JP2723341B2 - Photochromic composition - Google Patents

Description

The present invention relates to a photochromic composition having various colors such as gray, brown, and amber.

(Prior art) Photochromism is a phenomenon that has attracted attention in recent years. When a compound is irradiated with light containing ultraviolet rays such as sunlight or light from a mercury lamp, the color changes rapidly, and the light irradiation is stopped. It is a reversible action that returns to the original color when stopped and put in a dark place. A compound having this property is called a photochromic compound, and compounds having various structures have been conventionally synthesized and proposed, but no special common skeleton is recognized in the structure.

Chromene or a derivative thereof is known as a photochromic compound. The color tone of chromene or a derivative thereof is orange to yellow. On the other hand, spirooxazine compounds are also well known as photochromic compounds, and the color tone of these compounds is red to blue.

(Problems to be Solved by the Invention) However, when these compounds are used alone, a desired color tone may not be obtained. Especially,
When used as a photochromic lens, color tones such as gray, amber, and brown are preferred, but these color tones cannot be obtained with the above compounds alone.

Therefore, the present inventors have intensively studied to develop various intermediate colors such as gray, amber, and brown.

(Means for Solving the Problems) As a result, as a result of mixing the novel spirooxazine compound synthesized by the present inventors with chromene or a derivative thereof, various intermediate colors including gray, amber, and brown are obtained. And succeeded in completing the present invention.

That is, the present invention provides: (a) the following formula [I] (B) chromene or a derivative thereof in an amount of from 0.01 to 10,000 parts by weight.

The component (a) of the photochromic composition in the present invention is a spirooxazine compound represented by the general formula [I].

In the above general formula (I), Is an aromatic hydrocarbon group or an unsaturated heterocyclic group which may be substituted, respectively. Specific examples of the aromatic hydrocarbon group include a divalent group derived from one benzene ring such as a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring or a fused ring of 2 to 4 benzene rings. Further, a hydroxyl group, a nitro group, a cyano group, a fluoroalkyl group, a substituted amino group,
Examples include a substituted aromatic hydrocarbon group in which one or more heterocyclic groups such as a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a thienyl group, a furyl group, and a pyrrolyl group are substituted.

In the above general formula (I), Examples of the optionally substituted unsaturated heterocyclic group represented by are a 5- or 6-membered ring containing oxygen, sulfur and nitrogen atoms, or a heterocyclic group in which a benzene ring is fused to these. Specifically, it is derived from nitrogen-containing heterocycles such as pyridine ring, quinoline ring, pyrrole ring and indole ring; oxygen-containing heterocycle such as furan ring and benzofuran ring; and sulfur-containing heterocycle such as thiophene ring and benzothiophene ring. Divalent heterocyclic group. In particular, in the case of a bicyclic fused heterocycle of a benzene ring and a 5- or 6-membered heterocycle, a high color density can be obtained.

As the substituent of the unsaturated heterocyclic group, the substituent of the aromatic hydrocarbon group described above is employed without any limitation.

Further, in the general formula [I], R ₁ and R ₂ are a hydrogen atom or an alkyl group, and R ₁ and R ₂ may form a ring together. The alkyl group is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. More specific examples of the alkyl group include a methyl group, an ethyl group, and an isopropyl group. When R ₁ and R ₂ form a ring together, they are not particularly limited, but generally a cycloalkyl ring having 5 to 10 carbon atoms, a bicycloalkyl ring, or a tricycloalkyl ring is preferred. More specifically, these include 2 derived from a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, a norbornane ring and an adamantane ring.
Valence groups. One of these R ₁ and R ₂ is an alkyl group having 1 or more carbon atoms and the other is an alkyl group having 2 or more carbon atoms, or a compound in which they together form a ring Is preferred because of exhibiting good color density.

In the general formula [I], R ₃ is an alkoxycarbonylalkyl group. The alkoxy group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 carbon atom.
-10, preferably 1-4. The alkylene group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 to 10, preferably 1 to 4 carbon atoms. More specific examples of the alkoxycarbonylalkyl group include a methoxycarbonylmethyl group, a methoxycarbonylethyl group, a methoxycarbonylpropyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, an ethoxycarbonylbutyl group, and a butoxycarbonylethyl group.

In the general formula (I), R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogen atom, a cyano group, a trifluoromethyl group or an alkoxycarbonyl group, At least one of R ₄ and R ₅ is a cyano group, a trifluoromethyl group or an alkoxycarbonyl group.

Examples of the hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group. Among them, the alkyl group generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. More specific examples of the alkyl group include a methyl group, an ethyl group, and an isopropyl group. The aryl group has 6 to 10 carbon atoms.
Phenyl group, naphthyl group and the like, and the aralkyl group preferably has 7 to 14 carbon atoms, specifically, benzyl group, phenylethyl group, phenylpropyl group and the like. Group, naphthylmethyl group and the like. The alkoxy group preferably has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms,
Specifically, they are a methoxy group, an ethoxy group, and an isopropyloxy group. As the halogen atom, fluorine, chlorine,
Bromine and the like. The alkoxycarbonyl group is not particularly limited, but generally has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More specific examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

In the general formula [I], at least one of R ₄ and R ₅ must be a cyano group, a trifluoromethyl group or an alkoxycarbonyl group. By selecting these groups, the spirooxazine compound of the present invention exhibits a good photochromic action even in a high temperature range.

The component (b) of the photochromic composition of the present invention is chromene or a derivative thereof. Chromene has the formula It is a compound shown by these. Further, as the chromene derivative, the compound having the above chromene skeleton is employed without any limitation. In the present invention, a chromene derivative represented by the following formula [A] is particularly preferably used because it has excellent photochromic properties.

In the general formula [A], An aromatic hydrocarbon group and an unsaturated heterocyclic group represented by
Of the spirooxazine compound represented by the general formula (I) The group described for is employed. Further, the substituents of these aromatic hydrocarbon group and unsaturated heterocyclic group are the same as those in the above general formula [I]. The substituents of the aromatic hydrocarbon group and the unsaturated heterocyclic group represented by are adopted without any limitation.

Further, -R ⁵ -SR ⁶ , [However, R ⁵ is an alkylene group or O—R ⁸ _n (provided that R ⁸
Is an alkylene group, and n is a positive integer. R ⁶ and R ⁷ are the same or different alkyl groups, and X is -N <, -P <, It is. ] May be substituted one or more times.
The alkyl group or alkylene group represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ is preferably a long chain having 6 to 20 carbon atoms,
Further, _n of OR ⁸ _n is preferably a positive number such that the total number of carbon atoms is 6 to 20.

Next, in the general formula [A], the hydrocarbon groups represented by R ¹ , R ² , R ³ and R ⁴ are the R ₄ , R ₅ , and R _{4 of the} spirooxazine compound represented by the general formula [I]. _6, the same hydrocarbon group as described for R ₇ and R ₈ are employed.

Further, the substituted amino group has the general formula Indicated by R ⁹ and R ¹⁰ are preferably the same or different hydrogen atoms; and are preferably hydrocarbon groups such as alkyl groups, aralkyl groups, and aryl groups. As the hydrocarbon group, the same groups as those described above for R ^{1 to} R ⁴ are preferably used.

Furthermore, the substituted amino group has the general formula R ¹¹ is an alkylene group such as a tetramethylene group or a pentamethylene group; —CH ₂ OCH ₂ CH ₂ —, CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ O (oxyalkylene group such as CH _{2 3} ; —CH ₂ SCH ₂ CH ₂ —, —CH ₂ S (CH _{2 3} A thioalkylene group such as —CH ₂ CH ₂ SCH ₂ CH ₂ —; And the like.

Further, in the general formula [A], R ¹ and R ² may form a ring together, and in this case, the ring is the same as R ₁ and R ₂ in the general formula [I]. The rings described are employed without any restrictions.

Among the above-mentioned chromene or a derivative thereof, in the general formula (A), Is preferably a condensed ring of two or more rings because of high color density. Among them, compounds in which a ring is condensed at positions 7 and 8 of the chromene skeleton are more preferable. Further, in the general formula [A],
When R ¹ and R ² form a ring, the chromene skeleton
Compounds in which a ring is fused at the 5- or 6-position are also preferably used.

In the present invention, the mixing ratio of the above-mentioned spirooxazine compound and chromene or a derivative thereof can be arbitrarily selected according to the desired color tone.However, in order to adjust the color tone to brown, gray, amber or the like, generally, With respect to 100 parts by weight of the spirooxazine compound, chromene or a derivative thereof is 0.01 to 10,000 parts by weight, preferably 0.05 to 1000 parts by weight.
It is preferred to use parts by weight.

By dispersing the photochromic composition of the present invention in an organic solvent, a photochromic fluid that can be used for applications such as decoration can be obtained. Further, by dispersing the photochromic composition of the present invention in a polymer such as a thermoplastic resin or a thermosetting resin, a molded article such as a photochromic glass or a photochromic lens can be obtained.

Any thermoplastic resin may be used as long as it can uniformly disperse the spirooxazine compound and chromene or a derivative thereof. Optically preferred are, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, and polymethacryl. Ethyl acid, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate),
Examples thereof include polydimethylsiloxane and polycarbonate.

Dispersion of the photochromic composition of the present invention in a thermoplastic resin is the synthesis of a thermoplastic resin, that is, a method of performing polymerization in the presence of a photochromic composition, or a thermoplastic resin and a photochromic composition of a thermoplastic resin. A method of melting and kneading at a temperature higher than the melting temperature is exemplified.

Next, as the thermosetting resin, ethylene glycol diacrylate, diethylene glycol dimethacrylate,
Ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2
-Poly (acrylic acid) and poly (methacrylic acid ester) compounds such as bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl Polyvalent allyl compounds such as fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ) Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds such as ether and 1,4-bis (methacryloylthiomethyl) benzene; polymers of radically polymerizable polyfunctional monomers such as divinylbenzene: Is each of these monomers and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, and maleic anhydride; acrylic acid such as methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, and 2-hydroxyethyl methacrylate; Methacrylic acid ester compounds; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate; styrene, chlorostyrene, methylstyrene, vinyl Copolymers with radically polymerizable polyfunctional monomers such as vinyl compounds such as naphthalene and bromostyrene: ethanedithiol, propanetriol, hexanedithiol, pentaerythritol tetrakis Addition copolymers of polyvalent thiol compounds such as thioglycolate and di (2-mercaptoethyl) ether with the above-mentioned radically polymerizable polyfunctional monomers: polyadditions such as diphenylethane diisocyanate, xylene diisocyanate, p-phenylene diisocyanate, etc. An addition polymer of a polyvalent isocyanate compound with a polyhydric alcohol compound such as ethylene glycol, trimethylolpropane, pentaerythritol, and bisphenol A, or the above-mentioned polyvalent thiol compound may be used. These raw material monomers can be used alone or in combination of two or more.

For dispersing the photochromic composition in the thermosetting resin, a method of mixing the raw material monomer of the thermosetting resin and the photochromic composition and then polymerizing the mixture is generally adopted.

The amount of the photochromic composition of the present invention to be dispersed in such a polymer is 0.0% based on 100 parts by weight of the polymer.
The amount is from 01 to 20 parts by weight, preferably from 0.1 to 10 parts by weight.

By incorporating an ultraviolet stabilizer into the composition of the present invention, the durability of photochromic properties can be further improved. As the ultraviolet stabilizer, a known ultraviolet stabilizer added to various plastics can be used without any limitation.

In the present invention, considering the improvement in durability of the photochromic compound, among various ultraviolet stabilizers, a singlet oxygen quencher, a hindered amine light stabilizer, a hindered phenol antioxidant, and a sulfur-based antioxidant are preferably used. Is done. More specific examples of these ultraviolet stabilizers include Sheasorb UV1084 and Sheasorb 3346 (all manufactured by American Cyanamid); UV-Cek AM101 and UV-Cek AM105 (all manufactured by Ferro Corporation); 2002, Tinuvin 765, Tinuvin 144, Chimassorb 94
4, Tinuvin 622, Irganox 1010, Irganox 245
Reilex NBC (manufactured by Dupont); Sanol LS-1114, Sanol LS-744, Sanol LS-2626 (manufactured by Sankyo Co., Ltd.); Sumilizer
GA-80, Sumilizer GM, Sumilizer BBM-S, Sumilizer WX-R, Sumilizer S, Sumilizer BHT, Sumilizer TP-D, Sumilizer TPL-R, Sumilizer TPS, Sumilizer MB (all manufactured by Sumitomo Chemical Co., Ltd.); Mark AO- 50, mark AO-20, mark AO-30, mark AO-330, mark AO-23,
Mark LA-82, Mark LA-87 (above, manufactured by Adeka Argus); Antioxidant HPM-12 (manufactured by SFOS)
And the like. Each of the above names is a trade name.

The compounding ratio of the ultraviolet stabilizer is preferably in the range of 0.01 to 10,000 parts by weight, based on 100 parts by weight of the total amount of the spirooxazine compound and chromene or a derivative thereof, particularly, the photochromic composition of the obtained photochromic composition. From the viewpoint of properties, the amount of the ultraviolet stabilizer is preferably in the range of 10 to 500 parts by weight.

(Effects) As described above, the photochromic composition of the present invention changes from colorless to colored or darkened by light including ultraviolet rays such as sunlight or light from a mercury lamp, and the change is reversible. Shows excellent dimming properties. Further, the present invention has succeeded in easily obtaining various intermediate colors such as gray, brown, and amber by using a spirooxazine compound and chromene or a derivative thereof in combination.

Therefore, the photochromic composition of the present invention can be used in a wide range of fields, for example, various recording memory materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for cathode ray piping, photosensitive materials for lasers And various recording materials. In addition, the photochromic composition of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material, a light meter, a decoration, and the like.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. “Parts” in the examples is “parts by weight”.

In addition, the symbol in the following Examples and the brand name of an ultraviolet stabilizer show the following compounds.

・ BMDBP: 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane ・ Cl-St: chlorostyrene ・ TMB-TAC: trimethylolpropane triallyl carbonate ・ BADBP: 2,2-bis ( 4-allylcarbonate ethoxy-3,5-dibromophenyl) propane ・ ADC: allyl diglycol carbonate ・ DAP: diallyl phthalate ・ St: styrene ・ DCIPF: di (2-chloroisopropyl) fumarate ・ EGDMA: ethylene glycol dimethacrylate ・ PETTP : Pentaerythritol tetrakis (β-thiopropionate) ・ DME: di (2-mercaptoethyl) ether ・ DVB: divinylbenzene ・ XIC: xylylene diisocyanate ・ HPA: 3- (2,4-dibromophenoxy) -2- Hydroxypropyl acrylate • MMA: Methyl methacrylate • DEGDMA : Diethylene glycol dimethacrylate ・ TBBM: 3,4,5-tribromobenzyl methacrylate ・ HEMA: 2-hydroxyethyl methacrylate ・ BMA: Benzyl methacrylate ・ IPP: Diisopropyl peroxycarbonate ・ Perbutyl ND: (manufactured by NOF Corporation) t -Butyl peroxy-2-hexanate -BPO: benzoyl peroxide -Sanol LS-744 (trade name: manufactured by Sankyo) ・ MARK LA-82 (Product name: Adeka Argus) ・ MARK LA-87 (Product name: Adeka Argus) ・ Sanol LS-2626 (trade name: manufactured by Sankyo Co., Ltd.) ・ Sumilyzer GA-80 (trade name: Sumitomo Chemical Co., Ltd.) ・ Irganox 1010 (Product name: Ciba-Geigy) ・ Cyasorb UB1084 (Product name: American Cyanamid Co., Ltd.) ・ Tinuvin 765 (Product name: Ciba-Geigy) ・ UV-Chek AM 101 (trade name: manufactured by Ferro Corporation) ・ MARK AO-20 (Product name: Adeka Argus) - Sumilizer TP-D (trade name: manufactured by Sumitomo Chemical Co. _{(H 25 C 12 SCH 2 CH} 2 COOCH 2) 4 C · Sanol LS-1114 (trade name, manufactured by Sankyo Co., Ltd.) Production Example 1 Compound of the Following Formula 2.01g (0.0057mol) and the compound of the following formula 1.4 g (0.0057 mol) and 0.41 g (0.0058 mol) of pyrrolidine were dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours.

After the reaction, the solvent was removed, and purification was carried out by chromatography on silica gel to obtain 200 mg of a spirooxazine compound represented by the following formula.

Elemental analysis of this compound gave C 65.12%, H 4.90%, N
8.51%, O 9.74%, F 11.73%, which are calculated values for C ₂₇ H ₂₄ N ₃ O ₃ F ₃ C 65.45%, H 4.88%, N 8.48%, O 9.
It was very good agreement with 69% and F 11.50%. When the proton nuclear magnetic resonance spectrum was measured, δ 6.5 to 9 ppm
Near 9H peak based on quinoline ring proton, indoline ring proton and oxazine ring proton, δ 4pp
around m 2H peak based on bond protons, near δ3.7 ppm −
O-CH ₃ peak of 3H based on the binding of protons, δ1.3~2.
A broad peak of 10H based on the cyclohexane ring proton was observed at around 1 ppm. Further measurement of the ¹⁵ C-nuclear magnetic resonance spectrum revealed that the peak based on the carbonyl carbon at around 170 ppm, the peak based on the carbons of the benzene, quinoline and oxazine rings of indoline at around δ100 to 160 ppm, and the peak at around δ125 ppm. A peak based on a fluoromethyl group, a peak based on spiro carbon around δ99 ppm and δ52 ppm, and a peak based on a methyl group and carbon of a methylene chain around δ20 to 50 ppm were shown.

From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (I).

Production Example 2 Compound of the Following Formula 2.0 g (0.0057 mol) of the compound of the following formula 1.4 g (0.0057 mol) and 0.41 g (0.0057 mol) of pyrrolidine were dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours.
After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel to obtain 150 mg of a spirooxazine compound represented by the following formula.

Elemental analysis of this compound gave C 65.23%, H 5.21%, N
8.56%, O 9.71%, F 11.29%, which are calculated values for C ₂₇ H ₂₆ N ₃ O ₃ F ₃ C 65.18%, H 5.27%, N 8.45%, O 9.
This was very good agreement with 39% and F 11.46%. When the proton nuclear magnetic resonance spectrum was measured, δ 6.5 to 9 ppm
Near the aromatic proton peak, δ
A peak based on the methyl proton of the ethyl group was around 1.0 ppm, a peak based on the methylene proton of the ethyl group was around δ 2 ppm, and a peak based on the proton of N-CH ₂ CH ₂ COOCH ₃ was around δ 3.5 ppm. Also, when ¹³ C-NMR was measured, a peak based on carbon of carbonyl at around δ170 ppm, an aromatic carbon around δ100 to 160 ppm,
Peak based on carbon of oxazine ring and carbon of trifluoromethyl group, peak based on spiro carbon near δ99 ppm, peak based on carbon of methylene bonded to nitrogen near δ50 ppm, methyl group bonded to carbon near δ20-40 ppm And a peak based on the carbon of the methylene group. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (2).

Production Examples 3 to 17 Spirooxazine compounds shown in Table 1 were synthesized in the same manner as in Production Examples 1 and 2.

The obtained product was subjected to structure analysis using the same means for structure confirmation as in Production Example 1, and as a result, was confirmed to be a compound represented by the structural formula shown in Table 1.

Production Example 18 1 g of 1-hydroxy-2-acetonaphthone (0.054 mol
l) with 6.6 g (0.06 mol) of norcamphor and 8 g of pyrrolidine
(0.113 mol) was dissolved in 300 cc of toluene to prepare a solution. The mixture was boiled for 10 hours and the water was separated. After the completion of the reaction, the toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized with acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. By heating 7.47 g of this chromanol compound together with 4.5 g of anhydrous copper sulfate in a stream of carbon dioxide at 150 to 160 ° C. for 10 minutes, and purifying the brown viscous liquid by chromatography on silica gel, a chromene compound of the following formula was obtained. 6.3 g of the derivative were obtained.

Elemental analysis of this compound gave C 86.93%, H 6.89%, O
6.18%, which is the calculated value for C ₁₉ H ₁₈ O, C 87.0
Very good agreement was reached with 2%, H 6.87% and O 6.12%. When the proton nuclear magnetic resonance spectrum was measured,
δ 7.2-8.3 ppm based on naphthalene ring proton
The peak of 6H, the peak of 2H based on the proton of the alkene near δ5.6 to 6.7 ppm, and the broad peak of 10H based on the proton of the norbornylidene group near δ1.2 to 2.5 ppm were shown. When ¹³ C-nuclear magnetic resonance spectrum was further measured, a peak based on the carbon of the norbornylidene group near δ27 to 52 ppm, a peak based on the carbon of the naphthalene ring near δ110 to 160 ppm, and a peak based on the carbon of the alkene near δ80 to 110 ppm Appears. From the results shown above, it was confirmed that the isolated product was the compound represented by the above structural formula (18).

Production Example 19 A solution prepared by dissolving 10 g (0.054 mol) of 1-acetyl-2-naphthol, 8.29 g (0.06 mol) of bicyclo [3.3.1] nonan-9-one, and 8.7 g (0.10 mol) of morpholine in 300 cc of toluene was prepared. Prepared. The mixture was boiled for 5 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, and the remaining chromanone compound was recrystallized from acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and lithium aluminum hydride was added to obtain a chromanol compound. The chroman compound 6.49 g was heated at 170 to 180 ° C. for 10 minutes together with anhydrous copper sulfate in a stream of carbon dioxide, and the brown viscous liquid was purified by chromatography on silica gel to obtain 5.8 g of a chromene derivative of the following formula. Was.

Elemental analysis of this compound gave C 86.81%, H 7.62%, O
5.57%, calculated for C ₂₁ H ₂₂ O, C 87.9
Very good agreements were obtained with 0%, H 7.59% and O 5.52%. When the proton nuclear magnetic resonance spectrum was measured,
δ 7.2-8.3 ppm based on naphthalene ring proton
6H peak, 2H peak based on alkene protons near δ 6.0 to 7.0 ppm, bicyclo [3.
3.1] showed a broad peak at 14H based on the proton of the 9-nonylidene group. Further measurement of ¹³ C-nuclear magnetic resonance spectrum, bicyclo (3.3.1) around δ27 ~ 52 ppm
Peak based on carbon of 9-nonylidene group, δ 110-160p
A peak based on the carbon of the naphthalene ring around pm, δ80 to 11
A peak based on the carbon of the alkene appears at around 0 ppm.
From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (19).

Production Example 20 3.06 g (0.01 mol) of a chromanone compound represented by the following formula Was dissolved in 50 cc of anhydrous ether, the solution was cooled to 0 ° C., and a freshly prepared Grignard reagent CH ₃ MgCl (0.012 mol) was added dropwise to the solution over 50 minutes in 50 cc of anhydrous ether. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, then the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, and the ether was removed under reduced pressure. The compound was changed to a chromanol compound. Then, the chromanol compound was mixed with anhydrous copper sulfate in a stream of carbon dioxide at 200 ° C. for about 1 hour.
Heat for 0 min and produce a brown viscous fluid by chromatography on silica gel, chromene derivative of formula
2.47 g were obtained.

By elemental analysis, proton nuclear magnetic resonance spectrum, and measurement of ¹³ C-nuclear magnetic resonance spectrum as in Production Example 18,
This compound was confirmed to be the compound represented by the above structural formula (20).

Production Example 21 1-acetyl-2-naphthol 10 g (0.054 mol), norcamphor 6.6 g (0.06 mol) and morpholine 8.7 g (0.10 m
ol) was dissolved in 300 cc of toluene, boiled for 15 hours, and water was separated. After the reaction, the toluene was removed under reduced pressure,
The remaining product was recrystallized from acetone to obtain 7.53 g of a compound represented by the following formula.

Next, 7.53 g of this compound was dissolved in 100 cc of methanol and reacted with methyl iodide to obtain 6.95 g of a chromanone compound represented by the following formula.

Next, the produced chromanone compound was changed to a chromanol compound in the same manner as in Production Example 20, and a dehydration reaction was performed. After separation and purification, 5.84 g of a chromene derivative represented by the following formula was obtained.

This compound was confirmed to be the compound represented by the above structural formula (21) by elemental analysis, proton nuclear magnetic resonance spectrum and ¹³ C-nuclear magnetic resonance spectrum measurement in the same manner as in Production Example 18.

Production Example 22 5-n-octyloxy-1-hydroxy-2-acetonaphthone 10 g (0.0318 mol) and acetone 2.77 g (0.0477 m
ol) and 1.13 g (0.0159 mol) of pyrrolidine in 100 ml of toluene
Was prepared. The mixture was boiled for 10 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, the remaining chromanone compound was dissolved in 100 ml of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. 6.0 g of this chromanol compound was mixed with 4.0 g of anhydrous copper sulfate in a stream of carbon dioxide at 150 to 160 ° C.
The mixture was heated for 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel to obtain 3.8 g of a chromene derivative represented by the following formula.

As in Production Example 18, it was confirmed that the compound was the compound represented by the above structural formula (22) by elemental analysis, proton nuclear magnetic resonance spectrum, and measurement of ¹³ C-nuclear magnetic resonance spectrum.

Production Examples 23 to 31 The chromene derivatives shown in Table 2 were synthesized in the same manner as in Production Examples 18 to 22.

The obtained product was subjected to structure analysis using the same means for structure confirmation as in Production Example 18, and as a result, it was confirmed that the product was a compound represented by the structural formula shown in Table 2.

Example 1 70 parts of chlorostyrene, 2,2-bis (3,5-dibromo-4)
-Methacryloyloxyethoxyphenyl) propane 30
Spirooxazine compound of Preparation Example 1
0.4 part, 0.2 part of the chromene derivative of Production Example 18 was added, and 1 part of perbutyl ND was further added as a radical polymerization initiator,
Mix well. This mixture was poured into a mold composed of a gasket composed of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was carried out using an air furnace at 30 ° C. to 90 ° C. for 18 hours, gradually increasing the temperature, and maintaining the temperature at 90 ° C. for 2 hours. After the polymerization was completed, the mold was taken out of the air furnace, and after standing to cool, the polymer was removed from the glass of the mold. The obtained molded product having a thickness of 2 mm was converted to a Xenon Long Life Fade Meter FAL-2 manufactured by Suga Test Instruments Co., Ltd.
The fatigue life was measured by 5AX-HC.

Further, a change in color tone was visually observed. The fatigue life (T _1/2 ) is the time required for the spirooxazine compound and chromene or a derivative thereof to decrease the absorbance at the maximum absorption wavelength based on each compound to half of the initial (T ₀ ) absorbance. Expressed. However, the absorbance at T ₀ and T _1/2 is a value obtained by subtracting the absorbance of the unirradiated molded article at the maximum absorption wavelength based on each compound, and the absorbance at T ₀ is 60 seconds after light irradiation. It was measured after the passage.

 The results are shown in Table 3.

Examples 2 to 20 Example 1 was repeated except that the type and amount of the monomer, spirooxazine compound, chromene or a derivative thereof were changed and polymerization was carried out by a known means in accordance with the monomer. Same as. The results are shown in Table 3.

Example 21 2,2-bis- (4-methacryloyloxyethoxy-
The composition consisting of 40 parts of 3,5-dibromophenyl) propane and 60 parts of styrene was prepared by adding the spirooxazine compound of Production Example 1 to 0.1 part.
4 parts, 0.2 part of the chromene compound of Production Example 18, 0.6 parts of Sanol LS-744 as an ultraviolet stabilizer, and 1 part of perbutyl ND as a radical polymerization initiator were added and mixed well.

The obtained mixture was polymerized in the same manner as in Example 1 to obtain a thickness.
A molded product of 2 mm was obtained, and its photochromic performance was measured.

The results are shown in Table 4. In Table 4, the color tone at T1 _{/ 2} is the color tone of the spirooxazine compound at T1 _{/ 2} .

Examples 22 to 40 The monomers, spirooxazine compounds, chromene or derivatives thereof used in Example 21, and the amounts and types of the UV stabilizers were changed, and all the processes were carried out except that polymerization was carried out by known means according to the monomers. Same as Example 21. The results are shown in Table 4.

Example 41 To 100 parts by weight of chloroform, 0.8 g of the spirooxazine compound of Production Example 5 and 0.5 g of the chromene compound of Production Example 31 were added and dissolved. Put this solution in a quartz cell (1cm x 1cm x 4cm)
And irradiated with the xenon lamp of the fade meter described in Example 1 while stirring.

As a result of observing the change in color tone by visual observation, the color quickly changed from colorless to gray.

Claims (3)

(57) [Claims] (1) The following formula: A photochromic composition comprising: 100 parts by weight of a spirooxazine compound represented by the formula: and (b) 0.01 to 10,000 parts by weight of chromene or a derivative thereof. 2. A polymer composition comprising: (a) a polymer; and (b) 0.001 to 20 parts by weight of the photochromic composition according to claim (1). 3. A photochromic composition comprising (a) 100 parts by weight of the photochromic composition according to claim (1) and (b) 0.01 to 10,000 parts by weight of an ultraviolet stabilizer.