0356] Polycarbonate sheets each having a thickness of 400 m (first and second optical sheets; one would be an optical substrate and the other would be a layer without a photochromic compound) were coated with the adhesive for an adhesive layer using a coater (manufactured by TESTER SANGYO CO. LTD.) at a coating rate of 0.5 m/min and dried at a drying temperature of 110 C. for 3 minutes to obtain polycarbonate sheets with adhesive resin layers each having a thickness of 5 m.

[0357] Then, an OPP film (oriented polypropylene film) having a thickness of 50 m using a coater (manufactured by TESTER SANGYO CO. LTD.), was coated with the photochromic layer forming composition at a coating rate of 0.3 m/min and dried at a drying temperature of 100 C. for 5 minutes. Thus, a photochromic layer was formed. Then, the photochromic layer (thickness: 40 m) was placed onto the adhesive resin layer of the first optical sheet with the adhesive resin layer and laminated together.

[0358] Furthermore, a structure formed by releasing the OPP film from the thus-prepared one consisting of the first optical sheet/the adhesive resin layer/the photochromic layer/the OPP film laminated in this order was adhered to the polycarbonate sheet (second optical sheet) with the adhesive resin layer so that the photochromic layer and the adhesive resin layer on the polycarbonate sheet (second optical sheet) were bonded together. The resulting laminate was then left to stand at 40 C. under vacuum for 24 hours, subjected to heat treatment at 110 C. for 60 minutes and humidification treatment at 60 C. and 100% RH for 24 hours, and finally left to stand at 40 C. under vacuum for 24 hours to obtain a photochromic laminate. The resulting photochromic laminate was evaluated in the same manner as for Example 9.

Examples 36 to 38

[0359] Photochromic laminates were produced using the photochromic compounds of Formula (46), Formula (48), and Formula (70) in the same manner as in Example 35 and evaluated in the same manner as for Example 9. The results are presented in Table 5.

TABLE-US-00005 TABLE 5 Color devel- Color Maximum opment fading Resid- absorption density at half-life ual Compound wavelength 23 C. at 23 C. ratio No. (nm) () (sec) (%) Example Formula 436 0.49 57 94 35 (27) 550 0.92 57 94 Example Formula 460 0.36 20 93 36 (46) 586 0.68 20 93 Example Formula 472 0.83 40 96 37 (48) 563 0.70 40 96 Example Formula 457 0.67 41 94 38 (70) 567 0.62 41 95

[0360] Preferred embodiments of the present invention will be described in addition.

[1]

[0361] A photochromic compound having a backbone represented by Formula (1) below:

##STR00084##

in which [0362] M is C, Si, or Ge; [0363] R.sup.1 is a haloalkyl group having 1 or more and 20 or less carbon atoms; [0364] R.sup.2 is a substituted or unsubstituted alkyl group having 1 or more and 20 or less carbon atoms or a substituted or unsubstituted haloalkyl group having 1 or more and 20 or less carbon atoms; [0365] Ring A is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to any of the above-mentioned rings, or Ring A may not be present; and [0366] Ring B is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to any of the above-mentioned rings.
[2]

[0367] The photochromic compound according to [1], having a backbone represented by Formula (2) below:

##STR00085##

in which R.sup.1, R.sup.2, and M are each the same as in Formula (1).
[3]

[0368] The photochromic compound according to [1] or [2], represented by Formula (3) below:

##STR00086##

in which R.sup.1, R.sup.2, and M are each the same as in Formula (1); R.sup.3 and R.sup.4 are each independently a hydroxyl group, an optionally substituted alkyl group, an optionally substituted haloalkyl group, an optionally substituted cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, an optionally substituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, an optionally substituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an optionally substituted aralkyl group, an optionally substituted aralkoxy group, an optionally substituted aryloxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or an optionally substituted cycloalkylthio group, an optionally substituted silyl group, an optionally substituted oxysilyl group, a group represented by Formula (X) below, a group represented by L.sup.1-R.sup.400 below, or a group represented by Formula (Y) below; [0369] c is an integer from 0 to 4; when c is 2 to 4, a plurality of R.sup.3s may be the same as or different from each other; [0370] when c is 2 to 4 and adjacent R.sup.3s are present, two adjacent R.sup.3s may be taken together with a carbon atom to which R.sup.3s are attached to form a ring optionally including an oxygen atom, a carbon atom, a sulfur atom, or a nitrogen atom, and the ring is optionally substituted; [0371] d is an integer from 0 to 4; when d is 2 to 4, a plurality of R.sup.4s may be the same as or different from each other; [0372] when d is 2 to 4 and adjacent R.sup.4s are present, two adjacent R.sup.4s may be taken together with a carbon atom to which R.sup.4s are attached to form a ring optionally including at least one atom selected from the group consisting of an oxygen atom, a carbon atom, a sulfur atom, and a nitrogen atom and the ring is optionally substituted; and [0373] R.sup.5 and R.sup.6 are each independently an optionally substituted aryl group or an optionally substituted heteroaryl group;

##STR00087##

in formula (X), [0374] E is an oxygen atom or NR.sup.101 in which R.sup.101 is a hydrogen atom or an alkyl group; [0375] F is an oxygen atom or a sulfur atom; [0376] G is an oxygen atom, a sulfur atom, or NR.sup.202 in which R.sup.202 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; [0377] g is 0 or 1; [0378] R.sup.201 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; and [0379] when G is an oxygen atom or a sulfur atom, R.sup.201 is a group other than a hydrogen atom; [0380] in L1-R.sup.400, [0381] R.sup.400 is a hydrogen atom, an alkyl group, an aryl group, a polymerizable group, a photochromic group, or a silyl group with an alkyl group, an alkoxyl group, or an aryl group as a substituent; and [0382] L.sup.1 is a group represented by Formula (X2) below;

##STR00088##

in Formula (X2),

[0383] J is a divalent group, each independently being directly attached, a substituted methylene group, an oxygen atom, a sulfur atom, or NR.sup.301 in which R.sup.301 is a hydrogen atom or an alkyl group; [0384] L is an oxygen atom or a sulfur atom; [0385] R.sup.300 is an alkylene group, or a silylene group having an alkyl group or an aryl group as a substituent; [0386] R.sup.302, R.sup.303, and R.sup.304 are each independently an alkylene group; h, j, k, and l are an integer of 0 or 1; [0387] i is an integer from 1 to 200, and values of a plurality of units i may be the same as or different from each other; and [0388] a dashed line represents an attachment to R.sup.400;

-Q.sup.1-(X.sup.1Q.sup.2)a-X.sup.2Q.sup.3(Y)

in which [0389] Q.sup.1 is an alkylene group optionally including a halogen atom as a substituent; [0390] Q.sup.2 is an alkylene group optionally including a halogen atom as a substituent; [0391] Q.sup.3 is an alkyl group optionally including a halogen atom as a substituent; [0392] X.sup.1 and X.sup.2 are each independently O, S, NR.sup.700, PR.sup.701, or P(O); [0393] R.sup.700 is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group; [0394] R.sup.701 is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group; and [0395] a is 0, or 1 or more and 10 or less.
[4]

[0396] The photochromic compound according to any one of [1] to [3], in which R.sup.1 is a haloalkyl group having 2 or more and 10 or less carbon atoms.

[5]

[0397] The photochromic compound according to any one of [1] to [4], in which R.sup.2 is a haloalkyl group having 1 or more and 20 or less carbon atoms.

[6]

[0398] The photochromic compound according to any one of [1] to [3], in which R.sup.1 is a group represented by Formula (1a) below:

(CH.sub.X.sup.11.sub.).sub.CH.sub.X.sup.12.sub.(1a)

in Formula (1a),

[0399] X.sup.11 and X.sup.12 are each independently a halogen atom; [0400] and are independently 0 or 1 or 2; [0401] +=2; [0402] is 0 or 1 or 2; [0403] is 1 or more and 3 or less; [0404] +=3; and [0405] is 0, or 1 or more and 10 or less.
[7]

[0406] The photochromic compound according to [3], represented by Formula (4) below:

##STR00089##

in which [0407] R.sup.1, R.sup.2, R.sup.3, R.sup.4, c, and d are each independently the same as in Formula (3); [0408] R.sup.7 and R.sup.8 are each independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, an optionally substituted arylthio group having 6 to 10 carbon atoms, or the group represented by L.sup.1-R.sup.400; [0409] e is an integer of 0 to 5; [0410] when e is 2 to 5, R.sup.7s may be the same as or different from each other; [0411] when adjacent R.sup.7s are present, two adjacent R.sup.7s may be taken together with a carbon atom to which R.sup.7s are attached to form a ring optionally including at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom and the ring is optionally substituted; [0412] f is an integer of 0 to 5; [0413] when f is 2 to 5, R.sup.8s may be the same as or different from each other; and [0414] when adjacent R.sup.8s are present, two adjacent R.sup.8s may be taken together with a carbon atom to which R.sup.8s are attached to form a ring optionally including at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom and the ring is optionally substituted.
[8]

[0415] The photochromic compound according to [3] or [6], in which R.sup.1 and R.sup.2 are the same substituent as each other.

[9]

[0416] A curable composition including: [0417] the photochromic compound according to any one of [1] to [8]; and [0418] at least one selected from the group consisting of a radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerization reactive group, and a (thio)urethane(urea) polymer.
[10]

[0419] An optical article including a cured product of the curable composition according to [9].

[11]

[0420] A lens including a cured product of the curable composition according to [9].

[12]

[0421] Eyeglasses including the lens according to [11].

[13]

[0422] A naphthol derivative having a backbone represented by Formula (5) below:

##STR00090##

in which [0423] M is C, Si, or Ge; [0424] R.sup.1 is a haloalkyl group having 1 or more and 20 or less carbon atoms; and [0425] R.sup.2 is a substituted or unsubstituted alkyl group having 1 or more and 20 or less carbon atoms or a substituted or unsubstituted haloalkyl group having 1 or more and 20 or less carbon atoms.