JPH03115385A - Chromene composition - Google Patents

Abstract

PURPOSE:To obtain a chromene composition having persistent photochromism by mixing a chromene (derivative) and an ultraviolet stabilizer at a specified ratio. CONSTITUTION:An objective composition comprises 100 pts.wt. chromene (derivative) preferably of formula I or II [wherein the group of formula III is a (substituted) aromatic hydrocarbon or a (substituted) heterocyclic ring; R4 to R7 are each H, alkyl, aralkyl, aryl or substituted amino; the group of formula IV is (substituted) norbornylidene, (substituted) bicyclo(3,3,1)9-nonlylidene or (substituted) adamantylidene] and 0.01-10,000 pts.wt. ultraviolet stabilizer preferably comprising, e.g. a hindered phenol oxidation stabilizer or a sulfur-containing secondary oxidation inhibitor.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a romen composition having good durability of photochromic action.

(Prior Art and Problems to be Solved by the Invention) Photochromism is a phenomenon that has attracted attention over the past few years.When a certain compound is irradiated with light containing ultraviolet light, such as sunlight or light from a mercury lamp, photochromism immediately This is a reversible effect in which the color changes and returns to the 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 among them.

Chromene or its derivatives are known as photochromic compounds. Chromene or its derivatives rapidly changes from a colorless form to a colored form upon irradiation with ultraviolet rays (Japanese Patent Laid-Open No. 63-66178). However, due to the high thermal stability of the colored form, it is difficult to return to the colorless form at room temperature even if UV irradiation is stopped, that is, the rate of discoloration is not very fast.

As a result, chromene compounds have the disadvantage of poor reversible durability.

Therefore, in order to expand the use of chromene or its derivatives as photochromic products, it was necessary to improve the durability.

(Means for Solving the Problem) As a result of intensive research to improve the durability of the above-mentioned chromene or its derivative, the present inventors combined an ultraviolet stabilizer with the above-mentioned chromene or its derivative. The inventors have discovered that a composition with extremely excellent photochromic durability can be obtained by doing so, and have completed the present invention.

That is, the present invention is a chromene composition characterized by comprising 100 parts by weight of fal chromene or a derivative thereof and (b) 0.01 to 10,000 parts by weight of an ultraviolet light stabilizer.

Chromene, which is one component of the chromene composition of the present invention, is a compound represented by the following formula. Further, as the chromene derivative, any compound having the above-mentioned chromene skeleton can be employed without any restriction. In the present invention, the following formula (A) or [B
] Chromene or a derivative thereof is preferably used because it has excellent photochromic properties.

The groups shown are substituted or unsubstituted aromatic hydrocarbon groups or substituted or unsubstituted unsaturated heterocyclic groups. Specific examples of aromatic hydrocarbon groups include 2 derived from one benzene ring or fused rings of 2 to 4 benzene rings such as benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, etc.
Examples include valence groups. In addition, the aromatic hydrocarbon group mentioned above can be replaced with a hydroxyl group, a nitro group, a cyano group, a fluoroalkyl group, a substituted amino group, a halogen atom, an alkyl group, and alkoxy is an alkylene group or +o-R0+-F- (however, Ro is an alkylene group) , n is a positive integer), and R1
and R7° each contain one or two heterocyclic groups such as the same or different arthienyl group, furyl group, or pyrrolyl group.
Examples include substituted aromatic hydrocarbon groups substituted with one or more substituted aromatic hydrocarbon groups.

As a ring group, a 5-membered ring containing oxygen, sulfur, and nitrogen atoms,
Examples include a 6-membered ring or a heterocyclic group in which a benzene ring is fused to the 6-membered ring. Specifically, 2 derived from nitrogen-containing heterocycles such as a pyridine ring, quinoline ring, and pyrrole ring; oxygen-containing heterocycles such as a furan ring and benzofuran ring; and sulfur-containing heterocycles such as a thiophene ring and benzothiophene ring. valent heterocyclic groups. Furthermore, substituted unsaturated heterocyclic groups in which these unsaturated heterocyclic groups are substituted with the substituents described in the description of the aromatic hydrocarbon group described above are also employed without any limitations in the present invention.

Further, in the above-mentioned - Sailor (A) and CB), R4, Rs,
The groups represented by Rh and R9 are the same or different hydrogen atoms, alkyl groups, aralkyl groups, aryl groups, or substituted amino groups, respectively. The above alkyl group is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.
It is preferable that The alkylene group in the aralkyl group generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. More specific examples of these alkyl groups and aralkyl groups include methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups. Further, as the aryl group, for example, phenyl group, tolyl group, xylyl group, naphthyl group, etc. are suitable.

Furthermore, in the above-mentioned shipmen (A) and (B), R4, R,
The substituted amine group represented by R, and R7 is here RI2
, Ru3, either one of RI2 and R43 is a hydrogen atom and the other is an alkyl group, or each represents the same or different alkyl group. The alkyl group is not particularly limited, but specifically, the same groups as the above-mentioned examples of the alkyl group can be employed.

Furthermore, RI4 is a tetramethylene group, a pentamethylene group, etc.
3 to 3 carbon atoms, such as zcHz-CLO(C)b)i-
6 Oxydialkyl/7 groups KHzSC) IzClh
--C) Its(CH2)ICHzCHzSCHzCH
A thizoalkylene group having 3 to 6 carbon atoms such as z~ is preferably employed.

bornylidene group, Bicyclo (3, 3, 13 9-Noniri 9-nonylidene group, adamantylidene group It is.

Specific examples of the substituent include, for example, hydroxy group: substituted amino groups such as methylamino group and diethylamino group; alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, and tart-butoxy group; benzyloxy group Aralkoxy groups having 7 to 15 carbon atoms, such as phenoxy groups, 1-naphthoxy groups, etc.; 6 to 1 carbon atoms, such as phenoxy groups, 1-naphthoxy groups, etc.
4-ruoxy group; lower alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, t-butyl group; halogen atom such as fluorine, chlorine, oxaline; cyano group; carboxyl group; ethoxycarbonyl group Alkoxycarbonyl group having 2 to 1 carbon atoms such as; carbon number 1 such as trifluoromethyl group
or 2 halogen W-substituted alkyl group; nitro group; aryl group such as phenyl group, tolyl group; aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, etc., and these substituents include l-substituted It may be included not only as a polysubstituted product, but also as a polysubstituted product having multiple substituents of 2N or more substitution (and even if the substituents in a polysubstituted product are of the same type or different types) There is no problem and the position of the substituent can be changed depending on the purpose or use.

Among the above-mentioned chromenes or derivatives thereof, a condensed ring with a pre-ring or more is preferable because of its high coloring density. Among these, compounds in which a ring is condensed at the 7.8-position of a chromene derivative are more preferred. Moreover, in the above-mentioned -Shipin CB), a compound in which a ring is condensed at the 5.6-position of a chromene derivative is also suitably used.

Another component of the chromene compositions of the present invention is a UV stabilizer. As the UV stabilizer, any known UV stabilizer added to various plastics can be used without any limitations.

Considering the improvement in photochromic properties of the chromene composition obtained in the present invention, among various UV stabilizers, -
Items Oxygen quenchers, hindered amine light stabilizers (including light stabilizers having a hindered amine structure and a hindered phenol structure in the molecule), hindered phenol antioxidants, and sulfur-based secondary antioxidants are preferably used. obtain.

Among these, light stabilizers having a hindered amine structure and a hindered phenol structure in the molecule are most preferred, followed by other hindered amine light stabilizers, oxygen quenchers, and hindered phenol antioxidants, which have almost the same effect. have. In addition, these above-mentioned ultraviolet stabilizers are
By combining more than one species, better effects can be obtained even when used alone. Among them, - a light stabilizer having a hindered amine structure and a hindered phenol structure in the molecule, and other hindered amine light stabilizers, hindered phenol antioxidants, or - oxygen quenchers added.
Combinations of species are preferred. Furthermore, the best effect can be obtained by a combination of three types in which - a light stabilizer having a hindered amine structure in the molecule, another hindered amine light stabilizer, and an oxygen quencher are added.

Singlet oxygen quenchers preferably used in the present invention include complexes of Ni'' and organic ligands, cobalt (III
)-) Lis-di-n-butyldithiocarbamate, iron (
III)-diisopropyldithiocarbamate and cobalt(II)-diisopropyldithiocarbamate. Among these oxygen quenchers, complexes of Ni" and organic ligands are particularly preferred. Specific examples of such complexes are as follows.

C2,2'-thiobis(4-(Ll, 3.3-tetramethylbutyl)phenolato)butylamine]nickel, nickelbis[0 ethyl(3,5-diert-butyl-4-hydroxybenzyl)]bophospho Natonityl-dibutyldithiocarbamate, (1) bis(2,2'-thiobis-4-(1,1,3,3-tetramethylbutyl)phenolad) nickel, etc., UV-tinylated from Ferro Corporation. AM105, U
Mention may be made of the Ni complexes commercially available under the trade names V-Chek M126 and UV Chek AM205.

Further, specific examples of the aforementioned hindered amine light stabilizers suitable as ultraviolet stabilizers are as follows.

5 (CziHstN,,).

(Co) R) (However, the above formula () () () () ) () () () () % formula % is an alkyl group, R'' and R8 are hydrogen atoms or alkyl groups, and RII' is a benzoyl group, an acryloyl group, or a methacryloyl group, and m and n are positive integers.) The above (e), (force), (ki), (ri), (ke), (co)
, Kusu), (C) and (S), the alkyl group is,
The number of carbon atoms is not particularly limited, but is generally preferably in the range of 1 to 12 for reasons such as ease of obtaining these compounds.

Furthermore, as a hindered amine light stabilizer, Sumisorb L S-2 manufactured by Sumitomo Chemical ■ is used.
000 and LS-2001 (both are trade names).

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

(NU) (However, the above formula (C), (SO), (YU), (CH), (TS), (TE), (T), (SU), (D), (NU) (NE) and ()), R1, RZ, R4, R5R6, R7, and R11 are alkyl groups, R3 is hydrogen or an alkyl group, RI9 is a hydrogen atom, an alkyl group, or an acryloyl group, and n is a positive is an integer. ) Above (C), (S), (Even), (C), (T), (T)
, (g), (su), (d), (nu), (ne) and ())
Among them, the number of carbon atoms in the alkyl group is not particularly limited, but is generally preferably in the range of 1 to 20 for reasons such as ease of obtaining these compounds.

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

CHzGHzCOOR' (c) CHzCHzCOOR"(R' 5CHzC1(zcOOcHz)tc(hi) and R7 is an alkyl group, and R3 is a hydrogen atom or an alkyl group.) In the above (c), (h), ()), (e), and (e), the alkyl group has a particular number of carbon atoms. Although not limited, in general, 1 to 1 are used due to the ease of obtaining these compounds.
A range of 20 is preferred.

The blending ratio of the above-mentioned chromene or its derivative and the UV stabilizer is 0.01 to 100 parts by weight of the former and 0.01 to 100 parts by weight of the latter.
The range is 10,000 parts by weight. UV stabilizer is 0.0
When the amount is less than 1 part by weight, there is almost no improvement effect on the repeated durability of photochromic properties, and when the amount is less than 1 part by weight,
If the amount exceeds 1 part by weight, it is not preferable because molding of the resin becomes difficult when the chromene composition is dispersed in the resin described later. In particular, from the viewpoint of photochromic properties of the resulting 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 satisfactorily exhibit the desired photochromic function as described above by being uniformly dispersed in various polymer matrices. The synthetic resin constituting the polymer matrix in which the chromene composition of the present invention is dispersed may be any synthetic resin as long as it can uniformly disperse chromene or its derivatives, and optically preferably, for example, polyacrylic methyl acid, polyethyl acrylate, polymethyl methacrylate,
Polymers such as polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly(2-hydroxyethyl methacrylate), polydimethylsiloxane, polycarbonate, poly(allyl diglycol carbonate), or monomers forming these polymers. Polymers formed by copolymerizing each other or these monomers with other monomers are preferably used. The amount of the chromene composition of the present invention to be dispersed in such a resin is -0.OO1 to 10 parts by weight, preferably 0.1 parts by weight, per 100 parts by weight of the resin.
~10 parts by weight.

The chromene composition of the present invention is particularly suitable for use in photochromic lenses. The method for producing photochromine lenses is not particularly limited as long as there is a method that provides uniform dimming performance, and a specific example is one in which the above-mentioned chromene or its derivative and an ultraviolet stabilizer are uniformly dispersed. There is a method of sandwiching a polymer film into the lens.

Alternatively, there is a method in which the chromene composition is dispersed in silicone oil and impregnated onto the lens surface at, for example, 200° C. for 15 minutes, and then the surface is coated with a curable substance to form a photochromic lens. Another method is to apply the above polymer film to the lens surface and coat the surface with a curable substance to make a photochromin lens.

(Effects) As explained above, the chromene composition of the present invention, by uniformly dispersing it in various types of resins, can be colored or darkened from colorless to colored or deep colored when exposed to sunlight or light containing ultraviolet rays such as mercury lamp light. This change is reversible and has excellent dimming properties. Furthermore, the present invention has succeeded in dramatically improving the durability against repeated use without reducing the color density by using chromene or a derivative thereof in combination with an ultraviolet stabilizer.

Therefore, the chromene 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, window phosphors for printing, recording materials for cathode ray tubes, and photosensitive materials for lasers. It can be used as a variety of recording materials such as. In addition, the chromene 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.

(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.

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

Cyasorb U V 1 8 (Product name: American Cyamide) ・Irgastab 0 (Product name: Ciba Geigy) ・Rylex N B C (Product name:
UV-Chek A M 101 (Product name: manufactured by Ferro Corporation) U■-Chek M105 (Product name: manufactured by Ferro Corporation) Tinuvin C novin) 7 (Product name: Ciba Geigy) - Tinuvin 76 (Product name: Ciba Geigy) H - Chimassorb (Product name: Ciba Geigy) C (CH3)! Cyasorb 3 (Product name: manufactured by American Cyanamid Company) / Tinuvin 6 (Product name: manufactured by Ciba Geigy Company) C) + 3 ・MARK A-87 (Product name: manufactured by Niadeka Argus Company)・Sanol LS-2626 (Product name: Manufactured by Sankyo Co., Ltd.) CH3 ・Sumilizer〇A (Product name: Manufactured by Sumima Kagaku Co., Ltd.) ・Irganox (Product name: Manufactured by Ciba Geigy Co., Ltd.) ・MARK 0-50 (Product name) : Manufactured by Adeka Agarth Co., Ltd.) - Sumilizer GM (Product name: Manufactured by Sumima Kagaku Co., Ltd.) CH.

CH5 ・Sumilizer 88M-3 (Product name: Manufactured by Sumima Kagaku Co., Ltd.) ・Sumilizer X-R (Product name: Manufactured by Sumima Kagaku Co., Ltd.) Shi13 C (CH3) Tosumilyzer・ (Product name: Manufactured by Sumima Kagaku Co., Ltd.) H ・Sumilizer HT (Product Name: Manufactured by Sumima Kagaku Co., Ltd.) H H3 ・MARK 0-20 (Product Name: Manufactured by Adeka Argus Co., Ltd.) (manufactured by Ciba-Geigy) ・Mark (on MAR) 0-33 (Product name: Niadeca Argus) H ・Irganox 24 (Product name: Ciba Geigy) ・MARK A O-23 (Product name: Niadeca Argus)・Sumilizer TP-D (Product name: Made by Sumitomo Chemical) (F128CI□5C)IzCHzCOOCHz) 4
C Sumilizer TPL-R (Product name: Jumin Chemical) CI (zC) 1 zcOOc +□) 125GHzcI
(zcOOc +□fizs Sumilizer TPS (Product name: Jumin Chemical Co., Ltd.) cozcHzcOOc+ l37 CHzCH□C00C+sRs.

・Sumilizer MB (Product name: Manufactured by Sumima Kagaku Co., Ltd.) Production example 1 1-Hydroxy-2-acetonaphthone 10g (0.05
4taol) and norkampfy -6,6g (0,0
611 ol) and 8 g of pyrrolidine (0,113 moj
A solution was prepared by dissolving 1 liter in 3QOcc of toluene. The mixture was boiled for 10 hours and the water was separated. After the reaction was completed, toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized from acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to form a chromanol compound. 7.47 g of this chromanol compound was mixed with 4.5 g of anhydrous copper sulfate in a carbon dioxide stream at 150 to 16 g.
By heating at 0 °C for 10 min and purifying the brown viscous liquid by chromatography on silica gel.
6.3 g of a chromene derivative of the following formula was obtained.

The elemental analysis values of this compound are CB 6.93%, H6,
89%, 06.18%, and C+ q H+ s
Calculated values for O: C87.02%, H6,87
%, 06.12%. In addition, when proton nuclear magnetic resonance spectra were measured, the results were 67.2~
<, 6H peak based on the proton of the naphthalene ring near 8.3 ppn+, <2H peak based on the alkene proton near δ5.6-6.7 ppm, 61.2-2
．． A broad peak of 10H based on the proton of norbornylidene group was shown around 5 ppm.

Furthermore, when the l30-nuclear magnetic resonance spectrum was measured, a peak based on the carbon of the norbornylidene group was measured near δ27 to 52 ppm, a peak based on the carbon of the naphthalene ring was measured near 6110 to 160 ppm, and a peak based on the carbon of the naphthalene ring was measured at 680 to 110 ppm.
A peak based on the carbon of the alkene appears nearby. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (11).

Production example 2 1-acetyl-2-naphthol 10 g (0,054
mojrito bicyclo(3,3,1)nonan-9-one 8
．． 29g (0°061IIol) and morpholine 8.7
A solution was prepared by dissolving g (0.10 mo1) in 300 cc of toluene. Boil this mixture for 10 hours,
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 mixed with 200 cc of methanol.
by adding lithium aluminum hydride,
It was made into a chromanol compound. This chromanol compound 6
．． 49 g with anhydrous copper sulfate in a stream of carbon dioxide.
After heating at 0-180°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%, calculated values for CZIH2□O C 86.90%, H7, 59%, 05.
There was a very good agreement of 52%. In addition, when proton nuclear magnetic resonance spectra were measured, 67.2 to 8.3 p
Based on the proton of the naphthalene ring near pm, 6H
peak, δ6. O~7. <2H peak based on alkene proton near OppIrl, 61.2-2,
A broad peak of < 14 H based on the proton of bicyclo(3,3,139-nonylidene group) was observed around 5 ppm.Furthermore, when the 13C-nuclear magnetic resonance spectrum was measured, bicyclo(3 ,3
, 1) Peak based on carbon of 9-nonylidene group, 611
A peak based on the carbon of the naphthalene ring appears around 0 to 160 ppm, and a peak based on the carbon of the alkene appears around δ80 to 110 ppn+. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (2).

Production Example 3 3.06 g (0,
01 mol) in 50 cc of anhydrous ether, cool the solution to 0 °C, and dissolve the freshly prepared Grignard reagent CH3Mgj2 (0,012 mo#) in 50 cc of anhydrous ether.
was added dropwise into the solution over a period of about 1 hour. After the addition was completed, the ether solution was stirred for another 2 hours at room temperature, the ether solution was poured gently 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 with anhydrous copper sulfate in a carbon dioxide stream at 200°C for about 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel to obtain 2.47 g of a chromene derivative of the following formula. Ta.

As in Production Example 1, by elemental analysis, proton nuclear magnetic resonance spectrum, and +30-nuclear magnetic resonance spectrum measurements,
This compound was confirmed to be a compound represented by the above structural formula (3).

Production example 4 1-acetyl-2-naphthol 10 g (0,054
mob) and Norkampfy-6,6g (0,06mo
A) and 8-7 g (0.10 moJ) of morpholine were dissolved in 300 cc of toluene, boiled for 15 hours, and water was separated. After the reaction is complete, toluene is removed under reduced pressure,
The remaining product was recrystallized with amethane 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, in the same manner as in Production Example 3, the produced chromanone compound was converted into a chromanol compound, subjected to a dehydration reaction, and after separation and purification, a chromene derivative 5.84 of the following formula was obtained.
I got g.

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

Production Example 5 10 g (0,0318 moA) of 5-n-octyloxy-1-hydroxy-2-acetonaphthone and 2.
77 g (0,0477 mol) and 1.1 pyrrolidine
A solution was prepared by dissolving 3 g (0,0159 mol) in 100 parts of toluene. The mixture was boiled for 10 hours and the water was separated. After the reaction, toluene was removed under reduced pressure, and the remaining chromanone compound was dissolved in methanol (100 tf).
and gradually added sodium borohydride to obtain a chromanol compound. This chromanol compound 6
．． By heating 0 g with 4.0 g of anhydrous copper sulfate in a stream of carbon dioxide at 150-160 °C for 10 minutes and purifying the brown viscous liquid by chromatography on silica gel, chromene derivative 3 of the following formula was obtained. .8g was obtained.

As in Production Example 1, this compound was confirmed to be a compound represented by the above structural formula (5) by elemental analysis, proton nuclear magnetic resonance spectrum, and '3C-nuclear magnetic resonance spectral measurements.

Production Examples 6-14 The chromene derivatives shown in Table 1 were synthesized in the same manner as in Production Examples 1-5.

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.

Example 1 100 parts of benzene, 10 parts of polymethyl methacrylate, 0.2 parts each of the chromene derivative (11) obtained in Production Example 1 and Sheasorb UV1084 as an ultraviolet stabilizer were added and dissolved, and a slide glass (11, 2X 3.7
A cast film was made on the

The thickness was adjusted to 0.1 u+. The fatigue life of this photochromic film was measured using a xenon long life fade meter FAL25AX-HC manufactured by Suga Test Instruments Co., Ltd. Fatigue life (T%) is defined as the time required for the color density to decay to half of its initial value when the above film is exposed to a fade meter. The results are shown in Table 2.

Examples 2 to 35 The same procedures as in Example 1 were carried out 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.

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

Comparative Example 2 The same procedure as in Example 36 was carried out except that no ultraviolet stabilizer was used. The results are shown in Table 3.

Examples 71 to 86 Examples 1.7.13 and 18, except that the amount of UV stabilizer added was changed.
Same as 8. The results are shown in Table 4.

Examples 87 to 106 in Table 1 In Examples 1.7.13.18 and 32, two or three ultraviolet stabilizers were added to 100 parts of the chromene derivative.
Everything was the same as in Example 1 except that 100 parts of each seed were combined. The results are shown in Table 5.

Examples 107 to 114 In Examples 8 and 97, all procedures were the same as in 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 the chromene derivative was further prepared in Production Examples 3 to 126.
The same procedure as in Example 97 was carried out except that the chromene derivative obtained in Step 14 was used. The results are shown in Table 7.

Table 7 Example 127 Add and dissolve 100 parts of benzene, 10 parts of polymethyl methacrylate, and 0.2 parts of the chromene derivative obtained in Production Example 1, and cast a cast film on a slide glass (11.2 x 3.7 cm). I made it. The thickness was adjusted to 0.1 mm. A mercury lamp 5HL-100 made by Toshiba was attached to this photochromic film at a distance of 1 at 25℃±1℃.
The film was irradiated for 60 seconds at 0 cm to develop color, and its photochromic properties were measured. The photochromic properties were expressed as follows. The results are shown in Table 8.

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

ε (0 seconds); at the maximum absorption wavelength during light irradiation,
Absorbance of unirradiated film.

Examples 128 to 140 The chromene derivative in Example 127 was prepared in Production Examples 2 to 1.
The same procedure as in Example 127 was carried out except that the chromene derivative obtained in Step 4 was used. The results are shown in Table 8.

Table 8

Claims (1)

[Claims] (1) A chromene composition comprising (a) 100 parts by weight of chromene or its derivative and (b) 0.01 to 10,000 parts by weight of an ultraviolet stabilizer.