JPH0523315B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photochromic composition having a photochromic effect and having good durability. (Prior art and its problems) Photochromism is a phenomenon that has attracted attention over the past few years. Photochromism is a phenomenon in which when a certain compound is irradiated with light containing ultraviolet rays, such as sunlight or light from a mercury lamp, the color immediately changes. This is a reversible effect in which the color returns to its original color when you stop exposing it to light and place it in a dark place. Compounds having this property are called photochromic compounds, and various compounds have been synthesized to date, but no particular common structure has been recognized. In recent years, among these various photochromic compounds, the following general formula [during the ceremony]

[Formula] represents a substituted or unsubstituted adamantylidene group, R' represents hydrogen, an aryl group, an arylalkyl group, or a heterocyclic group, and X' represents oxygen or N-R'' (where R'' is hydrogen, an aryl group, an alkyl group, or an arylalkyl group),

[Formula] represents an aromatic group or an unsaturated heterocyclic group. The fulgide compounds represented by ] are known as a series of photochromic compounds that absorb ultraviolet light and become colored, and have high photosensitivity that rapidly returns to white light. However, such compounds tend to revert to a colorless form under white light and therefore exhibit no or little coloration in sunlight. It is known that the above-mentioned fulgide compound becomes a photochromic compound having the following structure that is colored by sunlight when heated or irradiated with ultraviolet light (Japanese Patent Application Laid-Open No. 155179/1982). (in the formula

[Formula] R′, X′ and

[Formula] is the same as above) The above photochromic compound has a rigid, unstrained cage-shaped adamantylidene group, which weakens the single bonds that form part of the six-membered ring, allowing it to be exposed to sunlight. It is believed that this facilitates electron cyclic ring opening, resulting in colored forms. However, probably due to its bulky adamantylidene group, the colored form is relatively stable and the rate of discoloration due to ambient temperature is not very fast. the result,
This photochromic compound has the disadvantage of poor reversible durability. In order to improve the durability of the photochromic compounds described above, the present inventors have discovered and already proposed a novel photochromic compound represented by the general formula shown below (Japanese Patent Application No. 133370/1982). [During the ceremony,

[Formula] represents a substituted or unsubstituted norbornylidene group, R' represents hydrogen, an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic group, and X' represents oxygen or N
-R″ (where R″ is hydrogen, an aryl group, an alkyl group, or an arylalkyl group);

[Formula] represents an aromatic group or an unsaturated heterocyclic group. ] The photochromic compound represented by the above general formula shows excellent reversible durability, but in order to expand the uses of photochromic products and extend their useful life (life), this reversible durability is required. needs to be further improved. (Means for Solving the Problem) As a result of intensive research to further improve the durability of the photochromic compound described above, the present inventors have found that it becomes colorless when exposed to light containing ultraviolet light such as sunlight or light from a mercury lamp. We have succeeded in synthesizing a photochromic compound that changes from an amorphous to a colored or darkly colored form, is reversible, and exhibits excellent durability. As a result of further research, the present inventors discovered that a more durable photochromic composition could be obtained by combining the photochromic compound described above with an ultraviolet stabilizer. I came up with a proposal. That is _{, the} present invention is based on the general _formula ( ₎ ), (C), (D) or (E), and R is a divalent organic group. (However, in formulas (A) to (E),

[Formula] is a phenyl group, a thienyl group, which may be substituted, respectively.
a furanyl group, pyrrolyl group, benzothienyl group, benzofuranyl group or indolyl group,

[Formula] is substituted or unsubstituted norborni It is a lidene group,

[Formula] is a substituted or unsubstituted adamantylidene group, R ₁ is an alkyl group or an aryl group, R ₂ is a hydrogen atom or an alkyl group, and R ₃ and R ₄ are an alkyl group or an aryl group. be. )] This is a photochromic composition characterized by comprising a fulgimide compound represented by the following formula and an ultraviolet light stabilizer. The fulgimide compound represented by the above general formula () is a new compound. (A), (B), (C) in the explanation of the above general formula (),
of the groups represented by (A) and (E)

[Formula] is a phenyl group, thienyl group, furanyl group, pyrrolyl group, benzothienyl group, benzofuranyl group or indolyl group, which may each be substituted. The substituent is particularly preferably an alkyl group, an alkoxy group, a nitro group, a phenyl group or a halogen group, and 1
One or more substitutions may be made. Next, the groups represented by (A), (B), (C), (A) and (E) above are

[Formula] is norbornylidene group

[Formula] or a substituted norbornylidene group, and is not particularly limited as long as it undergoes the Stoppe reaction. Specific examples of the substituent include, for example, hydroxy group; substituted amino groups such as methylamino group and diethylamino group; methoxy group; alkoxy groups having 1 to 4 carbon atoms such as ethoxy group and tert-butoxy group; benzyloxy group, etc. Arylalkoxy groups having 7 to 15 carbon atoms; Aryloxy groups having 6 to 14 carbon atoms such as phenoxy and 1-naphthoxy groups; 1 to 1 carbon atoms such as methyl, ethyl, and t-butyl groups
Lower alkyl group of 4; halogen atom such as fluorine, chlorine, silium; cyano group; carboxyl group; alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl; Halogen-substituted alkyl groups; examples include nitro groups, and these substituents are not only included as monosubstituted groups, but may also be included as polysubstituted groups having two or more substituents. Furthermore, there is no problem whether the substituents in the polysubstituted product are the same or different, and the positions of the substituents can be changed depending on the purpose or use. Next, the groups represented by (A), (B), (C), (D) and (E) above are

[Formula] is an adamantylidene group

[Formula] or a substituted adamantylidene group. As the substituent for the substituted adamantylidene group, the substituents described above for the substituted norbornylidene group can be used without any restrictions. Furthermore, R ₁ , R ₃ and R ₄ of the groups represented by (A), (B), (C), (D) and (E) are each an alkyl group or an aryl group. Moreover, R ₂ is a hydrogen atom or an alkyl group. The alkyl group mentioned above is not particularly limited, but generally an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, is suitably used. More specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, etc., and as an aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are preferable. X ₁ in the fulgimide compound of the present invention represented by the general formula () is a group represented by (A) or (B) described above, and X ₂ is a group represented by (A), (B), or (C) described above. ), (D) or
This is a group represented by (E). Further, R in the general formula () can be used without any restriction as long as it is a divalent organic group capable of connecting X ₁ and X ₂ . Examples include an alkylene group, an alkylidene group, an arylene group, or a group consisting of these groups and an oxy group, a carbonyl group, an oxycarbonyl group, a carbonate group, or an iminocarbonyl group. The number of carbon atoms in the above alkylene group, alkylidene group, and arylene group is not particularly limited, but for reasons such as ease of obtaining raw materials, the number of carbon atoms is 1 to 10 for alkylene groups and alkylidene groups, and 6 for arylene groups. -18 is preferred. Preferred alkylene groups in the present invention include:
Methylene group, ethylene group, trimethylene group, tetramethylene group, propylene group, butylene group, 2,
Examples of the alkylidene group include a 2-dimethyltrimethylene group, and examples of the alkylidene group include an ethylidene group, a propylidene group, and an isopropylidene group. Examples of the arylene group include a phenylene group, a diphenylene group, a naphthalene group, an anthracene group, a benzylene group, a phenylethylene group, and a phenylpropylene group. The general formula of the preferable R in the present invention is as follows. [However, A is -O-,

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[Formula] or

[Formula], R ₅ and R ₆ are the same or different hydrogen atoms or alkyl groups, and k, l, m and n are each an integer of 0 or more. ] The alkyl groups described above are suitable as the alkyl groups represented by R ₅ and R ₆ in the above formula. Also,
k and n are integers from 0 to 10, l and m are from 0 to
Preferably, it is an integer of 2. In the fulgimide compound represented by the above general formula (), in consideration of the durability of the photochromic action described below, in the above general formula (), X ₂ is a group represented by (C), (D) or (E). It is preferable. Furthermore, R ₂ of the group represented by (C), (D) or (E) is preferably an alkyl group. The fulgimide compound represented by the above-mentioned general formula () generally exists as a pale yellow solid at room temperature, and can generally be identified as a compound of the general formula () by the following methods (a) to (c). Can be confirmed. (a) Proton nuclear magnetic resonance spectrum (H ¹ −
By measuring NMR, we can determine the type and number of protons present in a molecule. In other words, there is a peak based on aromatic protons around δ7~8ppm, and a peak based on aromatic protons around δ1.2~2.5ppm.
A broad peak based on protons derived from the norbornylidene group or adamantylidene group appears in the vicinity, and a peak based on the alkyl groups of R ¹ , R ² , R ³ and R ⁴ appears around δ1.2 to 4.0 ppm. Also,
By relatively comparing the respective δ peak intensities, the number of protons in each bonding group can be determined. (b) The weight percentages of carbon, hydrogen, nitrogen, sulfur, and halogen can be determined by elemental analysis. Furthermore, the sum of the weight percent of each recognized element is
By subtracting from 100, the weight percent of oxygen can be calculated. The composition of the corresponding product can therefore be determined. (c) ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C-NMR)
By measuring , the type of carbon present in the molecule can be determined. Peak derived from carbon of norbornylidene group or adamantylidene group around δ27~52ppm, peak around δ15~35ppm
A peak based on the carbon of the alkyl group of R ₁ , R ₂ , R ₃ , R ₄ , a peak based on the carbon of the aromatic hydrocarbon group or unsaturated heterocyclic group around δ110 to 150 ppm,
A peak based on carbon of C=O appears around δ160 to 170 ppm. The method for producing the compound represented by the general formula () is as follows:
It is not particularly limited and may be obtained by any synthesis method. Representative methods that are generally suitably adopted will be explained below. A fulgide compound represented by the following formula (a) alone or a mixture of this and a fulgide compound represented by the following formula (b), (c), (d) or (e), or a fulgide compound represented by the following formula (b) fulgide compound alone or together with the following formula (c),
A mixture with the fulgide compound shown in (d) or (e), (However, in formulas (a) to (e),

【formula】

【formula】

[Formula] R ₁ , R ₂ , R ₃ and R ₄ are the same as in formulas (A) to (E) above, and R ₂ ' is an alkyl group. ) This method involves reacting with a diamine and then carrying out a cyclization reaction. As the raw material fulgide compound, the above general formula (a) is used.
Or, it is necessary to use the compound shown in (b). The compounds represented by the above general formula (a) or (b) may be used alone or in combination. Furthermore, it is a preferred embodiment to use a mixture of the compound represented by the above general formula (a) or (b) and the compound represented by the general formula (c), (d) or (e).
When using a mixture of different types of compounds as the raw material fulgimide compound, the mixing ratio is not particularly limited, but in order to make X ₁ and X ₂ in the general formula () of the obtained fulgimide compound have different structures, , the mixing ratio of different fulgide compounds is 1/2 to 2.
(molar ratio), particularly preferably within the same molar range. The diamine used as the other raw material is not limited to any known compound and is represented by the following formula (f) H ₂ N-R-NH ₂ (f) (where R is a divalent organic group). A compound is used. General formula (f) above
Among these, as R, the groups described in the above general formula () are particularly preferably used from the viewpoint of ease of synthesis and availability of diamine. The ratio of the above-mentioned fulgide compound and diamine to be used may be adopted from a wide range and is not particularly limited. In general, from the viewpoint of the yield of the fulgimide compound obtained, fulgide compound: diamine =
It is preferable to select from the range of 1:1 to 10:1. As the solvent used in the above reaction, polar aprotic solvents such as N-methylpyrrolidone, dimethylformamide, toluene, and tetrahydrofuran are preferably used. The above reaction is usually carried out at a temperature of 25 to 160°C and for a period of 1 to 24 hours. After the reaction is complete,
The above-mentioned fulgimide compound can be obtained by removing the solvent, dehydrating with a dehydrating agent such as acetyl chloride or acetic anhydride, and further performing a cyclization reaction on the obtained compound. For the above-mentioned cyclization reaction, for example, heating at 160 to 220°C, a combination of heating and ultraviolet irradiation, or contacting with a Lewis acid catalyst are suitably employed. As the Lewis acid catalyst, known compounds such as SnCl ₄ , TiCl ₄ ,
SbCl ₅ , AlCl ₃ and the like can be used without any restrictions. The amount of Lewis acid catalyst used is also not particularly limited, but it is usually
It is preferable to use it in a range of 0.001 to 1 mol. In the present invention, in addition to the fulgimide compound represented by the general formula [], the following general formula [],
It is preferable to use at least one of the compounds represented by [ ] and [ ] because the resulting photochromic composition will have better durability. [However, in the above formulas (), () and (), R ₁ ,
_R2 , _R3 , _R4 ,

【formula】

[Formula] and

[Formula] is the same as the above general formula (), and X is an oxygen atom or N-R ₇ (However, R ₇ is a substituted or unsubstituted hydrocarbon group.)] The above general formula [], [] The hydrocarbon group represented by R ₇ in and [] is already R ₃ in the general formula []
and each group explained for R ₄ . The blending ratio of the compound represented by these general formulas [], [] and [] and the fulgimide compound represented by general formula [] is not particularly limited, and the former: the latter = 1:100 to 100: 1 can be selected from a wide range, but from the viewpoint of improving the durability of the resulting photochromic composition, the former: the latter =
A range of 1:10 to 10:1 is particularly preferred. Next, another component of the photochromic composition of the present invention is a UV stabilizer. As the ultraviolet stabilizer, any known ultraviolet stabilizer added to various plastics can be used without any limitation.
In the present invention, in view of improving the durability of the resulting photochromic composition, among various UV stabilizers, singlet oxygen quenchers and hindered amine light stabilizers can be particularly preferably used. The singlet oxygen quencher preferably used in the present invention includes a complex of Ni ⁺² and an organic ligand, cobalt()-tris-di-n-butyldithiocarbamate, iron()- Examples include diisopropyldithiocarbamate and cobalt()-diisopropyldithiocarbamate. Among these singlet oxygen quenchers, a complex of Ni ⁺² and an organic ligand is particularly preferred. Specific examples of such complexes are as follows. [2,2'-thiobis(4-(1,1,3,3-tetramethylbutyl)phenolato)butylamine]
Nickel, Nickel-bis[O-ethyl (3,5-di-
tert-butyl-4-hydroxybenzyl)] phosphonate, nickel-dibutyldithiocarbamate, Bis[2,2'-thiobis-4-(1,1,3,
3-Tetramethylbutyl) phenolate] Nickel Other UV-
Mention may be made of the Ni complexes which are commercially available under the trade names CHIEKU AM105, UV-CHEKU 126 and UV CHIEKU AM205. Further, specific examples of the aforementioned hindered amine light stabilizers suitable as ultraviolet stabilizers are as follows. (C ₂₆ H ₅₂ N ₄ ) _n (NU) (However, the above formulas (E), (F), (G), (CH), (RI) and (NU)
During,
R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are alkyl groups, R ³ and R ⁸ are hydrogen atoms or alkyl groups, and m and n are positive integers. ) Among the above (e), (f), (g), (ch), (li) and (n), the alkyl group is not particularly limited by the number of carbon atoms, but in general, the ease of obtaining these compounds For reasons such as 1
It is preferably in the range of ~12. Furthermore, as a hindered amine light stabilizer,
Sumisorb LS-2000 and LS- manufactured by Sumitomo Chemical Co., Ltd.
2001 (both are product names). Among the ultraviolet stabilizers described above, the compounds that can be particularly preferably used as compounds for improving the durability of the photochromic action of the fulgimide compound represented by the general formula () are the compounds represented by the general formula (A),
These are each ultraviolet stabilizer represented by (c), (e), (f), (ch), and (li). The blending ratio of the fulgimide compound represented by the above general formula () and the above ultraviolet stabilizer can be selected from a wide range, but considering the durability of the generally obtained photochromic composition and the elution of the components, the fulgimide compound 100% by weight 0.01 to 10,000 parts by weight of UV stabilizer, more preferably
The amount is preferably 50 to 400 parts by weight. The photochromic composition of the present invention can satisfactorily exhibit the desired photochromic function as described above by being uniformly dispersed not only in a glass matrix but also in various polymer matrices. The synthetic resin of the polymer matrix used in which the photochromic composition of the present invention is dispersed may be any resin in which the compound represented by the general formula () is uniformly dispersed, and optically preferably, for example, polyester is used. methyl acrylate,
Polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly(2-hydroxyethyl methacrylate), polydimethylsiloxane, polycarbonate, poly(allyl diglycol carbonate), etc. Polymers or polymers formed by copolymerizing the monomers forming these polymers with each other or with other monomers are preferably used. The amount of the photochromic composition of the present invention dispersed in such a resin is 0.001 to 70 parts by weight, preferably 0.005 to 30 parts by weight, and more preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the resin. be. (Effects) As explained above, the photochromic composition obtained by the present invention can be colored from colorless to colored by sunlight or light containing ultraviolet light such as mercury lamp light by uniformly dispersing it in various resins. Alternatively, it changes to a darker color, and this change is reversible and has excellent dimming properties. In addition, the present invention provides the following method, by adding and using a compound represented by the general formula [], [] or [] in combination with the above ultraviolet stabilizer,
The reversible durability of the fulgimide compound of general formula () can be dramatically improved due to their synergistic effect. Therefore, the photochromic composition of the present invention
It can be used in a wide range of fields, for example, as a variety of recording materials in place of silver salt photosensitive materials, photographic materials, photoreceptors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, and the like. others,
The photochromic composition of the present invention can also be used as a material for photochromic lenses, optical filter materials, display materials, photometers, decorations, and the like. For example, when used in a photochromic lens, there are no particular restrictions as long as the method can obtain uniform dimming performance, and specific examples include:
There is a method of sandwiching a polymer film in which a fulgimide compound represented by the above general formula () and the above ultraviolet absorber are uniformly dispersed in a lens. At this time, a compound of general formula (), (), or () may be added as a mixture, if necessary. Alternatively, the photochromic composition described above is dispersed in silicone oil and impregnated onto the lens surface at 200° C. for 15 minutes, for example.
Furthermore, there is a method of coating the surface with a curable substance to make a photochromic lens. There is also a method of applying the above-mentioned polymer film to the lens surface and coating the surface with a curable substance to make a photochromic lens. (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. Note that parts in the examples indicate parts by weight. In addition, the ultraviolet stabilizer used in the following examples is the following compound. ●Cyasord UV1084 (Product name: American Cyanamid Company) ●Irgastab 2002 (Product name: Ciba Geigy) ●Rylex NBC (Product name: Manufactured by Dupont) ●UV-Chek AM101 (Product name: Manufactured by Ferro Corporation) ●UV-Chek AM105 (Product name: Manufactured by Ferro Corporation) ●Tinuvin 765 (Product name: Manufactured by Ciba Geigy) ●Tinuvin 144 (Product name: Manufactured by Ciba Geigy) ●Chimassorb 944 (Product name: Ciba Geigy) ●Cyasorb 3346 (Product name: American Cyanamid Company) ●Tinuvin 622 (Product name: Manufactured by Ciba Geigy) ●Spinuvex A-36 (Product name: BorgWarner) C ₂₆ H ₅₂ N ₄ Production example 1 11 g of (5-brom-3-thienyl)ethylidene-2-norbornylidene succinic anhydride of the following formula
(0.03mol) and 2 g (0.01 mol) of ethylene dianiline were dissolved in N-methylpyrrolidone and heated at 100°C under a nitrogen atmosphere.
It was heated for 6 hours. After the reaction, the solvent was removed, the solution was dissolved in acetyl chloride, and the mixture was refluxed for 1 hour for cyclization. By refluxing the obtained compound in O-dichlorobenzene for 6 hours, it was rearranged to the following fulgimide compound (1). The compound was purified by chromatography on silica gel using benzene and ether as eluent and was obtained in 23% yield as yellow needles (melting point 151-153 °C) from chloroform and hexane. . The elemental analysis values of this compound are C62.93%, H4.50%, N2.92%, O6.65%,
S6.31%, _{Br16.69%, and the calculated values for C50H42N2S2Br2 are C62.90} %, _H4.43 %, _N2.93
%, O6.70%, S6.30%, and Br16.74%. In addition, when we measured the proton nuclear magnetic resonance spectrum, we found that there was a 10H peak based on aromatic protons around δ7~7.5ppm,
2H peak with 1-5 rearrangement near δ3.8ppm,
A 6H peak based on the proton of the C-CH ₃ bond was shown around δ2.7 ppm, and a broad peak of 22H based on the proton of the -CH ₂ - bond and the proton of the norbornylidene group was shown around δ1.3 to 2.5 ppm. Furthermore, ¹³ C− nuclear magnetic resonance spectrum ( ¹³ C−
NMR), a peak derived from the carbon of the norbornylidene group was found around δ27 to 52 ppm.
A peak based on the carbon of the methyl group around δ15.6ppm,
A peak based on the carbon of the thiophene ring appears around δ120 to 160 ppm, and a peak based on the carbon of C═O appears around δ160 to 170 ppm. From the above results, it was confirmed that the isolated product was fulgimide compound (1) shown by the following structural formula. Production example 2 3-thienylethylidene-2-adamantylidene succinic anhydride of the following formula 10 g (0.03 mol) and 2 g (0.001 mol) of ethylene dianiline in N-
Dissolved in methylpyrrolidone and 100% under nitrogen atmosphere
Heated at ℃ for 6 hours. After the reaction, the solvent was removed, the solution was dissolved in acetyl chloride, and the mixture was refluxed for 1 hour for cyclization. The following fulgimide compound (2) was obtained by refluxing the obtained compound in O-dichlorobenzene for 8 hours.
was transferred to. The compound was purified by chromatography on silica gel using benzene and ether as eluent and was obtained in 20% yield as yellow needles (melting point 142-143 °C) from chloroform and hexane. . The elemental analysis values of _this compound are C74.96%, H6.17%, N3.35%, _S7.51 %, which are calculated _{values for C52H52N2O4S2} .
It matched extremely well with C75.00%, H6.25%, N3.37%, and S7.69%. In addition, when we measured the proton nuclear magnetic resonance spectrum, we found that there was a 12H peak based on aromatic protons around δ7~7.5ppm,
2H peak with 1-5 rearrangement near δ3.8ppm,
There is a 6H peak based on the proton of the C-CH ₃ bond around δ2.7ppm, a proton based on the proton of the _-CH2- bond, and a broad peak of 32H based on the proton of the adamantylidene group around δ1.3-2.5ppm. Indicated. Furthermore, ¹³ C− nuclear magnetic resonance spectrum ( ¹³ C−
When measuring NMR), a peak derived from the carbon of the adamantylidene group was found around δ26 to 53 ppm.
A peak based on the carbon of the methyl group around δ15.6ppm,
A peak based on the carbon of the thiophene ring and benzene ring appears around δ112 to 160 ppm, and a peak based on the carbon of C═O appears around δ165 to 172 ppm. From the above results, it was confirmed that the isolated product was fulgimide compound (2) represented by the following structural formula. Production Example 3 11 g of (5-bromo-3-thienyl)ethylidene-2-norbornylidene succinic anhydride of the following formula
(0.03mol) and 2 g (0.01 mol) of ethylene dianiline were dissolved in N-methylpyrrolidone and heated at 100°C under a nitrogen atmosphere.
It was heated for 6 hours. After the reaction, the solvent was removed, the solution was dissolved in acetyl chloride, and the mixture was refluxed for 1 hour for cyclization. By refluxing the obtained compound in O-dichlorobenzene for 4 hours, it was rearranged to the following fulgimide compound (3). The compound was purified by chromatography on silica gel using benzene and ether as eluent and was obtained in 15% yield as yellow needles (melting point 148-150 °C) from chloroform and hexane. . The elemental analysis values of this compound are C62.93%, H4.50%, N2.92%, O6.65%,
S6.31%, _{Br16.69%, and the calculated values for C50H42N2S2Br2 are C62.90} %, _H4.43 %, _N2.93
%, O6.70%, S6.30%, and Br16.74%. In addition, when we measured the proton nuclear magnetic resonance spectrum, we found that there was a 10H peak based on aromatic protons around δ7~7.5ppm,
1H peak with 1-5 rearrangement near δ3.8ppm,
A 6H peak based on the proton of the C--CH ₃ bond was shown around δ2.7 ppm, and a broad peak of 22H based on the proton of the -CH ₂ - bond and the proton of the norbornylidene group was shown around δ1.3 to 2.5 ppm. ¹³ more C
-Nuclear magnetic resonance spectrum ( ^13C -NMR) measurement showed peaks based on the carbon of the norbornylidene group around δ26-52ppm and around δ162ppm. This carbon peak around δ162ppm is not ring-closed.

This is a peak based on the carbon of [Formula]. Other carbon-based peaks were the same as in Example 1. From the above results, it was confirmed that the isolated product was fulgimide compound (3) shown by the following structural formula. Production Example 4 10 g (0.03 mol) of the following 3-thienylethylidene-2-adamantylidene succinic anhydride and 2 g (0.001 mol) of ethylene dianiline in N-
Dissolved in methylpyrrolidone and 100% under nitrogen atmosphere
Heated at ℃ for 6 hours. After the reaction, the solvent was removed, the solution was dissolved in acetyl chloride, and the mixture was refluxed for 1 hour for cyclization. By refluxing the obtained compound in O-dichlorobenzene for 2 hours, the following fulgimide compound (4) was obtained.
was transferred to. The compound was purified by chromatography on silica gel using benzene and ether as eluent and was obtained as yellow needles (melting point 140-142 °C) from chloroform and hexane in 17% yield. . The elemental analysis values of this compound are C75.12% _, H6.20%, N3.31%, _S7.65 %, which are calculated _values for _{C52H52N2O4S2 .}
It matched extremely well with C75.00%, H6.25%, N3.37%, and S7.69%. In addition, when we measured the proton nuclear magnetic resonance spectrum, we found that there was a 13H peak based on aromatic protons around δ7~7.5ppm.
1H peak with 1-5 rearrangement near δ3.8ppm,
It showed a 6H peak based on the proton of the C-CH ₃ bond around δ2.7ppm, and a broad peak of 32H based on the proton of the _-CH2- bond and the proton of the adamantylidene group around δ1.3 to 2.5ppm. . moreover
When ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C-NMR) was measured, peaks based on the carbon of the adamantylidene group were observed around δ27 to 52 ppm and around δ164 ppm. This carbon peak at δ164ppm is not ring-closed.

This is a peak based on the carbon of [Formula]. Other carbon-based peaks were similar to those in Example 2. From the above results, it was confirmed that the isolated product was fulgimide compound (4) shown by the following structural formula. Production Examples 5 to 50 According to Production Examples 1 to 4, one or two of the fulgide compounds shown in Table 1 and a diamine compound,
The reaction is carried out using N-methylpyrrolidone, dimethylformamide, toluene or tetrahydrofuran as a solvent, and the ring-closing rearrangement reaction of the product is carried out by heating or additionally by ultraviolet irradiation.
Fulgimide compounds shown in the table were obtained. The obtained products were subjected to elemental analysis, proton nuclear magnetic resonance spectrum and
From the results of measuring ¹³ C-nuclear magnetic resonance spectra,
Compounds represented by structural formulas (5) to (50) shown in Table 1 were confirmed.

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[Table] Example 1 100 parts of benzene, 10 parts of polymethyl methacrylate,
Fulgimide compound (1) obtained in Production Example 1 and Sheasorb UV1084 as an ultraviolet stabilizer were added at 0.5% each.
Add 50% of
3.7cm) to make a cast film. The thickness was adjusted to 0.1 mm. This photochromic film was used in the Xenon Long Life Fade Meter FAL- manufactured by Suga Test Instruments Co., Ltd.
Fatigue life was measured using 25AX-HC. Fatigue life (T1/2) is defined as the time required for the color density to attenuate to half of its initial value when the film is exposed to a fade meter. The results are shown in Table 2. Examples 2 to 12 All the procedures were the same as in Example 1 except that the type of ultraviolet stabilizer used was changed.
The results are shown in Table 2. Comparative Example 1 The same procedure as in Example 1 was carried out except that no ultraviolet stabilizer was used. The results are shown in Table 2.

[Table] Example 13 100 parts of benzene, 10 parts of polymethyl methacrylate,
Fulgimide compound (2) obtained in Production Example 2 and Sheasorb UV1084 as an ultraviolet stabilizer were each added at 0.2
Add 50% of
3.7cm) to make a cast film. After that, the fatigue life (T1/2) was determined in the same manner as in Example 1.
were measured and the results are shown in Table 3. Examples 14-24 In Example 13, everything was the same as in Example 13 except that the type of ultraviolet stabilizer used was changed. The results are shown in Table 3. Comparative Example 2 The same procedure as in Example 13 was carried out except that no ultraviolet stabilizer was used in Example 13. The results are shown in Table 3.

[Table] Examples 25 to 32 The same procedures as in Examples 1 and 7 were carried out except that the amount of ultraviolet stabilizer added in Examples 1 and 7 was changed. The results are shown in Table 4.

[Table] Examples 33 to 80 Everything was the same as in Example 1, except that the polymer matrix used in Example 1 was changed to polystyrene, and the fulgimide compound was changed to the fulgimide compound obtained in Production Examples 3 to 50. . The results are shown in Table 5.

【table】

【table】

[Table] Examples 81 to 86 The same procedures as in Example 1 were repeated except that 0.2 part of the compound shown in Table 6 was further added.
The results are shown in Table 6.

【table】

[Table] Examples 87 to 92 The same procedures as in Example 19 were carried out except that 0.2 part of the compound shown in Table 7 was further added. The results are shown in Table 7.

【table】

【table】

【table】

Claims (1)

[Claims] 1 The following formula X ₁ -R-X ₂ [However, X ₁ is a group represented by (A) or (B) below,
X ₂ is a group represented by (A), (B), (C), (D) or (E) below, and R is a divalent organic group. (However, in formulas (A) to (E), [formula] is a phenyl group, thienyl group, furanyl group, pyrrolyl group, benzothienyl group, benzofuranyl group, or indolyl group, which may each be substituted,
[Formula] is a substituted or unsubstituted norbornylidene group, [Formula] is a substituted or unsubstituted adamantylidene group, R ₁ is an alkyl group or an aryl group, and R ₂ is a hydrogen atom or an alkyl group. , and R ₃ and R ₄ are an alkyl group or an aryl group. )