JP2755444B2 - Chromen composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a chromene composition having good photochromic action durability.

(Problems to be Solved by the Prior Art and the Invention) Photochromism is a phenomenon that has attracted attention in recent years, and when a certain compound is irradiated with light containing ultraviolet light such as sunlight or light from a mercury lamp, it is quickly lost. It is a reversible effect that changes color and returns to the original color when the light is stopped and left in a dark place. A compound having this property is called a photochromic compound, and various compounds have been conventionally synthesized, but no special common structure is recognized in the structure.

Chromene or a derivative thereof is known as a photochromic compound. Chromene or a derivative thereof rapidly changes from a colorless form to a colored form by ultraviolet irradiation (Japanese Patent Application Laid-Open No. 63-66178). However, since the colored form has high thermal stability, it does not easily return to a colorless form at room temperature even when ultraviolet irradiation is stopped. That is, the fading speed is not so fast. As a result, chromene compounds have the disadvantage of poor reversible durability.

Therefore, in order to expand the use of chromene or a derivative thereof as a photochromic article, it was necessary to improve durability.

(Means for Solving the Problems) The present inventors have conducted intensive studies to improve the durability of the specified chromene or its derivative, and as a result, combine the specified chromene or its derivative with an ultraviolet stabilizer. As a result, they have found that a composition having extremely excellent photochromic durability can be obtained, and have completed the present invention.

That is, the present invention provides: (a) 100 parts by weight of a chromene derivative represented by the following formula [A] or [B]: And (b) a chromene composition comprising 0.01 to 10,000 parts by weight of an ultraviolet stabilizer. In the present invention, chromene or a derivative thereof represented by the following formula [A] or [B] is preferably used because it has excellent photochromic properties.

In the above general formulas (A) and (B), Is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group. Specific examples of the aromatic hydrocarbon group include a divalent group derived from one benzene ring such as a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring or a fused ring of 2 to 4 benzene rings. Further, a hydroxyl group, a nitro group, a cyano group, a fluoroalkyl group,
Substituted amino group, halogen atom, alkyl group, alkoxy group, -R ₈ -S-R ₉ , [However, R ₈ is an alkylene group or O—R _{11 n} (however, R
₁₁ is an alkylene group, and n is a positive integer. R ₉ and R ₁₀ are the same or different alkyl groups, and X is It is. And a substituted aromatic hydrocarbon group in which one or two or more heterocyclic groups such as a phenyl group, a phenyl group, a furyl group and a pyrrolyl group are substituted.

Also, Examples of the above unsaturated heterocyclic group represented by are a 5- or 6-membered ring containing oxygen, sulfur and nitrogen atoms, or a heterocyclic group in which a benzene ring is condensed to these. In particular,
Nitrogen-containing heterocyclic rings such as pyridine ring, quinoline ring and pyrrole ring; oxygen-containing heterocyclic rings such as furan ring and benzofuran ring; divalent heterocyclic groups derived from sulfur-containing heterocyclic rings such as thiophene ring and benzothiophene ring Is mentioned. Further, these unsaturated heterocyclic groups, substituted unsaturated heterocyclic group substituted by the substituent described in the description of the aromatic hydrocarbon group described above,
It is adopted without any limitation in the present invention.

Further, in the general formulas [A] and [B], R ₄ , R ₅ , R ₆
And R ₇ are the same or different hydrogen atoms, alkyl groups, aralkyl groups, aryl groups, and substituted amino groups, respectively. The alkyl group is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. The alkylene group in the aralkyl group is
In general, those having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms are suitable. More specific examples of these aralkyl groups and aralkyl groups include methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenylpropyl, and phenylbutyl. As the aryl group, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like are preferable.

Further, in the general formulas [A] and [B], R ₄ , R ₅ , R ₆
And the substituted amino group represented by R ₇ has the general formula Indicated by Groups represented here by R _12, R ₁₃ is, R ₁₂ and R ₁₃
Is either a hydrogen atom and the other is an alkyl group, or represents the same or different alkyl groups. The alkyl group is not particularly limited, but specifically, the same groups as those described above for the alkyl group can be employed. R ₁₄ is an alkylene group having 3 to 6 carbon atoms such as a tetramethylene group and a pentamethylene group; _{-CH 2 OCH 2 CH 2 -,} - CH 2 CH 2 OCH 2 CH 2 -, - CH 2 O (CH 2) 3
An oxyalkylene group having 3 to 6 carbon atoms such as-: -CH
_A thioalkylene group having 3 to 6 carbon atoms, such as ₂ SCH ₂ CH ₂ —, —CH ₂ S (CH ₂ ) ₃ —, and —CH ₂ CH ₂ SCH ₂ CH ₂ —; An azoalkylene group having 3 to 6 carbon atoms, such as, for example, is suitably employed.

In the general formula (B), Is a norbornylidene group Substituted norbornylidene group, bicyclo [3.3.1] 9-nonylidene group A substituted bicyclo [3.3.1] 9-nonylidene group; Specific examples of the substituent include a hydroxy group; a substituted amino group such as a methylamino group and a diethylamino group; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a tert-butoxy group, and a benzyloxy group. An aryloxy group having 7 to 15 carbon atoms such as a phenoxy group, 1-naphthoxy group, etc .; a lower alkyl having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a t-butyl group, etc. Groups; halogen atoms such as fluorine, chlorine, and oxine; cyano groups; carboxyl groups; alkoxycarbonyl groups having 2 to 10 carbon atoms such as ethoxycarbonyl groups; and halogen-substituted alkyl groups having 1 or 2 carbon atoms such as trifluoromethyl groups. Nitro group; aryl group such as phenyl group and tolyl group; aralkyl group such as benzyl group, phenylethyl group and phenylpropyl group. These substituents may be included not only as monosubstituents but also as polysubstituents having two or more substituents, and the substituents in the polysubstituents may be the same. Even
There is no problem even if they are different, and the position of the substituent can be changed according to the purpose or use.

Among the above-mentioned chromene or a derivative thereof, in the general formulas (A) and (B), Is preferably a condensed ring of two or more rings because of high color density. Among them, compounds in which a ring is condensed at the 7th and 8th positions of the chromene derivative are more preferable. In addition, the general formula [B]
In the above, a compound obtained by condensing a ring at the 5- or 6-position of the chromene derivative is also preferably used.

Another component of the chromene composition of the present invention is a UV stabilizer. As the ultraviolet stabilizer, known ultraviolet stabilizers added to various prostics can be used without any limitation.

Considering the improvement of the photochromic properties of the chromene composition obtained in the present invention, among various ultraviolet stabilizers,
A singlet oxygen quencher, a hindered amine light stabilizer (including a light stabilizer having a hindered amine structure and a hindered phenol structure in one molecule), a hindered phenol antioxidant, and a sulfur-based secondary antioxidant are preferably used. I can do it.

Among these, a light stabilizer having a hindered amine structure and a hindered phenol structure in one molecule is most preferable, and then other hindered amine light stabilizers, singlet oxygen quenchers, and hindered phenol antioxidants have almost the same effect. With. Further, by combining two or more of these ultraviolet stabilizers, even better effects can be obtained when used alone. Above all, a combination of two types in which a light stabilizer having a hindered amine structure and a hindered phenol structure in one molecule, and another hindered amine light stabilizer, a hindered phenol antioxidant or a singlet oxygen quencher is added. In addition, the best combination is obtained with a combination of a light stabilizer having a hindered amine structure in one molecule and another hindered amine light stabilizer and a singlet oxygen quencher.

The singlet oxygen quencher preferably used in the present invention includes a complex of Ni ²⁺ and an organic ligand, cobalt (III)
-Tris-di-n-butyldithiocarbamate, iron (II
I) -diisopropyldithiocarbamate and cobalt (II) -diisopropyldithiocarbamate. Among these singlet oxygen quenchers,
Particularly, a complex of Ni ²⁺ and an organic ligand is preferable. Specific examples of such a complex 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, Nityl-dibutyldithiocarbamate, Bis [2,2'-thiobis-4- (1,1,3,3-tetramethylbutyl) phenolato] nickel In addition, UV-CHECK AM from Ferro Corporation
105, UV-CHECK AM126 and UV-Check AM205 under the trade name of Ni complex.

Specific examples of the above hindered amine light stabilizer suitable as an ultraviolet stabilizer are as follows.

(However, the above formulas (e), (f), (g), (h),
(Q), (co), (sa), (shi) and (su), 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 a hydrogen atom or an alkyl group, R ¹⁸ is a benzoyl group, an acryloyl group or a methacryloyl group, and m and n are positive integers . ) Above (e), (f), (g), (h), (h),
In (ko), (sa), (si) and (su), the alkyl group is not particularly limited to the number of carbon atoms, but is generally in the range of 1 to 12 for reasons such as easy availability of these compounds. Preferably, there is.

Further, as hindered amine light stabilizers, Sumisorb LS-2000 and LS-2000 manufactured by Sumitomo Chemical Co., Ltd. are available.
2001 (all are trade names) and the like.

Further, specific examples of the hindered phenol antioxidant suitable as an ultraviolet stabilizer are as follows.

(However, the above formulas (se), (so), (ta), (h),
(Tsu), (te), (g), (na), (d), (nu),
In (ne) and (no), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are alkyl groups, R ³ is hydrogen or an alkyl group,
¹⁹ is a hydrogen atom, an alkyl group or an acryloyl group,
n is a positive integer. ) The above (S), (S), (T), (H), (T),
In (te), (g), (na), (d), (nu), (ne) and (no), the alkyl group is not particularly limited to the number of carbon atoms, but generally, these compounds are available. It is preferably in the range of 1 to 20 for reasons such as easiness.

Further, specific examples of the sulfur-based secondary antioxidant suitable as an ultraviolet stabilizer are as follows.

(However, in the above formulas (C), (H), (F), (F) and (E), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are alkyl groups; ³ is a hydrogen atom or an alkyl group.) In the above (c), (h), (f), (f) and (e),
The alkyl group is not particularly limited to the number of carbon atoms, but is generally 1 for reasons of availability of these compounds.
It is preferably in the range of 20 to 20.

The blending ratio of the above-mentioned chromene or a derivative thereof and the ultraviolet stabilizer is 0.01 to 10,000 for the latter with respect to 100 parts by weight of the former.
It is in the range of parts by weight. When the UV stabilizer is less than 0.01 part by weight, the effect of improving the photochromic repetition durability is scarcely recognized, and when it exceeds 10,000 parts by weight, the chromene composition is dispersed in a resin described below. It is not preferable because resin molding becomes difficult. Especially,
From the viewpoint of photochromic properties of the obtained chromene composition, the amount of the ultraviolet stabilizer is preferably in the range of 50 to 400 parts by weight.

The chromene composition of the present invention can exhibit the desired photochromic function as described above by being uniformly dispersed in various polymer matrices.
Examples of the synthetic resin constituting the polymer matrix used by dispersing the chromene composition in the present invention include:
It is sufficient that chromene or a derivative thereof can be uniformly dispersed, and optically preferable, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol , Polyacrylamide, poly (2-hydroxyethyl methacrylate),
Polymers such as polydimethylsiloxane, polycarbonate, and poly (allyl diglycol carbonate), or monomers forming these polymers or polymers obtained by copolymerizing the monomers with other monomers are preferably used. The amount of the chromene composition of the present invention dispersed in such a resin is 0.001 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the resin.

The chromene composition of the present invention is particularly suitably used for a photochromic lens. The method for producing a photochromic lens is not particularly limited as long as there is a method capable of obtaining uniform dimming performance, and specifically, a polymer film obtained by uniformly dispersing the above chromene or a derivative thereof and an ultraviolet stabilizer. There is a method of sandwiching in the lens. Alternatively, there is a method of dispersing the above chromene composition in silicone oil, impregnating the lens surface at, for example, 200 ° C. for 15 minutes, and further coating the surface with a curable substance to form a photochromic lens. There is also a method in which the above-mentioned polymer film is applied to the lens surface, and the surface is coated with a curable substance to form a photochromic lens.

(Effect) As described above, the chromene composition of the present invention
In particular, by uniformly dispersing in various resins, the color changes from colorless to colored or darkened by light including ultraviolet rays such as sunlight or light from a mercury lamp, and the change is reversible and excellent dimming properties are obtained. Have. Further, the present invention has succeeded in dramatically improving the repetitive durability without lowering the coloring concentration by using chromene or a derivative thereof and an ultraviolet stabilizer in combination.

Therefore, the chromene composition of the present invention can be used in a wide range of fields, for example, various recording storage materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, recording materials for lasers, etc. Can be used as various recording materials. In addition, the chromene composition of the present invention can also be used as a material for photochromic lens materials, optical filter materials, display material light meter, decoration and the like.

(Examples) Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, the part in an Example shows a weight part.

The UV stabilizers used in the following examples are the following compounds.

・ Cyasorb UV1084 (Product name: American Cyamide) ・ Irgastab 2002 (product name: Ciba-Geigy) ・ Rylex NBC (Product name: manufactured by DuPont) ・ UV-Chek AM101 (trade name: manufactured by Ferro Corporation) ・ UV-Chek AM105 (trade name: manufactured by Ferro Corporation) ・ Tinuvin 765 (Product name: Ciba Geigy) ・ Tinuvin 765 (Product name: Ciba-Geigy) ・ Chimassorb 944 (Product name: Ciba-Geigy) ・ Cyasorb 3346 (Product name: American Cyanamid Co., Ltd.) ・ Tinuvin 622 (Product name: Ciba-Geigy) ・ Sanol LS-1114 (trade name: manufactured by Sankyo) ・ Sanol LS-74 (trade name: manufactured by Sankyo) ・ MARK LA-82 (Product name: Adeka Argus) ・ MARK LA-87 (Product name: Adeka Argus) ・ Sanol LS-2626 (trade name: manufactured by Sankyo Co., Ltd.) ・ Sumilyzer GA-80 (trade name: manufactured by Sumitomo Chemical Co., Ltd.) ・ Irganox 1010 (Product name: Ciba-Geigy) ・ MARK AO-50 (Product name: Adeka Agarth) ・ Sumilyzer GM (Product name: Sumitomo Chemical Co., Ltd.) ・ Sumilyzer BBM-S (Product name: Sumitomo Chemical Co., Ltd.) ・ Sumilyzer WX-R (trade name: manufactured by Sumitomo Chemical Co., Ltd.) ・ Sumilyzer S (Product name: Sumitomo Chemical Co., Ltd.) ・ Sumilyzer BHT (Product name: Sumitomo Chemical Co., Ltd.) ・ MARK AO-20 (Product name: Adeka Argus) ・ MARK AO-30 (Product name: Adeka Argus) ・ MARK AO-330 (Product name: Adeka Argus) ・ Irganox 245 (trade name: Ciba-Geigy) ・ Antioxidant HPM12 (trade name: SFOS) ・ MARK AO-23 (Product name: Adeka Argus) - Sumilizer TP-D (trade name: manufactured by Sumitomo _{Chemical) (H 25 C 12 SCH 2} CH 2 COOCH 2) 4 C · Sumilizer TPL-R (trade name: manufactured by Sumitomo Chemical) ・ Sumilyzer TPS (Product name: Sumitomo Chemical) ・ Sumilyzer MB (Product name: manufactured by Sumitomo Chemical Co., Ltd.) Production Example 1 1-hydroxy-2-acetonaphthone 10 g (0.054mo
l) with 6.6 g (0.06 mol) of norcamphor and 8 g of pyrrolidine
(0.113 mol) was dissolved in 300 cc of toluene to prepare a solution. The mixture was boiled for 10 hours and the water was separated. After the completion of the reaction, the toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized with acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. By heating 7.47 g of this chromanol compound together with 4.5 g of anhydrous copper sulfate in a stream of carbon dioxide at 150 to 160 ° C. for 10 minutes, and purifying the brown viscous liquid by chromatography on silica gel, a chromene compound of the following formula was obtained. 6.3 g of the derivative were obtained.

Elemental analysis values of this compound were as follows: C86.93%, H6.89%, O6.
18%, a a, a calculated value for C ₁₉ H ₁₈ O C87.02
%, H6.87% and O6.12%. When the proton nuclear magnetic resonance spectrum was measured, it was found that δ7.2
A peak of 6H based on the proton of the naphthalene ring at about 8.3 ppm, a peak of 2H based on the protons at the 3rd and 4th positions of the chromene ring at about δ5.6 to 6.7ppm, and a norbornylidene group at about δ1.2 to 2.5ppm. It showed a broad peak at 10H due to protons. Further measurement of ¹³ C-nuclear magnetic resonance spectrum, a peak based on the carbon of the norbornylidene group around δ27 to 52 ppm, a peak based on the carbon of the naphthalene ring around δ110 to 160 ppm, the third position of the chromene ring around δ80 to 110 ppm, and A peak based on the carbon at position 4 appears.
From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (1).

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

Elemental analysis of this compound gave C86.81%, H7.62%, O5.
A 57%, a calculated value for C ₂₁ H ₂₂ O C86.90
%, H7.59% and O5.52%. When the proton nuclear magnetic resonance spectrum was measured, it was found that δ7.2
~ 8.3 ppm around 6H peak based on naphthalene ring proton, δ6.0 ~ 7.0 ppm around 2H peak based on 3rd and 4th protons of chromene ring, δ1.2 ~ 2.5 ppm around bicyclo [3.3 .1] showed a broad peak at 14H based on the proton of the 9-nonylidene group. Further, when ¹³ C-nuclear magnetic resonance spectrum was measured, a peak based on the carbon of the bicyclo [3.3.1] 9-nonylidene group around δ 27 to 52 ppm, a peak based on the carbon of the naphthalene ring around δ 110 to 160 ppm, δ 80 to A peak appears at about 110 ppm based on the carbons at the 3- and 4-positions of the chromene ring. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (2).

Production Example 3 3.06 g (0.01 mol) of a chromanone compound represented by the following formula Was dissolved in 50 cc of anhydrous ether, the solution was cooled to 0 ° C., and a freshly prepared Grignard reagent CH ₃ MgCl (0.012 mol) was added dropwise to the solution over 50 minutes in 50 cc of anhydrous ether. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, then the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, and then removed with ether under reduced pressure. The compound was changed to a chromanol compound. Next, this chromanol compound was heated at 200 ° C. for about 10 minutes together with anhydrous copper sulfate in a stream of carbon dioxide, and the brown viscous liquid was purified by chromatography on silica gel to obtain 2.47 g of a chromene derivative represented by the following formula.

Elemental analysis, proton nuclear magnetic resonance spectrum, and measurement of ¹³ C-nuclear magnetic resonance spectrum were performed in the same manner as in Production Example 1.
This compound was confirmed to be the compound represented by the above structural formula (3).

Production Example 4 1-acetyl-2-naphthol 10 g (0.054 mol), norcamphor 6.6 g (0.06 mol), and morpholine 8.7 g (0.10 m
ol) was dissolved in 300 cc of toluene, boiled for 15 hours, and water was separated. After the reaction, the toluene was removed under reduced pressure,
The remaining product was recrystallized from acetone to obtain 7.53 g of a compound represented by the following formula.

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

Next, the produced chromanone compound was changed to a chromanol compound in the same manner as in Production Example 3, and a dehydration reaction was performed. After separation and purification, 5.84 g of a chromene derivative represented by the following formula:
I got

As in Production Example 1, elemental analysis, proton nuclear magnetic resonance spectrum and ¹³ C-nuclear magnetic resonance spectrum measurement confirmed that this compound was the compound represented by the above structural formula (4).

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

As in Production Example 1, elemental analysis, proton nuclear magnetic resonance spectrum, and ¹³ C-nuclear magnetic resonance spectrum measurement confirmed that this compound was the compound represented by the above structural formula (5).

Production Examples 7-14 The chromene derivatives shown in Table 1 were synthesized in the same manner as in Production Examples 1 to 5.

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

Example 1 100 parts of benzene, 10 parts of polymethyl methacrylate, 0.2 part of each of the chromene derivative (1) obtained in Production Example 1 and Shiazov UV1084 as an ultraviolet stabilizer were added and dissolved, and a slide glass (11.2 × 3.7 cm) was dissolved. I made a cast film above.

The thickness was adjusted to be 0.1 mm. The fatigue life of this photochromic film was measured using a Xenon Long Life Fade Meter FAL-25AX-HC manufactured by Suga Test Instruments Co., Ltd. Fatigue life (T1 / 2) is defined as the time required for the color density to decay to half the initial value when the above film is irradiated to a fade meter. The results are shown in Table 2.

Examples 2 to 35 All of the procedures were the same as in Example 1 except that the kind of the ultraviolet stabilizer used was changed. The results are shown in Table 2.

Comparative Example 1 The procedure of Example 1 was repeated except that no ultraviolet stabilizer was used. The results are shown in Table 2.

Examples 36 to 70 The chromene derivative used in Example 1 was prepared in Production Example 2
All procedures were the same as in Example 1, except that the compound (2) obtained in was used. The results are shown in Table 3.

Comparative Example 2 The procedure of Example 36 was repeated except that no ultraviolet stabilizer was used. The results are shown in Table 3.

Examples 71 to 86 In all of Examples 1, 7, 13 and 18, except that the added amount of the ultraviolet stabilizer was changed, the same procedures as in Examples 1, 7, 13 and 18 were carried out. The results are shown in Table 4.

Examples 87 to 106 In Examples 1, 7, 13, 18, and 32, all were the same as Example 1 except that 100 parts of the chromene derivative was combined with 100 parts each of two or three UV stabilizers. did. The results are shown in Table 5.

Examples 107 to 114 In Examples 88 and 97, all were the same as Examples 88 and 97, except that the composition ratio of the ultraviolet stabilizer was changed. The results are shown in Table 6.

Examples 115 to 126 The polymer matrix used in Example 97 was changed to polystyrene, and chromene derivatives were further prepared.
Except for changing to the chromene derivative obtained in 14, all examples
Same as 97. The results are shown in Table 7.

Example 127 100 parts of benzene, 10 parts of polymethyl methacrylate, and 0.2 part of the chromene derivative obtained in Production Example 1 were added and dissolved, and a cast film was formed on a slide glass (11.2 × 3.7 cm). The thickness was adjusted to be 0.1 mm. This photochromic film was irradiated with a mercury lamp SHL-100 manufactured by Toshiba Corporation at 25 ° C. ± 1 ° C. at a distance of 10 cm for 60 seconds, and the film was colored to measure photochromic characteristics. The photochromic properties were expressed as follows. The results are shown in Table 8.

ε (60 seconds): Absorbance at the maximum absorption wavelength after 60 seconds of light irradiation of the film under the above conditions.

ε (0 seconds); absorbance of the unirradiated film at the maximum absorption wavelength upon light irradiation.

Examples 128 to 140 The chromene derivatives in Example 127 were prepared according to Production Examples 2 to 14.
Except for changing to the chromene derivative obtained in the above, all
Same as 127. The results are shown in Table 8.

Claims (1)

(57) [Claims] (A) 100 parts by weight of a chromene derivative represented by the following formula [A] or [B]: And (b) a photochromic composition comprising 0.01 to 10,000 parts by weight of an ultraviolet stabilizer.