JPH0439382A - Photochromic composition - Google Patents

Abstract

PURPOSE:To obtain the title composition containing a specific spirooxazine compound and chromene (derivative) at a specific ratio and capable of coloring into various neutral tints such as gray, amber and brawn. CONSTITUTION:The aimed composition obtained by blending (A) 100pts.wt. spirooxazine compound expressed by formula I [formula II and formula III are (substituted)aromatic hydrocarbons or (substituted)unsaturated hetero rings; R1 and R2 are alkyl and at least either one is >=2C alkyl and R1 and R2 may form a ring together; R4 and R5 are H, halogen, hydrocarbon, alkoxy, cyano, halogenoalkyl, (substituted)amino or alkoxycarbonyl] with (B) chromene or derivative thereof, at an amount of the component B of 0.01-10,000pts.wt. (preferably 0.05-1,000pts.wt.) based on the 100pts.wt. component A.

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 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 [I] 0, O1 to 10,000 heavy nail portion.

Component (a) of the photochromic composition of the present invention is a spirooxazine compound represented by spirooxa represented by the general formula (1), and (b) 100 parts by weight of chromene or a derivative thereof are the same or different, and are substituted. is an optionally substituted aromatic hydrocarbon group or an optionally substituted unsaturated heterocyclic group. Specific examples of aromatic hydrocarbon groups include those derived from rings having 6 to 18 carbon atoms, such as one benzene ring, or a condensed ring of 2 to 4 benzene rings, such as a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, etc. Examples include divalent groups.

Further, the above aromatic hydrocarbon group may contain many (5 in total, preferably up to 3vA) substituents. Examples of such substituents include fluorine, chlorine, oxaline, etc. Halogen atom; hydroquine group; cyano group; nitro group; amino group; alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group; methoxy group, ethoxy group, propoxy group, butoxy group, etc. Carbon number 1-2
0 alkoxy group; Aryl group having 6 to 10 carbon atoms such as phenyl group, tolyl group, naphthyl group; Alkylamino group having 1 to 4 carbon atoms such as methylamino group and ethylamino group; Dimethylamino group, diethylamino group, etc. dialkylamino group having 2 to 8 carbon atoms; halogenoalkyl group having 1 to 4 carbon atoms such as trifluoromethyl, thienyl group, furyl group,
An optionally substituted unsaturated heterocyclic group exemplified by a 5- or 6-membered single heterocyclic group containing 1 to 2 sulfur atoms, oxygen atoms, or nitrogen atoms, such as a pyrrolyl group or a pyridyl group Examples include a divalent group derived from a 5-membered ring, a 6-membered ring containing oxygen, sulfur, or a nitrogen atom, or a heterocycle in which a benzene ring is fused thereto. Specifically, nitrogen-containing heterocycles such as pyridine ring, quinoline ring, pyrrole ring, and isodole ring; oxygen-containing heterocycles such as furan ring and benzofuran ring; sulfur-containing heterocycles such as thiophene ring and benzofuran ring, etc. Examples include divalent heterocyclic groups derived from. In particular, when the ring is a two-ring fused heterocycle consisting of a benzene ring and a 5- or 6-membered heterocycle, high color density can be obtained.

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 general formula CI), R1 and R7 are the same or different alkyl groups, and at least one of them is an alkyl group having 2 or more carbon atoms, or
They may join together to form a ring. The alkyl group mentioned above is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the alkyl groups mentioned above include methyl, ethyl, and isopropyl groups. In addition, when R1 and R1 are combined to form a ring, although not particularly limited, a cycloalkyl ring, bicycloalkyl ring, or tricycloalkyl ring having 5 to 10 carbon atoms is generally preferred. More specific examples of these include divalent groups derived from a cyclopentyl ring, a cycloalkyl ring, a cyclohebutyl ring, a norbornane ring, an adamantane ring, and a bicyclo(3,3,l:l nonane ring. These rings may be substituted with a substituent.

Specific examples of the substituent include hydroxy group,
Alkylamino groups having 1 to 4 carbon atoms such as methylamino group and diethylamino group; methoxy group, ethoxy group, tert
- Alcokyne group with 1 to 4 carbon atoms such as butoxy group; aralkoxy group with 7 to 15 carbon atoms such as benzyloxy group, aryloxy group with 6 to 14 carbon atoms such as phenoxy group, 1-naphthoxy group, methyl group, ethyl group lower alkyl group having 1 to 4 carbon atoms such as t-butyl group: halogen atom such as fluorine, chlorine, oxalin, etc. Nidiano group: carbokylene group; alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl group nitrifluoro Halogen-substituted alkyl groups with 1 or 2 carbon atoms such as methyl groups, nitro groups; aryl groups with 6 to 11 carbon atoms such as phenyl groups and tolyl groups, pencil groups,
7 or more carbon atoms such as phenylethyl group and phenylpropyl group
15 aralkyl groups, alkylthio groups having 1 to 4 carbon atoms, etc., and these substituents are not only included as 1-substituted groups, but also polysubstituted groups having 2 to 7 substituents. Furthermore, there is no problem whether the substituents in the polysubstituted product are the same or different, and the position of the substituent can be changed depending on the purpose or use.

One of these R and R2 is an alkyl group having 1 or more carbon atoms, and the other is an alkyl group having 2 or more carbon atoms, or they form a ring together. is essential in order to exhibit good color density in a high temperature range.

In the general formula [11], R3 is a hydrogen atom, a hydrocarbon group,
It is an alkoxycarbonylalkyl group or an anoalkyl group. The hydrocarbon group described above is not particularly limited, but generally includes an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms,
They are an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 14 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, isopropyl, etc., aryl groups include phenyl, naphthyl, etc., and aralkyl groups include benzyl, phenylethyl, phenylpropyl, and naphthyl. Examples include methyl group. 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.
Preferably. The alkylene group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, 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, a butoxycarbonylethyl group, and the like.

In addition, the above cyanoalkyl group is not particularly limited, but
Generally, it is suitable that the number of carbon atoms is 1 to 10, preferably 1 to 4. Specific examples of this cyanoalkyl group include a cyanomethyl group, a cyanoethyl group, and a cyanopropyl group.

In the general formula CI), R4 and R5 are 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.

The above hydrocarbon group is not particularly limited, but the hydrocarbon group described above for R2 is suitable.

The alkoxy group mentioned above is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, methoxy group, ethoxy group, solobo, 1
- group, butoxy;
Chlorine, bromine, etc., and the alkyl group preferably has 1 to 4 carbon atoms. Specific examples include trifluoromethyl group, trichloromethyl group, and tribromomethyl group.

In the amino group or substituted amino group, the general formula and R7 are preferably the same or different hydrogen atoms; a hydrocarbon group such as an alkyl group, an aralkyl group, or an aryl group. The same hydrocarbon group as shown for R8 above is preferably used.

In this case, R8 is an alkylene group such as a tetramethylene group or a pentamethylene group; CIIzC110CII□-CIIzUCIItC! I
tC11zCIIzOCII□CI+, -1-CI+
20 (oxyalkylene group such as CI! 2-'n; -C11xSCllzCIIt Cl1tS
(Cllzt'T, -C11, ClI23CII2C1
12-Thioalkylea groups such as CIIJCIIxCII
t cl12N(cll!tr, CllxCt
An azoalkylene group such as bNCIItCIl- is preferred.

The alkoxycarbonyl group mentioned above is not particularly limited, but
Generally, it is suitable that the number of carbon atoms is I to 5, preferably 1 to 3. More specific examples of this alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

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. Further, as the chromene derivative, the above-mentioned compound having the .n-category of chromene can be employed without any restriction. In the present invention, a chromene derivative represented by the following formula (A) is particularly preferably used because it has excellent photochromic properties.

RI' is an alkylene group or +0-R''9- (however, R1
is an alkylene group, and n is a positive integer. ), and R1 and R7 are hydrocarbon groups having the same or different alkyl groups and unsaturated heterocyclic groups, and are employed without any of the above general limitations.

may be substituted with one or two or more heterocyclic groups such as thienyl group, furyl group or pyrrolyl group.Next, in the general formula [A], represented by R', R1, R' and R4 The hydrocarbon group and substituted amino group are R1 of the spirooxazine compound represented by the above general formula [1].
The same hydrocarbon groups and substituted amino groups as described for and Ri are employed.

Furthermore, in the general formula (A), R1 and R2 may be taken together to form a ring, and in this case, the ring described for R1 and R1 in the general formula (1) is the same as the ring described for R1 and R1 in the general formula (1). It will be adopted without any restrictions.

A ring is preferable because the coloring density is high.

Among these, compounds in which rings are condensed at the 7- and 8-positions of the chromene skeleton are more preferred. Furthermore, in the general formula (A), R1 and R
When 1 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 , chromene or its derivative was added in an amount of 0.00% per 100 heavy weight parts of the spirooxazine compound. O1 to toooo parts by weight, preferably o
, os to 100 parts by weight.

By dispersing the photochromic composition 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. Ethyl acid, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly(2-hydroxyethyl methacrylate),
Examples include 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 divinylbenzene or each of these monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, 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 radically polymerizable polyfunctional monomers such as vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, and bromostyrene; furthermore, ethanedithiol, propanetriol, hexanedithiol, pentaerythritol tetrakisthioglycolate , addition copolymers of polyvalent thiol compounds such as di(2-mercaptoethyl) ether and the above-mentioned radically polymerizable polyfunctional monomers; polyvalent isocyanate compounds such as diphenylethane diisocyanate, xylene diisocyanate, p-phenylene diisocyanate, etc. and polyhydric alcohol compounds such as ethylene glycol, trimethylolpropane, pentaerythritol, and bisphenol A, or the above-mentioned polyhydric thiol compounds. These raw material monomers 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 monomer 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 UV stabilizer, any known UV stabilizer added to various plastics can be used without any limitations.

In the present invention, considering the improvement in the durability of the photochromic compound, among various UV stabilizers, -heavyt oxygen quenchers, hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants are preferred. used. A more specific example of these UV stabilizers is Sheasorb UV 1084. Sheasorb 33
46 (manufactured by American Cyanamid Company); UV-
Check AM 101. UV-Chek AM105 (manufactured by FerroCorporation Co., Ltd.); Irgastab 200
2. Tinuvin 765° Tinuvin 144. Kimasorbu 9
44. Tinuvin 622° Irganox 1010. Irganox 245 (manufactured by Ciba Geigy); Lilex NBC (manufactured by DuPont); Sanol LS-1
114, Sanol LS744, Sanol LS-26
26 (manufactured by Sankyo Company); Sumilizer GA-80,
Sumilizer GM, Sumilizer BBM-3, Sumilizer WX-R, Sumilizer S, Sumilizer BIT,
Sumilizer TP-D, Sumilizer TPL-R, Sumilizer TPS, Sumilizer MB (manufactured by Sumitomo Chemical Co., Ltd.); Mark A (II-50° Mark AO-20, Mark AO-30, Mark 80-330° Mark 80 -2
3, Mark LA-82, Mark LA-87 (manufactured by Adeka Argus); Antioxidant) HPM-1
2 (S, F, 0.S, manufactured by the company), etc. Note that all the above names are product 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 by sunlight or light containing ultraviolet rays such as light from a mercury lamp, and this change is reversible. It shows excellent dimming properties. 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 can also be used as a material for photochromic lens materials, optical filter materials, display materials, photometers, decorations, and the like.

(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 cz-st: chlorstyrene ・TMP-TAC: )limethylolpropane triallyl carbonate ・BADBP: 2,2-bis( 4-Allyl carbonate ethoxy-3,5-dibromophenyl)propane/ADC: Allyl diglycol carbonate/DAP
Nidialyl phthalate, St: Styrene, DCIPF Nidi(2-chloroisopropyl) fumarate, EGDMA: Ethylene glycol dimethacrylate, PETTP: Pentaerythritol tetrakis (β-thiopropionate), DME Nidi(2-mercaptoethyl)ether, DVB Ni Divinylbenzene-xic: xylylene diisocyanate/HPA
: 3-(2,4-dibromophenoxy)2-
Hydroxypropyl acrylate/MMA: Methyl methacrylate/DECDMA
Nidiethylene glycol dimethacrylate/TBBM: 3.4.5-tribromobenzyl methacrylate-IIEMA: 2-hydroxyethyl methacrylate/BMA: Benzyl methacrylate/IPP
Nidiisopropyl peroxycarbonate/barbutyl ND: (Nippon Oil & Fats Corporation) t-butyl peroxy-2-hexanate/BPO: Benzoyl peroxide/Sanol LS-744 (Product name: Sankyo Co., Ltd.) ns MARK L A, -82 (Product name: Manufactured by Adeka Argus) MARK L A -87 (Product name: Manufactured by Adeka Argus) ・Irganox (Product name: Manufactured by Ciba Geigy) Cyasorb U V 1084 (Product Sanol LS-2626 (Product name: manufactured by Sankyo Corporation) - Sumilizer A-80 (Product name: manufactured by Sumitomo Chemical Co., Ltd.) - Tinuvfn (Product name: Manufactured by Ciba Geigy Co., Ltd.) ) UV-Chek A Mot (Product name: Manufactured by Ferro Corporation) ・MARK A O-20 (Product name: Manufactured by Near Deca Argus Company) Writing Nord t, s-1114 (Product name: Manufactured by Sankyosha) (:Ih If υ■ ・Sumilizer '!' I) -D (Product name: Manufactured by Sumitomo Chemical) (LsC+ *5CII*CHzCOOC11g) *C
Production Example 1 2.01g (0,0059mol) of the compound of the following formula and Compound 1 of the following formula
, 02 g (0,0059a+ol) and 0.43 g (0,006 mo 1 ) of pyrrolidine were dissolved in 50-ethyl alcohol and heated under reflux for 2 hours.

After the reaction, the solvent was removed and the mixture was purified by chromatography on silica gel to obtain spirooxazine compound 400 of the following formula.

The elemental analysis value of this compound is C81, 35%, 86.60
%, N 7.62%, 04.43%, Cts
CB1.49%, which is the calculated value for ll□N20,
86.57%, N 7.60%, and 04.34%. In addition, when proton nuclear magnetic resonance spectra were measured, δ6.5 to 8. Based on the protons of the naphthalene ring, the protons of the indoline ring, and the protons of the oxazine ring near Oppm, the peak of <IIH, 62.8
Based on the proton of the N-CHI bond in the vicinity of ppm <3
H peak, δ 1.3-2. A broad peak of <1ull based on the proton of the cyclohexane ring was shown near Oppm.

Furthermore, when the 13C-nuclear magnetic resonance spectrum was measured, peaks based on the carbons of the benzene ring, naphthalene ring, and oxazine ring of indoline were observed around δ 100 to 160 ppm, and peaks based on the spiro carbons were found around δ OD ppm and δ 5 G ppm at 2.620 to 160 ppm. A peak based on carbon of cyclohexane group and methyl group was shown around 35 ppm.

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

Production Example 2 Spirooxazine compound 200■ of the following formula was obtained by purification by the following compound mudgraphy.

2. Og (0,0057moj'), the following compound i1 0.98g (0,0057n+o1) and 0.41g of pyrrolidine (0°0057mol!) were dissolved in 50ml of ethyl alcohol and heated under reflux for 2 hours. .

After the reaction, the solvent was removed and the elemental analysis of this compound on silica gel was C78.66%, i(6.09%, N
11.05%, 04.2%, and C, +1.
.

Calculated value for NsO C 78.71%, if
6.08%, N 11.02%, and 04.2%. In addition, when proton nuclear magnetic resonance spectra were measured, a peak of <10) 1 based on protons of the quinoline ring, protons of the indoline ring, and protons of the oxazine ring was observed near δ6.5 to 9ppIrl, and a peak of δ2.7p
3F1 based on the proton of N-CHI bond near pm
, and a broad peak of <10) based on the proton of the norbornane ring around δ 1.3 to 2.5 ppm.

Furthermore, when we measured the IC-nuclear magnetic resonance spectrum, we found that
Peaks based on the carbons of the benzene ring, quinoline ring, and oxazine ring of indoline were shown around 6100 to δ16Uppm, peaks based on the spiro carbons were shown around δ99ppm and 652ppm, and peaks based on the carbons of the norbornane ring were shown around δ27 to 52ppm. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (2).

Production Examples 3-25 The spirooxazine compounds shown in Table 1 were synthesized in the same manner as in Examples 1-2.

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 26 1-hydroxy-2-acetonaphthone lOg (0,05
4moi') and Norkampfy -6,6g (0,06
mo1) and pyrrolidine 8 g (0,113 mof)
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. By heating 7.47 g of this chromanol compound with 4.5 g of anhydrous sulfuric acid steel at 150 to 160°C for 10 minutes in a carbon dioxide stream and purifying the brown viscous liquid by chromatography on silica gel, the following formula 6.3 g of chromene derivative was obtained.

The elemental analysis values of this compound are CH6,93%, H6,8
9%, 06.18% and C+ s tl. The calculated value for 0 is 6C87.02%, HG, 87%, 06
．． It was in very good agreement with 12%. In addition, when proton nuclear magnetic resonance spectra were measured, δ7.2-8.3p
A <6H peak based on the naphthalene ring proton near pm, a <2H peak based on the alkene proton near δ5.6 to 6.7 ppm, and a <2H peak based on the proton of the norbornylidene group around 2 to 2.5 ppm. showed a broad peak of <IOH. Furthermore, when a nuclear magnetic resonance spectrum was measured from 13C to
A peak based on the carbon of the naphthalene ring near 0 ppm, 6
A peak based on the carbon of the alkene appears around 80 to 110 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (26).

Production example 27 1-acetyl-2-naphthol lOg (0,0545
ol) and Bisik o (3,3,13 nonan-9-one 8
．． 29 g (0.06 mo1) and 8.7 g of morpholine
(0,10SO1) was dissolved in 300 cc of 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 200 cc of methanol, and lithium aluminum hydride was added to obtain a chromanol compound. This chromanol compound 6.49
170-18 g with anhydrous copper sulfate in a stream of carbon dioxide.
After heating at 0° C. for 10 minutes, the brown viscous liquid was purified by chromatography on silica gel to obtain 5.8 g of a chromene derivative of the following formula.

The elemental analysis values of this compound are C86,81%, H7,6
2%, 05.57%, which is the calculated value for Cx+Ilt*O C 87.90%, H7, 59%, 05
．． The proton nuclear magnetic resonance spectrum was measured to be 67.2-8.39.
Based on the proton of the naphthalene ring near 1 m < 6) 1
peak, δ6.0-7. Peak of (2■) based on alkene proton near Oppm, 61.2-2.5p
A broad peak of 14H based on the proton of the bicyclo(3,3,1)9-nonylidene group was observed near pm.

Furthermore, when we measured the 3C-nuclear magnetic resonance spectrum, we found that
Bisik o C3,3,1) around 627-52ppm
Peak based on carbon of 9-nonylidene group, δ 110 ~
A peak based on the carbon of the naphthalene ring appears around 160 ppm, and a peak based on the carbon of the alkene appears around 680 to 11Oppm. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (27).

Production Example 28 3.06 g of chromanone compound represented by the following formula (n,
111mp e) in 50 cc of anhydrous ether, cool the solution to 0°C, and add freshly prepared Grignard reagent C! in 50 cc of anhydrous ether. ItMgCl (0,012sol
) 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 chromanol compound was then heated at 200°C for about 10 minutes with anhydrous copper sulfate in a stream of carbon dioxide, and a brown viscous liquid was produced by chromatography on silica gel to obtain 2.47 g of a chromene derivative of the following formula. Ta.

As in Production Example 26, elemental analysis, proton nuclear magnetic resonance spectrum, and 13C-nuclear magnetic resonance spectrum measurements confirmed that this compound was the compound represented by the above structural formula (28).

Production example 29 1-acetyl-2-naphthol log (0,054
+t+o l ) and Norkampf y −6,(ig (0
,06mof) and molpoline 8.7g (0,lOm
ol) was 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 with acetone to obtain 7.53 g of a compound represented by the following formula.

Next, 7.53 g of this compound was mixed with 100 c of methanol.
By dissolving in c and reacting with methyl iodide,
6.95 g of a chromanone compound represented by the following formula was obtained.

Next, the generated chromanone compound was converted into a chromanol compound in the same manner as in Production Example 28, a dehydration reaction was performed, and after separation and purification, a chromene derivative 5.84 of the following formula was obtained.
I got g.

Similarly to Production Example 26, this compound was confirmed to be a compound represented by the above structural formula (29) by elemental analysis, proton nuclear magnetic resonance spectrum, and IC-nuclear magnetic resonance spectrum measurements.

Production Example 30 10 g (0,0318 moi') of 5-n-octyloxy-1-hydroxy-2-acetonaphthone, 2,77 g (0,0477 moi) of acetone, and 1.13 g (0,59 moi) of pyrrolidine were added to toluene. A solution of 100ml was prepared. 1 of this mixture
It was boiled for 0 hours and the water was separated. After the reaction is complete, toluene is removed under reduced pressure, the remaining chromanone compound is dissolved in methanol+00i, and sodium borohydride is gradually added to dissolve the chromanol compound! I strained it. This chromanol compound6. Og to anhydrous copper sulfate 4 in a carbon dioxide stream
．． By heating at 150-160° C. for 10 minutes with 0 g and purification of the brown viscous liquid by chromatography on silica gel, chromene derivatives of formula 3.
8g was obtained.

As in Production Example 26, it was confirmed by elemental analysis, proton nuclear magnetic resonance spectrum, and 1C-nuclear magnetic resonance spectrum that this compound was a compound represented by the above structural formula (30).

Production Examples 31-39 The chromene derivatives shown in Table 2 were synthesized in the same manner as Production Examples 26-30.

As a result of structural analysis of the obtained product using the same structural confirmation method as in Production Example 26, 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 26 were added to a composition consisting of 70 parts of chlorstyrene and 30 parts of 2,2-bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane. chromene derivative of 0.2
1 part of Barbutyl ND as a radical polymerization initiator was added thereto, 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. over 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 from the air oven, and after cooling, the polymer was removed from the glass mold. Obtained thickness 2
The fatigue life of the molded product I 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
17. ) is expressed as the time required for the absorbance at the maximum absorption wavelength to decrease to 1/2 of the initial absorbance (To) based on each compound for spirooxazine compounds and chromene or its derivatives.

However, To and T1/! The absorbance of T is the value obtained by subtracting the absorbance of the unirradiated molded article at the maximum absorption wavelength based on each compound, and the absorbance of T was measured 60 seconds after light irradiation.

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-
0.4 parts of the spirooxazine compound of Production Example 2I, 0.2 parts of the chromene compound of Production Example 26, and Sanol LS-744 as an ultraviolet stabilizer were added to a composition consisting of 4υ parts of 3,5-dibromophenyl)propane and 60 parts of styrene. and 1 part of Perbutyl ND as a radical polymerization initiator were added and thoroughly mixed.

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

The results are shown in Table 4. In Table 4, the color tone at T, 72 is the color tone at T1/2 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.

Show the results in Table 4.

Example 41 0.8 g of the subiroxazine compound of Production Example I and 0.8 g of the chromene compound of Production Example 31 were added to the heavy nail part of chloroform 10 ().
．． 5g was added and dissolved. This solution was poured into a quartz cell (1c
1 cm x 4 cm) and irradiated with the xenon lamp of the fade meter described in Example 1 while 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. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ are the same or different, respectively.
It is an optionally substituted aromatic hydrocarbon group or an optionally substituted unsaturated heterocyclic group, and R_1 and R_2 are the same or different alkyl groups, and at least one of them has 2 or more carbon atoms. It is an alkyl group, or these may be taken together to form a ring, R_3 is a hydrogen atom, a hydrocarbon group, an alkoxycarbonylalkyl group, or a cyanoalkyl group, and R_4 and R_5 are each the same or a different hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, cyano group, halogenoalkyl group, amino group, substituted amino group or alkoxycarbonyl group. ] A polymer composition comprising 100 parts by weight of a spirooxazine compound represented by the following and 0.01 to 10,000 parts by weight of (b) chromene or a derivative thereof. (2) A photochromic composition comprising (a) 100 parts by weight of a polymer, and (b) 0.001 to 20 parts by weight of the photochromic composition described in 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.