JPH0453893A - photochromic composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to photochromic compositions having various color tones such as gray, brown, and amber.

(Prior art) Photochromism is a phenomenon that has attracted attention over the past few years.When a certain compound is irradiated with light containing ultraviolet rays, such as sunlight or mercury lamp light, the color changes immediately, and when the compound is irradiated with light, it immediately changes color. This is a reversible effect that returns to the original color when you stop using it and leave it in a dark place. Compounds having this property are called photochromic compounds, and compounds with various structures have been synthesized and proposed, but no particular common skeleton has been recognized in their structures.

Chromene or its derivatives are known as photochromic compounds. The color tone of chromene or its derivatives is orange to yellow. On the other hand, spirooxazine compounds are also well known as photochromic compounds, and the color tones of these compounds range from red to blue.

(Problems to be Solved by the Invention) However, when each of these compounds is used alone, a desired color tone may not be obtained. In particular, when used as a photochromic lens, gray,
Colors such as amber and brown are preferred, but these colors cannot be obtained with the above-mentioned compounds alone.

Therefore, the inventors of the present invention have conducted extensive research in order to develop various intermediate colors including gray, amber, and brown.

(Means for Solving the Problem) As a result, as a result of mixing the novel spirooxazine compound synthesized by the present inventors with chromene or its derivative, various intermediate colors including gray, amber, brown, etc. We succeeded in developing a color, and completed the present invention.

That is, the present invention is a photochromic composition characterized by comprising (a) the following formula (1) (b) 0.01 to 10,000 parts by weight of chromene or a derivative thereof.

Component (a) of the photochromic composition in the present invention is a spirooxazine compound represented by the above-mentioned -Funenin [1).

100 parts by weight of the spirooxazine compound represented by the following is an optionally substituted aromatic hydrocarbon group or unsaturated heterocyclic group. Specific examples of aromatic hydrocarbon groups include divalent groups derived from one benzene ring or 2 to 4 condensed rings thereof, such as a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. In addition, the above aromatic hydrocarbon groups include hydroxyl group, nitro group, cyano group,
fluoroalkyl group, substituted amino group, halogen atom, alkyl group, alkoxy group, phenyl group or thienyl group,
Examples include substituted aromatic hydrocarbon groups substituted with one or more heterocyclic groups such as furyl or pyrrolyl groups.

Examples of the unsaturated heterocyclic group which may be unsaturated include a 5-membered ring, a 6-membered ring containing oxygen, sulfur, or nitrogen atom, or a heterocyclic group in which a Hensen ring is fused to these rings.

Specifically, derivatives include nitrogen-containing heterocycles such as a pyridine ring, quinoline ring, pyrrole ring, and indole ring; oxygen-containing heterocycles such as a furan ring and hensifuran ring; and sulfur-containing heterocycles such as a thiophene ring and hendithiophene ring. and divalent heterocyclic groups. In particular, high coloring density can be obtained when the ring is a two-ring condensed heterocycle consisting of a -Zenzene ring and a 5- or 6-membered heterocycle.

Furthermore, as the substituent for the unsaturated heterocyclic group, the above-mentioned substituents for the aromatic hydrocarbon group can be employed without any restrictions.

Furthermore, in the above-mentioned - Shipman CI), R3 and R2 are a hydrogen atom or an alkyl group, and R5 and R2 may be taken together to form a ring. The above alkyl group is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
Preferably, the number is 6. More specific examples of the alkyl groups mentioned above include methyl, ethyl, and isopropyl groups. Further, when R8 and R2 are combined to form a ring, it is not particularly limited, but generally a cycloalkyl ring, bicycloalkyl ring, or tricycloalkyl ring having 5 to 10 carbon atoms is suitable. More specific examples of these include cyclopentyl ring, cyclohexyl ring,
Examples include divalent groups derived from a cyclohebutyl ring, a norbornane ring, and an adamantane ring. These R1 and R
2 is a compound in which 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 compound in which these two groups are combined to form a ring has good coloring. Preferred for indicating concentration.

In the above-mentioned shipman [I], R3 is an alkoxycarbonyl alkyl group. The alkoxy group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 carbon number.
-10, preferably 1-4 are suitable. The alkylene group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
4 is preferred. 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, a butoxycarbonylethyl group, and the like.

In the above general 2 (1), R4, R3, R6, R.

and R8 is a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogen atom, a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group, and at least one of R4 and R3 is a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group. .

The above hydrocarbon groups include alkyl groups, aryl groups,
Examples include aralkyl groups.

Among these, the alkyl group generally has 1 to 10 carbon atoms.
, preferably 1 to 4. More specific examples of this alkyl group include a methyl group, an ethyl group, an isopropyl group, and the like.

Further, the above aryl group preferably has 6 to 10 carbon atoms, specific examples include phenyl group, naphthyl group, etc., and the aralkyl group preferably has 7 to 14 carbon atoms. (Specifically, Hensyl group, phenylethyl group, phenyl 7'.

Examples include pyru group and naphthylmethyl group. The alkoxy group preferably has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specifically includes a methoxy group, an ethoxy group, and an isopropyloxy group. Examples of the halogen atom include fluorine, chlorine, and bromine. 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 this alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

In general 2 (1), at least one of R4 and R6 must be a di-ano group, [-lifluoromethyl group or an alkoxycarbonyl group. By selecting these groups, the spirooxazine compound of the present invention exhibits a good photochromic effect even in a high temperature range.

Component (b) of the photochromic composition of the present invention is chromene or a derivative thereof. Chromene is a compound represented by the following formula. In addition, the chromene derivatives include compounds having the above-mentioned chromene skeleton (which may be employed without any restrictions. In the present invention, chromene derivatives represented by the following formulas (A, ) are particularly preferred because they have excellent photochromic properties. used for.

As the aromatic hydrocarbon group and the unsaturated heterocyclic group, the spirooxazine compound shown in the above-mentioned --- Funato [I] is employed. Further, as the substituents for these aromatic hydrocarbon groups and unsaturated heterocyclic groups, the substituents for the above-mentioned Funato (1) group hydrocarbon groups and unsaturated heterocyclic groups can be employed without any restriction.

The same hydrocarbon group as .

R5 is an alkylene group or +O-R'+i (wherein R3 is an alkylene group and n is a positive integer),
Rh and R7 are the same or different alkyl groups, respectively, and X is -N<, -P<.

One or more may be substituted. R' above
The alkyl group or alkylene group represented by R'R' and RB is preferably a long chain with 6 to 20 carbon atoms, and n in (-0-R'+t-) has a total carbon number of 6 to 2.
Preferably, it is a positive number that is 0.

Next, the - Sailor (in Al, R1, RZ, R3 and R
The hydrocarbon group represented by 4 is the same or different hydrogen atom; alkyl The hydrocarbon group is preferably a hydrocarbon group such as a group, an aralkyl group, or an aryl group.As the hydrocarbon group, the same one as shown for R'-R' above is preferably used.

When shown, R11 is an alkylene group such as a tetramethylene group or a pentamethylene group;
3 CHzOCHzCHz-1CHzCHzOCHzCHz
Oxyalkylene group such as -CI(zo(CHz+T); CH25CH2CH2CHzS(CHz)rCHz
Thioalkylene group such as CHzSCHzCH2-; CH
3C1h CHzNCHzCHz CH□N(C8zh
CH: Preferably, it is an abu alkylene group such as 1 CHzCI (zNCHzCHz-).

In addition, R' and R2 in the above general 2 (A) may be joined together to form a ring, and in this case, the ring is as explained for R1 and R2 in the above - boatman (1). The rings given above will be adopted without any restrictions.

Among the above-mentioned chromenes or derivatives thereof, a metal ring is preferable because it has a high color density.

Among these, compounds in which a ring is fused to the 7.8-position of the chromene skeleton are more preferred. In addition, among the above-mentioned mariners (A), R1 and R
When 2 forms a ring, 5.6 of the chromene skeleton
Compounds in which a ring is condensed at this position are also preferably used.

In the present invention, the mixing ratio of the spirooxazine compound and chromene or its derivatives can be arbitrarily selected depending on the desired color tone, but in order to adjust the color tone to brown, gray, amber, etc., generally , 0.01 to 10,000 parts by weight of chromene or its derivatives, preferably 0.
．． The amount is preferably 05 to 1000 parts by weight.

By dispersing the photochromic glue of the present invention in an organic solvent, it can be made into a photochromic fluid that can be used for purposes such as decoration.

Furthermore, by dispersing the photochromic composition of the present invention in a polymer such as a thermoplastic resin or a thermosetting resin,
Molded objects such as photochromic glass and photochromic lenses can be obtained.

Any thermoplastic resin may be used as long as it can uniformly disperse the spirooxazine compound and chromene or its derivatives, and optically preferable examples include polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, and polymethacrylate. Examples include ethyl acid, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly(2-hydroxyethyl methacrylate), polydimethylsiloxane, and polycarbonate.

Dispersion of the photochromic composition of the present invention in a thermoplastic resin can be carried out by a method of synthesizing the thermoplastic resin, that is, by carrying out polymerization in the presence of the photochromic composition, or by combining the thermoplastic resin and the photochromic composition into a thermoplastic resin. Examples include a method of melting and kneading at a temperature higher than the melting temperature.

Next, as thermosetting resins, ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis(4-methacryloyloxyethoxyphenyl)propane, 2,
Polyacrylic acid and polymethacrylic acid ester compounds such as 2-bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate,
Polyvalent allyl compounds such as diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 1,2-bis(methacryloylthio) Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds such as ethane, bis(2-acryloylthioethyl)ether, and 1,4-bis(methacryloylthiomethyl)benzene; radically polymerizable polyfunctional monomers such as divinylhenzene; or each of these monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride; methyl acrylate, methyl methacrylate, hensyl methacrylate, phenyl methacrylate, 2-
Acrylic acid and methacrylic acid ester compounds Th 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; Styrene, chlorstyrene′,
Copolymers with radically polymerizable polyfunctional intermediates such as vinyl compounds Th such as methyphrestyrene, vinylnaphthalene, and bromostyrene; furthermore, ethanedithiol, propanetriol, hexanedithiol, pentaerythritol tetrakisthioglycolate, di( Addition copolymers of polyvalent thiol compounds such as 2-mercaptoethyl) ether and the above-mentioned radically polymerizable polyfunctional monomers Polyvalent isocyanates such as nidiphenylethane diisocyanate, xylene diisocyanate, p-phenylene diisocyanate l- compound and utilene glycol,.

Examples include polyhydric alcohol compounds such as trimethylolpropane, pentaerythritol, and bisphenol A, and addition polymers with the above-mentioned polyhydric thiol compounds. These raw materials can be used alone or in combination of two or more.

For dispersing the photochromic composition in the above-mentioned thermosetting resin, a method is generally adopted in which the raw material of the thermosetting resin and the photochromic composition are mixed and then polymerized.

The amount of the photochromic composition of the present invention to be dispersed in such a polymer is 0 to 100 parts by weight of the polymer.
．． 0.001 to 20 parts by weight, preferably 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, any known ultraviolet stabilizer added to various types of plastics may be used without any limitations.

In the present invention, considering the improvement in the durability of the photochromic compound, among various UV stabilizers, heavy oxygen quenchers, hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants are preferably used. be done. A more specific example of these UV stabilizers is Sheasorb UV 1084. Sheasorb 33
46 (manufactured by American Cyanamid Company); UV-
Check AM 101. IJ■-Cheku AM105 (manufactured by Ferro Corporation); Irgastab 20
02 Tinuvin 765 Tinuvin 144. Kimasorbu 9
44. Tinuvin 622 Irganox 1010. Irganonx 245 (manufactured by Chiha Geigy); Rylenx NBC (manufactured by DuPont); Sanol L S-1
114, Sanol LS744, Sanol LS-26
26 (manufactured by Sankyo Co., Ltd.); Sumilizer GA-80,
Sumilizer GM, Sumilizer BBM-5, 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 A
O-30, Mark AO-330.

Mark AO-23, Mark LA-82, Mark LA-8
7 (manufactured by Adeka Argus); Antioxidant 1 (PM-12 (S, F, O, S, manufactured by Adeka Argus), etc.). All of the above names are trade names.

The blending 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 its derivative. In terms of photochromic properties, UV stabilizers are
Preferably, the amount is in the range of 500 parts by weight.

(Effects) As explained above, the photochromic composition of the present invention changes from colorless to colored or darkly colored form when exposed to sunlight or light containing ultraviolet rays such as light from a mercury lamp, and this change is reversible. It shows excellent dimming performance. Furthermore, the present invention has succeeded in easily obtaining various intermediate colors including 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, such as various recording and storage materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for cathode ray piping, and photosensitive materials for lasers. It can be used as a variety of recording materials such as. In addition, the photochromic composition of the present invention includes photochromic lens materials, optical filter materials,
It can also be used as a display material, light meter, decoration material, etc.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

"Parts" in Examples are "parts by weight."

In addition, symbols and trade names of ultraviolet stabilizers in the following examples indicate the following compounds.

・BMDBP: 2,2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane cp-st: chlorstyrene ・TMP-TAC: )limethylolpropane triallyl carbonate ・BADBP: 2,2-bis( 4-allyl carbonate ethoxy-3,5-dibromophenyl)propane DC=allyl diglycol carbonate DAP
Diaryl phthalate, St: Styrene, DCIPF Nidi(2-chloroisopropyl) fumarate, EGDMA: Ethylene glycol dimethacrylate, PETTP: Pentaerythritol tetrakis (β-thiopropionate), DME Nidi(2-mercaptoethyl) ether, DVB: Divinylhenzen, XIC: Xylylene diisocyanate, HP8: 3-(2,4-siphyromophenoxy)2-hydroxypropyl acrylate, MMA: Methyl methacrylate, DECDMA
Nidiethylene glycol dimethacrylate/TBBM: 3,4.5-tribromohensyl methacrylate/HEMA: 2-hydroxyethyl methacrylate/B
MA: Benzyl methacrylate/IPP diisopropyl peroxycarbonate/perbutyl ND: (Nippon Oil & Fats Co., Ltd.) t-butylpaoxy-2-hexanate/BPO: Henzyl peroxide/Sanol LS-744 (Product name: Sankyo Co., Ltd.) Sanol LS-2626 (Product name manufactured by Nisankyo Co., Ltd.) CH3 ・MARK LA-82 (Product name manufactured by Near Deca Argus Co., Ltd.) CH.

・MARK LA-87 (Product name: Made by Neardeca Argus) ・Sumilizer〇A-80 (Product name: Manufactured by Sumitomo Chemical Co., Ltd.) CH.

Irganox (Product Name: Manufactured by Chiha Geigy) Cyasorb UB 1084 (Product Name: Manufactured by American Cyanamid Company) (Product name: Sumitomo Chemical ()! Z5CI zSCHzC) IzCOOCHz)
, C. Tinuvin (Product name: manufactured by Chiha Geigy) V Chek M (Product name: Ferro Corporation? [) M3 M3 M3 +1: I ・Sanol S (Product name: manufactured by Kyodo) Manufacturer Example 1 A compound of the following formula C) lZcOOcH3 2,01 (0,0057 mol) and a compound N of the following formula.

Fff 1-4 g (0,0057 mol) and pyrrolidine 0
．． 41 g (0,0058 mol) of 1,000 liters of alcohol 5
To 0mf? The mixture was heated under reflux for 2 hours.

After the reaction, the solvent was removed, and 200 mg of the spirooxazine compound of the following formula was obtained by purification by chromatography on silica gel.

The elemental analysis values of this compound are C65,12%, H4,9
0%, N 8.51%, 09.74%,
F 11.73%, CzJz4NxO: +F+
Calculated value for C65.45%, H4,88
%, N 8.48%, 09.69%.

It was in excellent agreement with F 11.50%. In addition, when proton nuclear magnetic resonance spectra were measured, the results were 66.5~
A <9H peak based on the quinoline ring proton, indoline ring proton, and oxazine ring proton near 9 ppm, <2H peak based on the N-CH2-C-bond proton near 64 ppm, 63. <3H peak based on the proton of -0-CH3 bond near 7 ppm, δ
A broad peak of 10H based on the proton of the cyclohexane ring was observed around 1-3 to 2.1 ppm. Further l
5 (- When nuclear magnetic resonance spectrum was measured, 170
Peak based on carbonyl carbon near ppm, 610
Peaks based on the carbons of the benzene ring, quinoline ring, and oxazine ring of indoline around 0 to 160 ppm, 612
A peak based on the trifluoromethyl group was shown around 5 ppm, a peak based on spiro carbon around 699 ppm and 652 pp+m, and a peak based on the methyl group and methylene chain carbon around 620 to 50 ppn+.

From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (1).

Production Example 2 Compound H of the following formula: ICH2CCH2CH3 CHzCHzCOOCH3 2-Og (0,0057 mol) and compound N of the following formula
.

1.4 g (0,0057111 ol) of F3 and 0.41 g (0,0057 mol) of pyrrolidine were dissolved in 50 mf of ethyl alcohol and heated under reflux for 2 hours. After the reaction, the solvent is removed and the spirooxazine compound 1 of the following formula is purified by chromatography on silica gel.
50 mg was obtained.

0OCHI The elemental analysis values of this compound are C65,23%, H5,2
1%, N 8.56%, O9,71%, F
11.29%, CZ7H26N:10:lF
Calculated values for 3: C65.18%, H5°27%
, N 8.45%, 09.93% F 11.46%
In addition, when the proton nuclear magnetic resonance spectrum was measured, there was a peak based on aromatic protons around 66.5 to 9 ppm, and a peak of δ 1.
A peak based on the methyl proton of the ethyl group near 0 ppII, a peak based on the methylene proton of the ethyl group near δ2 ppn+, and a peak based on the methylene proton of the ethyl group near 63 and 5 ppm.
Peaks based on protons of CH2CHHzCOOCHz are shown. In addition, when we measured ``(, -NMR, it was found that 61
A peak based on carbonyl carbon around 70 ppm, 6
Aromatic carbon around 100-160 ppm,
A peak based on the carbon of the oxazine ring and the carbon of the trifluoromethyl group, a peak based on the spiro carbon around 699 ppm, a peak based on the methylene carbon bonded to nitrogen around 650 ppm, and a methyl group bonded to the carbon around 620 to 40 ppm and a peak based on the carbon of the methylene group. From the above results, the isolated product has the above structural formula (2
) was confirmed to be a compound shown by

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

As a result of structural analysis of the obtained product using the same structural confirmation method as in Production Example 1, it was confirmed that it was a compound represented by the structural formula shown in Table 1.

Production example 18 1-hydroxy-2-acetonaphthone 10g (0.05
4 mol) and norkampfy -6,6 g (0,0
6 mol) and pyrrolidine 8 g (0,113 mol)
A solution was prepared by dissolving this in 300 cc of toluene. The mixture was boiled for 10 hours and the water was separated. After the reaction was completed, toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized from acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to form a chromanol compound. 7.47 g of this chromanol compound was mixed with 4.5 g of anhydrous copper sulfate in a carbon dioxide stream at 150 to 160 g.
By heating at °C for 10 min and purifying the brown viscous liquid by chromatography on silica gel.
6.3 g of a chromene derivative of the following formula was obtained.

The elemental analysis values of this compound are C86,93%, H6,8
C 87.02%, H6, 87%, 06.9%, 06.18%, which is the calculated value for C,,H,,0.
It was in very good agreement with 12%. In addition, when proton nuclear magnetic resonance spectra were measured, δ7.2-8.3pp
<6H peak based on the naphthalene ring proton near m, <2H peak based on the alkene proton near 65.6 to 6.7 ppm, and norbornylidene group proton near 61.2 to 2.5 ppm. It showed a broad peak of 10H based on Furthermore, when the 13c-nuclear magnetic resonance spectrum was measured, it was found that the peak was based on the carbon of the norbornylidene group near 627-52pp111 (peak, 6110-1
A peak based on the carbon of the naphthalene ring around 60 ppm,
A peak based on alkene carbon appears around 680 to 110 ppm.

From the above results, the isolated product has the above structural formula (18)
It was confirmed that the compound was

Production example 19 1-acetyl-2-naphthol 10 g (0,054
mol) and bicyclo(3,3,1)nonan-9-one8
．． 29 g (0.06+ol) and 8.7 g of morpholine
(0.1 Oa+ol) was added to 300 cc of 1-toluene to prepare a solution. The mixture was boiled for 5 hours and the water was separated. After the reaction was completed, toluene was removed under reduced pressure, and the remaining chromanone compound was recrystallized from acetone. Next, this chromanone compound was dissolved in methanol 200
cc and added lithium aluminum hydride to form a chromanol compound. 6.49 g of this chromanol compound was heated with anhydrous copper sulfate in a stream of carbon dioxide at 170-180°C for 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel.
5.8 g of a chromene derivative of the following formula was obtained.

The elemental analysis values of this compound are C86,81%, H7,6
2%, 05.57%, calculated values for CZI8220: C 87.90%, H7, 59%, 05.
There was a very good agreement of 52%. In addition, when pro-1-one nuclear magnetic resonance spectra were measured, 67.2 to 8.3p
<6H peak based on the proton of the naphthalene ring near pm, 66.0-7. Based on Lukene's protons near Oppm <2) A peak, 61.2-2.5 pp
A broad peak of 14H based on the proton of the bicyclo[3,3,1]9-nonylidene group was shown near m. Further +
When 3C-nuclear magnetic resonance spectrum was measured, 627
Peak based on carbon of bicyclo C3,3,1,:19-nonylidene group around ~52 ppm, 6110-160p
Peak based on carbon of naphthalene ring near pm, 680
A peak based on the carbon of the alkene appears around ~110 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (19).

Production Example 20 3.06 g (0,
01 mol) in 50 cc of anhydrous ether, cooled the solution to O'C and dissolved 1 g of freshly prepared Grignard reagent CH3 (0,012 mol
) was added dropwise into the solution over about 1 hour. After the addition was completed, the ether solution was stirred for another 2 hours at room temperature, the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, the ether was removed under reduced pressure, and the chromanone The compound was changed to a chromanol compound. This chroma-71 compound was then heated with anhydrous copper sulfate in a stream of carbon dioxide at 200°C for about 10 minutes, and a brown viscous liquid was chromatographed on silica gel to form a chromene derivative of formula 2. 47 g was obtained.

As in Production Example 18, it was confirmed by elemental analysis, proton nuclear magnetic resonance spectrum, and 13C-nuclear magnetic resonance spectrum that this compound was a compound represented by the above structural formula (2o).

Production example 21 1-acetyl-2-naphthol 10 g (0,054
mol) and norkampfy -6,6g (0,06mol
1) and 7 g (0.10 mol) of morpholine B were dissolved in 300 cc of toluene, boiled for 15 hours, and water was separated. After the reaction was completed, toluene was removed under reduced pressure, and 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 added to methanol at 100C.
2 and reacted with methyl iodide to obtain 6.95 g of a chromanone compound Th represented by the following formula.

Next, in the same manner as in Production Example 20, the generated chromanone compound was converted into a chromanol compound, subjected to a dehydration reaction, and after separation and purification, a chromene derivative 5.84 of the following formula was obtained.
I got g.

Similarly to Production Example 18, this compound was confirmed to be a compound represented by the above structural formula (21) by elemental analysis, proton nuclear magnetic resonance spectroscopy, and C-C-nuclear magnetic resonance spectroscopy.

Production Example 22 5-n-octyloxy-1-hydroxy-2acetonaphthone 10 g (0,0318 mol) and acetone 2
, 77 g (0,0477 mol) and pyrrolidine 1.
13 g (0,0159 mol) in toluene 100mf
A solution was prepared by dissolving . The mixture was boiled for 10 hours and the water was separated. After the reaction, toluene was removed under reduced pressure and the remaining chromanone compound was dissolved in methanol (100ml).
ff and gradually added sodium borohydride to obtain a chromanol compound. 6.0 g of this chromanol compound was mixed with 4.0 g of anhydrous copper sulfate in a carbon dioxide stream. By heating with Og at 150-160° C. for 10 minutes and purifying the brown viscous liquid by chromatography on silica gel, 3.8 g of a chromene derivative of the following formula was obtained.

As in Production Example 18, it was confirmed by elemental analysis, proton nuclear magnetic resonance spectrum, and +3C-nuclear magnetic resonance spectrum that this compound was a compound represented by the above structural formula (22).

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

As a result of structural analysis of the obtained product using the same structural confirmation method as in Production Example 18, it was confirmed that it was a compound represented by the structural formula shown in Table 2.

Example 1 0.4 part of the spirooxazine compound of Production Example 1 and Production Example] 8 chromene derivative 0.2
Part of barbutyl NDI was added thereto as a radical polymerization initiator, and the mixture was thoroughly mixed. This mixed solution was poured into a mold consisting of a glass plate and a gasket made of ethylene-vinyl acetate copolymer, and cast polymerization was performed.

Polymerization was carried out using an air oven at 30'C to 90°C for 18 hours, gradually increasing the temperature and holding at 90°C for 2 hours. After the polymerization was completed, the mold was taken out from the air oven, and after cooling, the polymer was removed from the glass mold. The fatigue life of the obtained molded product having a thickness of 2 m was measured using a xenon long life fade meter FAL-25AX-11c manufactured by Suga Test Instruments Co., Ltd.

In addition, changes in color tone were visually observed. Fatigue life (T
Iy□) is the absorbance at the maximum absorption wavelength based on each compound for the spirooxazine compound and chromene or its derivatives, which is 1/2 of the initial absorbance ("ro").
It is expressed as the time required for the temperature to decrease to . However, the absorbance of To and TI/□ is the value obtained by subtracting the absorbance of the unirradiated molded product at the maximum absorption wavelength based on each compound, and the absorbance of To is measured 60 seconds after light irradiation. did.

The results are shown in Table 3.

Examples 2 to 20 Example 1 except that the type and amount of the monomers, spirooxazine compound, chromene or its derivatives used were changed, and polymerization was carried out by known means according to the monomers.
I did the same thing. The results are shown in Table 3.

Example 21 2,2-bis-(4-methacryloyloxyethoxy-
To a composition consisting of 40 parts of 3,5-dibromophenyl)propane and 60 parts of styrene, 0.4 part of the spirooxazine compound of Production Example 1, 0.2 part of the chromene compound of Production Example 18,
Adding 0.6 parts of Sanol LS744 as an ultraviolet stabilizer and part of Perbutyl NDI as a radical polymerization initiator,
Mixed thoroughly.

The obtained mixed solution was polymerized in the same manner as in Example 1 to a thickness of 2
A molded article with a diameter of 7 mm was obtained, and its photochromic properties were measured.

The results are shown in Table 4. In Table 4, the color tone at TI/□ is the color tone at TI/□ of the spirooxazine compound.

Examples 22 to 40 All procedures were carried out except that the amounts and types of monomers, spirooxazine compound, chromene or its derivatives, and ultraviolet stabilizer used in Example 21 were changed, and polymerization was carried out by known means according to the monomers. The same procedure as Example 21 was carried out. The results are shown in Table 4,
Ta.

Example 41 0.8 g of the spirooxazine compound of Production Example 5 and 0.8 g of the chromene compound of Production Example 31 were added to 100 parts by weight of chloroform.
5 g was added and dissolved. This solution was poured into a quartz cell (1c
Example 1
The xenon lamp of the fade meter described in 1 was irradiated with stirring.

As a result of visually observing the change in color tone, it quickly changed from colorless to gray.

Claims (3)

[Claims] (1) (a) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ are respectively optionally substituted aromatic hydrocarbon groups or unsaturated heterocyclic groups , R_1 and R_2 are hydrogen atoms or alkyl groups, R_1 and R_2 may be taken together to form a ring, R_3 is an alkoxycarbonyl alkyl group, R_4, R_5, R_6, R_7 and R_8 is a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogen atom, a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group, and at least one of R_4 and R_5 is a cyano group, a trifluoromethyl group, or an alkoxycarbonyl group. A photochromic composition comprising 100 parts by weight of a spirooxazine compound represented by the following formula and (b) 0.01 to 10,000 parts by weight of chromene or its derivative. (2) (a) Polymer (b) A polymer composition comprising 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.