JP2735676B2 - Photochromic molding - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photochromic molded article having excellent photochromic action durability.

(Prior art) Photochromism is a phenomenon that has been attracting attention for the past several years. When a compound is irradiated with light containing ultraviolet light 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.

The present inventors have continued research on a series of photochromic compounds and have succeeded in synthesizing a novel spirooxazine compound having an oxazine skeleton, and have found that the spirooxazine compound has an excellent photochromic action, They have been proposed (Japanese Patent Application No. 2-42347 and Japanese Patent Application No. 2-78637).

(Problems to be Solved by the Invention) Further, the present inventors have continued research on producing a photochromic molded product represented by a photochromic lens by dispersing the above spirooxazine compound in a resin. As a result, they have found that the durability of the photochromic action of the spirooxazine compound is improved depending on how the spirooxazine compound is present in the resin.

Therefore, an object of the present invention is to obtain a photochromic molded article having excellent durability.

(Means for Solving the Problems) That is, the present invention provides the following formula [I] And a thermochromic resin layer on both surfaces of a resin layer containing a spirooxazine compound dispersed therein.

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.

Next, in the general formula [I], Is It is.

Here, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different, respectively, a hydrogen atom, a halogen atom, a hydrocarbon group,
An alkoxy group, a cyano group, a halogenoalkyl group, an amino group, a substituted amino group or an alkoxycarbonyl group,
At least one of R ₄ and R ₅ is a cyano group, a halogenoalkyl group or an alkoxycarbonyl group, Is an optionally substituted aromatic hydrocarbon group or an unsaturated heterocyclic group.

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

Examples of the hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group. Among them, the alkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
It is preferably from 4 to 4. More specific examples of the alkyl group include a methyl group, an ethyl group, and an isopropyl group. Further, the aryl group preferably has 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. The aralkyl group preferably has 7 to 14 carbon atoms. Specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, and a naphthylmethyl group.

Next, the alkoxy group is not particularly limited, but generally preferably has 1 to 10 carbon atoms, and preferably 1 to 4 carbon atoms. Specific examples include a methoxy group, an ethoxy group, and an isopropyloxy group. it can.

The halogen atom in the above halogenoalkyl group is fluorine, chlorine, bromine or the like, and the alkyl group preferably has 1 to 4 carbon atoms. Specifically, a trifluoromethyl group,
Trichloromethyl group, tribromomethyl group and the like.

An amino group or a substituted amino group has the general formula Indicated by R ₁₁ and R ₁₂ are preferably the same or different hydrogen atoms and hydrocarbon groups, respectively. As the hydrocarbon group, the same groups as those described for R _{4 to} R ₁₀ are preferably used. Furthermore, the substituted amino group has the general formula In the case represented by, R ₁₃ is an alkylene group such as a tetramethylene group and a pentamethylene group; _{-CH 2 OCH 2 CH 2 -,} CH 2 CH 2 OCH 2 CH 2 -, - oxyalkylene groups such as _{CH 2 O (CH 2 8;} -CH 2 SCH 2 CH 2 -, - CH 2 S (CH 2
_{8, -CH 2 CH 2 SCH 2} CH 2 - thioalkylene groups such as; 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 halogenoalkyl group or an alkoxycarbonyl group. By selecting these groups, the spirooxazine compound used in the present invention exhibits a good photochromic action even in a high temperature range.

next Is an aromatic hydrocarbon group or an unsaturated heterocyclic group which may be substituted. These groups are already The groups described for are employed without any limitation.

Is the general formula [I] And the spirooxazine compound used in the present invention exhibits a good photochromic action even at a high temperature range.

Next, in the general formula [I], When R ₁ and R ₂ are a hydrogen atom or an alkyl group, R ₁ and R ₂ may form a ring together,
R ₃ is an alkoxycarbonylalkyl group, When R ₁ and R ₂ are a hydrogen atom or an alkyl group, at least one of which is an alkyl group having 2 or more carbon atoms,
Or they may together form a ring,
R ₃ is a hydrogen atom, a hydrocarbon group, an alkoxycarbonylalkyl group or a cyanoalkyl group.

The alkyl group is not particularly limited, but generally preferably has 1 to 20 carbon atoms, and more preferably has 1 to 6 carbon atoms. Specific examples of the above alkyl group include a methyl group, an ethyl group, and an isopropyl group. Also, R ₁ and R ₂
When they together form a ring, they are not particularly limited, but generally a cycloalkyl ring having 5 to 10 carbon atoms, a bicycloalkyl ring, and a tricycloalkyl ring are preferred.
When these are exemplified more specifically, a cyclopentyl ring,
And a divalent group derived from a cyclohexyl ring, a scroheptyl ring, a norbornane ring, an adamantane ring, or a bicyclo [3.3.1] nonane ring. These R ₁ and R ₂ are
Either one 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 combination of these forms a ring to provide a good color density in a high temperature range. It is suitable for indicating

In the general formula [I], the hydrocarbon group represented by R ₃ is not particularly limited, and the groups described in R _{4 to} R ₁₀ are employed.

The alkoxy group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. 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.

The cyanoalkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the cyanoalkyl group include a cyanomethyl group, a cyanoethyl group, and a cyanopropyl group.

The spirooxazine compound represented by the general formula [I] in the present invention generally develops a color from red to blue. Therefore,
When the photochromic molded article of the present invention is used for applications such as decorative articles, the compound of the above general formula [I] may be used alone. When the photochromic molded article of the present invention is used for applications such as sunglasses, the color tone is generally preferred to be brown or gray. Therefore, the color tone is preferably adjusted in combination with another photochromic compound.
As other photochromic compounds, those generally called chromene or derivatives thereof are preferably used in the present invention because they can be adjusted to a brown or gray color by using the compound of the general formula [I] in combination. Can be The amount of the above-mentioned chromene or a derivative thereof may be appropriately selected depending on the required color tone. Generally, in order to obtain a brown or gray color tone, 0.01 to 10,000 based on 100 parts by weight of the compound of the general formula [I]. Parts by weight, preferably 0.05 to 1
It is better to select from the range of 000 parts by weight.

The above chromene has the following 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 0-R ⁸ _n (however, 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 carbon number of the above alkyl group and alkylene group is preferably in the range of 6 to 20, and _n of 0-R ⁸ n
Is preferably an integer such that the total number of carbon atoms is 6 to 20.

Next, in the general formula [A], the hydrocarbon group and the substituted amino group represented by R ¹ , R ² , R ³ and R ⁴ correspond to R ₄ to R _{4 of the} spirooxazine compound represented by the general formula [I]. similar hydrocarbon groups and substituted amino groups as described for R ₁₀ is employed.

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.

The resin of the resin layer containing a dispersed photochromic compound such as the spirooxazine compound or chromene or a derivative thereof, the photochromic compound can be uniformly dispersed,
A resin that does not swell or dissolve in the thermosetting resin monomer is preferably used. More specifically exemplified such a resin, polyvinyl alcohol, polyvinyl butyral,
Hydrophilic resins such as polyhydroxyethyl methacrylate, polyacrylonitrile and cellulose; polyolefin resins such as polyethylene and polypropylene; halogen-containing resins such as polytetrafluoroethylene and polyvinyl chloride;
Examples thereof include a thermosetting resin described below.

The mixing ratio of the resin and the photochromic compound is as follows:
It may be determined according to the concentration of the color development of the desired photochromic molded body, generally, the photochromic compound is 0.001 to 60 parts by weight, particularly 0.1 to 100 parts by weight of the resin.
It is preferably in the range of 40 parts by weight.

The thickness of the resin layer containing the photochromic compound is not particularly limited, but in general, from the viewpoint of the coloring density of the photochromic molded article and the durability of the photochromic property, 0.01 to
It is in the range of 2 mm, preferably 0.02 to 1 mm.

The method for producing the resin layer containing the photochromic compound is not limited at all, and examples thereof include the following method.

A method in which a thermoplastic resin and a photochromic compound are melt-kneaded at a temperature equal to or higher than the melting point of the thermoplastic resin and then extruded.

A method in which a thermoplastic resin is dissolved in an appropriate solvent, a photochromic compound is mixed therein, and the solvent is removed by evaporation or the like.

A method in which a raw material monomer of a thermoplastic resin or a thermosetting resin is mixed with a photochromic compound, and the resulting mixture is subjected to emulsion polymerization or suspension polymerization to form an emulsion or suspension on the surface of a thermosetting resin described later.

A method in which a raw material monomer of a thermoplastic resin or a thermosetting resin is mixed with a photochromic compound and cast polymerization is performed.

Next, as the thermosetting resin laminated on the resin layer containing the spirooxazine compound dispersed therein, ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4- Polyacrylic acid and polymethacrylic acid ester compounds such as methacryloyloxyethoxyphenyl) propane and 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate , Diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylol Polyvalent allyl compounds such as lopantriallyl carbonate; polyvalent thioacrylic acids such as 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether and 1,4-bis (methacryloylthiomethyl) benzene And a polyvalent thiomethacrylic acid ester compound; a polymer of a radically polymerizable polyfunctional monomer such as divinylbenzene; or an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, or maleic anhydride; Methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2
Acrylic acid and methacrylic acid ester compounds such as hydroxyethyl methacrylate; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate; Copolymers with radical polymerizable polyfunctional monomers such as vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, and bromostyrene: ethanedithiol, propanetriol, hexanedithiol, pentaerythritol tetrakisthioglycolate Copolymer of a polyvalent thiol compound such as di (2-mercaptoethyl) ether and the above-mentioned radically polymerizable monofunctional monomer: diphenylethane diisocyanate, xy Diisocyanate, p- phenylene polyvalent isocyanate compound and ethylene glycol such as isocyanate, trimethylolpropane, pentaerythritol, addition polymers such as of a polyhydric alcohol compound or a polyvalent thiol compound described above, such as bisphenol A and the like. These monomers can be used alone or in combination of two or more.

As a method of molding a photochromic molded body, any known method may be used as long as a resin layer containing a photochromic compound dispersed therein is laminated between thermosetting resins. A method of injecting the raw material monomer of the thermosetting resin on both sides of the resin layer containing the compound dispersed therein and then heating and curing the same, and using a suitable adhesive on both sides of the resin layer containing the photochromic compound to form the thermosetting resin. A method of laminating layers, a resin layer containing a photochromic compound dispersed on a thermosetting resin molded body is adhered using an appropriate adhesive, and a raw material monomer of the thermosetting resin is poured thereon and heat-cured. And the like. Further, in order to improve the adhesion between the resin layer containing the photochromic compound dispersed therein and the thermosetting resin, the surface of the resin layer may be coated with an adhesion reinforcing coat.
Examples of the adhesive reinforcing coating agent include an epoxy primer, a polyurethane primer, a silicone primer, and a polyalcohol primer.

The durability of the photochromic property can be further improved by adding an ultraviolet stabilizer to the resin layer containing the photochromic compound dispersed in the photochromic molded article of the present invention. 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, Sheasorb 3346 (all manufactured by American Cyanamid Co.), UV-Cek AM101, and UV-Cek
AM105 (all manufactured by Ferro Corporation), Ilgastab 2002, Tinuvin 765, Tinuvin 144, Chimasorb 944, Tinuvin 622, Irganox 1010, Irganox 245 (all manufactured by Ciba Geigy), Rilex NBC (DuPont), Sheasorb 3346 ( Manufactured by American Cyanamid Co., Ltd.), SANOL LS-1114, SANOL LS-744, SANOL LS
−2626 (above 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
(Manufactured by Sumitomo Chemical Co., Ltd.), Mark AO-50, Mark AO-20, Mark AO-30, Mark AO-330, Mark AO-23 (above, manufactured by Adeka Argus Co.), Antioxidant HPM-12 (S.
FOS). Each of the above names is a trade name.

(Effect) In the photochromic molded article of the present invention, the durability of the photochromic compound is improved by allowing the photochromic compound to be present in the resin.

The photochromic molded article of the present invention can be used in a wide range of fields, for example, various recording memory materials, copying materials, printing photoconductors, cathode ray tube recording materials, laser photosensitive materials, etc. It can be used as a recording material. In addition, the photochromic molded article 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”.

 The symbols in the following examples indicate the following compounds.

・ BMDBP: 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane ・ Cl-St: chlorostyrene ・ TMP-TAC: trimethylolpropane triallyl carbonate ・ BADBP: 2,2-bis ( 4-allyl carbonate 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-Diboromophenoxy) -2 -Hydroxypropyl acrylate-MMA: methyl methacrylate-DEGDMA: diethylene glycol Dimethacrylate-TBBM: 3,4,5-tribromobenzyl methacrylate-HEMA: 2-hydroxyethyl methacrylate-BMA: benzyl methacrylate-PVA: polyvinyl alcohol-PHEMA: polyhydroxyethyl methacrylate-PAN: polyacrylonitrile Production Example 1 Compound of 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 values of this compound were C65.12%, H4.90%, N8.51
%, O9.74%, a F11.73%, C65.45% is calculated values for _{C 27 H 24 N 3 O 3} F 3, H4.88%, N8.48%, O9.69%, F11.5
This was in very good agreement with 0%. When the proton nuclear magnetic resonance spectrum was measured, the peak of 9H based on the proton of the quinoline ring, the proton of the indoline ring, and the proton of the oxazine ring was found at around δ6.5 to 9 ppm, and around δ4 ppm. 2H peak based on the proton of
3H peak based on proton of CH ₃ bond, δ 1.3 to 2.1 ppm
In the vicinity, a broad peak of 10H based on the cyclohexane ring proton was shown. Further measurement of ¹³ C-nuclear magnetic resonance spectrum, a peak based on carbon of carbonyl at around 170 ppm, a peak based on carbon of benzene ring, quinoline ring and oxazine ring of indoline around δ100 to 160 ppm, and a trifluoro peak around δ125 ppm A peak based on a methyl 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 (1).

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.

The elemental analysis value of this compound was C65.23%, H5.21%, N8.56
%, O9.71%, a F11.29%, C65.18% is calculated values for _{C 27 H 26 N 3 O 3} F 3, H5.27%, N8.45%, O9.93%, F11.4
This was very good agreement with 6%. In addition, when the proton nuclear magnetic resonance spectrum was measured, a peak based on an aromatic proton was observed around δ 6.5 to 9 ppm, a peak based on a proton of an ethyl group methyl around δ 1.0 ppm, and a peak based on an ethyl group methylene around δ 2 ppm. Peak based on proton, δ
And a peak based on protons of N-CH ₂ CH ₂ COOCH ₃ near 3.5 ppm. Further, when ¹³ C-NMR was measured, δ 17
A peak based on carbonyl carbon at around 0 ppm, δ100-1
Aromatic carbon around 60 ppm, peak based on carbon of oxazine ring and carbon of trifluoromethyl group, δ99
A peak based on spiro carbon near ppm, a peak based on carbon of methylene bonded to nitrogen near δ50 ppm, δ20 ~
The peak based on the carbon of the methyl group and the methylene group bonded to carbon was shown at around 40 ppm. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (2).

Production Example 3 Compound of the Following Formula 2.01g (0.0059mol) and the following compounds 1.02 g (0.0059 mol) and 0.43 g (0.006 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 give a spirooxazine compound (400 mg) of the following formula.

Elemental analysis values of this compound were C81.35%, H6.60%, N7.62
%, O 4.43%, which is a calculated value for C ₂₅ H ₂₄ N ₂ O
The values agreed very well with 81.49%, H6.57%, N7.60% and O4.34%. Further, when the proton nuclear magnetic resonance spectrum was measured, the peak of 11H based on the proton of the naphthalene ring, the proton of the indoline ring, and the proton of the oxazine ring at around δ 6.5 to 8.0 ppm, and N- The peak of 3H based on the proton of the CH ₃ bond and the broad peak of 10H based on the proton of the cyclohexane ring were shown around δ1.3 to 2.0 ppm. When further measured ¹³ C-nuclear magnetic resonance spectrum, peaks based on carbon of benzene ring, naphthalene ring and oxazine ring of indoline at around δ100 to 160 ppm, peaks based on spiro carbon around δ99 ppm and δ56 ppm, around δ20 to 35 ppm Shows the peaks based on the carbons of the cyclohexane group and the methyl group.

From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (3).

Production Example 4 The following compound 2.0g (0.0057mol) and the following compounds 0.98 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 purification was carried out by chromatography on silica gel to obtain 200 mg of a spirooxazine compound represented by the following formula.

Elemental analysis values of this compound were C78.66%, H6.09%, N11.0
5%, O4.2%, which is a calculated value for C ₂₅ H ₂₃ N ₃ O
The values agreed very well with 78.71%, H6.08%, N11.02% and O4.2%. Further, when the proton nuclear magnetic resonance spectrum was measured, a peak of 10H based on a proton of a quinoline ring, a proton of an indoline ring and a proton of an oxazine ring near δ 6.5 to 9 ppm, and an N-CH ₃ bond near δ 2.7 ppm A 3H peak based on a proton, and a broad 10H peak based on a norbornane ring proton were shown around δ1.3 to 2.5 ppm. Further measurement of ¹³ C-nuclear magnetic resonance spectrum, the peak based on carbon of benzene ring, naphthalene ring and oxazine ring of indoline around δ100 to 160 ppm,
peaks based on spiro carbon around δ99ppm and δ52ppm,
A peak based on the carbon of the norbornane ring was shown around δ27 to 52 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (4).

Production Examples 5 to 21 Spirooxazine compounds shown in Table 1 were synthesized in the same manner as in Production Examples 1 to 4.

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 22 1-hydroxy-2-acetonaphthone 10 g (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.

The elemental analysis value of this compound was C86.93%, H6.89%, O6.18
%, Calculated value for C ₁₉ H ₁₈ O, C87.02%, H
This was very good agreement with 6.87% and O6.12%. When the proton nuclear magnetic resonance spectrum was measured, δ 7.2 to 8.3 pp
A peak of 6H based on the proton of the naphthalene ring near m,
A peak of 2H based on the proton of the alkene was shown at about δ5.6 to 6.7 ppm, and a broad peak of 10H was shown at about δ1.2 to 2.5 ppm based on the proton of the norbornylidene group. Further ¹³ C
-Nuclear magnetic resonance spectrum was measured, δ27 ~ 52pp
Near m, a peak based on carbon of the norbornylidene group, δ1
A peak based on carbon of the naphthalene ring around 10 to 160 ppm,
A peak based on the carbon of the alkene appears around δ80 to 110 ppm. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (22).

Production Example 23 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.

The elemental analysis value of this compound was C86.81%, H7.62%, O5.57
%, Calculated value for C ₂₁ H ₂₂ O, C87.90%, H
It was in good agreement with 7.59% and O5.52%. When the proton nuclear magnetic resonance spectrum was measured, δ 7.2 to 8.3 pp
A peak of 6H based on the proton of the naphthalene ring near m,
A peak of 2H based on alkene protons at around δ 6.0 to 7.0 ppm, and a bicyclo [3.3.1] -9-at around δ 1.2 to 2.5 ppm
It showed a broad peak at 14H based on the proton of the nonylidene group. Further measurement of ¹³ C-nuclear magnetic resonance spectrum, a peak based on carbon of bicyclo [3.3.1] -9-nonylidene group around δ27 to 52 ppm, a peak based on carbon of naphthalene ring around δ110 to 160 ppm, δ80 to A peak based on the carbon of the alkene appears at around 110 ppm. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (23).

Production Example 24 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, 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.
After heating for 0 minutes, a brown viscous liquid is generated by chromatography on silica gel, and a chromene derivative of the following 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 22,
This compound was confirmed to be the compound represented by the above structural formula (24).

Production Example 25 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 24, and a dehydration reaction was performed. After separation and purification, 5.84 g of a chromene derivative represented by the following formula was obtained.

As in Production Example 22, it was confirmed by an elemental analysis, a proton nuclear magnetic resonance spectrum and a ¹³ C-nuclear magnetic resonance spectrum measurement that this compound was the compound represented by the above structural formula (25).

Production Example 26 10 g (0.0318 mol) of 5-n-octyloxy-1-hydroxy-2-acetonaphthone and 2.77 g (0.0477 m) of acetone
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 22, it was confirmed by an elemental analysis, a proton nuclear magnetic resonance spectrum and a ¹³ C-nuclear magnetic resonance spectrum measurement that this compound was the compound represented by the above structural formula (26).

Production Examples 27 to 35 The chromene derivatives shown in Table 2 were synthesized in the same manner as in Production Examples 22 to 26.

The obtained product was subjected to structure analysis using the same means for structure confirmation as in Production Example 22, and as a result, it was confirmed to be a compound represented by the structural formula shown in Table 2.

Example 1 A polyvinyl alcohol film (0.2 mm thick) in which 5 parts by weight of the spirooxazine compound of Production Example 1 and 3 parts by weight of the chromene derivative of Production Example 22 were dispersed in 100 parts by weight of polyvinyl alcohol, and the surface was coated with an adhesion reinforcing coat ) Is set in the center of a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and allyl diglycol carbonate containing 3.0% by weight of isopropyl percarbonate is injected into the cavity on both sides thereof, 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 fatigue life of the obtained molded product was measured with a Xenon Long Life Fade Meter FAL-25AX-HC manufactured by Suga Test Instruments Co., Ltd.

Further, a change in color tone was visually observed. The fatigue life (T _1/2 ) was represented by the time required for the absorbance at the maximum absorption wavelength of the spirooxazine compound to fall to half of the initial (T ₀ ) absorbance. 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 the spirooxazine compound, and T ₀
Was measured 60 seconds after light irradiation.

 The results are shown in Table 3.

Examples 2 to 21 In Example 1, the type and amount of the raw material monomers of the resin containing the used photochromic compound dispersed therein, the photochromic compound, and the thermosetting resin were changed, and polymerization was performed by a known means in accordance with the raw material monomer. Other than that, it carried out similarly to Example 1. The results are shown in Table 3.

Comparative Example 1 The fatigue life of a polyvinyl alcohol film containing the photochromic compound obtained in Example 1 dispersed therein was measured in the same manner as in Example 1. The results are shown in Table 3.

Claims (1)

(57) [Claims] (1) The following formula: A photochromic molded article comprising a thermosetting resin layer laminated on both sides of a resin layer containing a spirooxazine compound dispersed in the formula (1).