JP2731877B2 - Photochromic composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic composition, and more particularly to a photochromic composition which changes into a colored form upon irradiation with light including ultraviolet rays such as sunlight or light from a mercury lamp, the change being reversible and excellent durability. And a photochromic composition showing

[0002]

2. Description of the Related Art Photochromism is a phenomenon that has attracted attention for several years. When a compound is irradiated with light containing ultraviolet rays such as sunlight or light from a mercury lamp, the color changes rapidly, and the light irradiation is performed. It is a reversible action that returns to the original color when it is stopped and placed in a dark place. A compound having this property is called a photochromic compound, and various compounds have been conventionally synthesized, but their structures have no particular commonality. JP-A-61-228402 discloses the following formula (A):

Embedded image

[0003] Spirooxazine represented by

[0004]

This compound has a photochromic effect in a solution or in a polymer matrix. However, although the photochromic action of this compound in the polymer matrix is remarkable at 20 ° C. or lower, it is not good near room temperature (20 to 30 ° C.) and further in a higher temperature range than room temperature.

[0005] The inventors of the present invention have conducted intensive studies to improve the photochromic properties of the above-mentioned compounds near room temperature or at a temperature higher than that, and as a result, have succeeded in synthesizing a novel spirooxazine compound. The spirooxazine compound has been found to exhibit a very good photochromic action not only near room temperature but also in a high temperature range (30 to 40 ° C.), and has already been proposed (Japanese Patent Application No. 3-138052).

The inventors of the present invention have conducted intensive studies with the aim of improving the durability of the photochromic action of the above spirooxazine compound and developing a photochromic lens of practical value. It has been found that the above object can be achieved by dispersing an ultraviolet stabilizer in a specific polymer, and the present invention has been completed.

[0007]

That is, the present invention provides: (1) The following general formula [I]

Embedded image

[0008] (wherein, R ₁ and R ₂ are the same or different alkyl group, and they may form a cyclohexane ring together, R ₃ is an alkyl group, R ₄ Is a hydrogen atom or a halogen atom.)

(2) 0.001 to 20 parts by weight of a mixture of the ultraviolet stabilizer with respect to 100 parts by weight of the copolymer of 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane It is a photochromic composition that is blended.

In the general formula [I], the alkyl groups represented by R ₁ and R ₂ are not particularly limited in the number of carbon atoms. Generally, an alkyl group having 1 to 10 carbon atoms is preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. The above R ₁ and R ₂ may together form a cyclohexane ring.

In the general formula [I], as R ₃ , the alkyl groups described above for R ₁ and R ₂ can be used.

In the general formula [I], R ₄ is a hydrogen atom or a halogen atom. Examples of the halogen atom include fluorine, chlorine, iodine, and iodine atoms.

Specific examples of the spirooxazine compound represented by the general formula [I] preferably used in the present invention are as follows.

(1) 1,3,3-trimethylspiro [2
H-indole-2,3 '-[3H] pyrido [4,3-
f] [1,4] benzoxazine]

(2) 4-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine]

(3) 5-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine]

(4) 6-fluoro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine]

(5) 5-chloro-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine]

(6) 5-bromo-1,3,3-trimethylspiro [2H-indole-2,3 '-[3H] pyrido [4,3-f] [1,4] benzoxazine]

(7) 1'-methyldispiro [cyclohexane-1,3 '-[3H] indole-2' (1 '
H), 3 "-[3H] pyrido [4,3-f] [1,4]
Benzoxazine)

(8) 4-fluoro-1'-methyldispiro [cyclohexane-1,3 '-[3H] indole-
2 '(1'H), 3 "-[3H] pyrido [4,3-f]
[1,4] benzoxazine]

(9) 5-Fluoro-1'-methyldispiro [cyclohexane-1,3 '-[3H] indole-
2 '(1'H), 3 "-[3H] pyrido [4,3-f]
[1,4] benzoxazine]

(10) 6-Fluoro-1'-methyldispiro [cyclohexane-1,3 '-[3H] indole-2'(1'H), 3 "-[3H] pyrido [4,3-
f] [1,4] benzoxazine]

(11) 5-chloro-1'-methyldispiro [cyclohexane-1,3 '-[3H] indole-
2 '(1'H), 3 "-[3H] pyrido [4,3-f]
[1,4] benzoxazine]

(12) 5-bromo-1'-methyldispiro [cyclohexane-1,3 '-[3H] indole-
2 '(1'H), 3 "-[3H] pyrido [4,3-f]
[1,4] benzoxazine]

[0026] The second component of the photochromic composition of the present invention is an ultraviolet light stabilizer.

As the UV stabilizer, known UV stabilizers added to various plastics can be used without any limitation. In the present invention, considering the durability of the photochromic action of the spirooxazine compound, among various UV stabilizers, a singlet oxygen quencher, a hindered amine light stabilizer (a hindered amine structure and a hindered phenol structure in one molecule). Light stabilizers), hindered phenol antioxidants, and sulfur-based antioxidants are preferably used.

Among these, a singlet oxygen quencher, a hindered amine light stabilizer and a hindered phenol antioxidant are preferable, and a hindered amine light stabilizer is particularly preferable.

Further, by combining two or more of these ultraviolet stabilizers, better results can be obtained than when they are used alone. Particularly preferred are hindered amine light stabilizers, or a combination of a hindered amine light stabilizer and a singlet oxygen quencher or a hindered phenol antioxidant.

Further, a combination of two kinds of hindered amine light stabilizers and a hindered phenol antioxidant, or a combination of three kinds of hindered amine light stabilizers, singlet oxygen quenchers and hindered phenol antioxidants Is preferred

The singlet oxygen quencher preferably used in the present invention includes a complex of Ni ²⁺ with an organic ligand, cobalt (III) -tris-dibutyldithiocarbamate, iron (II) -diisopropyldithiocarbamate and Cobalt (II) -diisopropyldithiocarbamate and the like can be mentioned. 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, for example.

Embedded image

Other examples include a complex of Ni ²⁺ and an organic ligand which is commercially available from American Cyanamid Co. under the trade name of cyansorb 108 (ACC).

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

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

(However, the above formulas (a), (c), (d),
In (e), (f) and (g), R ¹ , R ² , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are alkyl groups, R ³ and R ⁸ are hydrogen atoms or alkyl groups, and R ¹³ is a benzoyl group, acryloyl group or methacryloyl. R ¹⁴ is an alkyl group or an acyl group, and m and n are positive integers. )

The above (a), (c), (d), (e),
In (f) and (g), the alkyl group is not particularly limited to the number of carbon atoms, but is generally preferably in the range of 1 to 12 for reasons such as easy availability of these compounds.

Further, as a hindered amine light stabilizer, Sumisorb (Sumisor) manufactured by Sumitomo Chemical Co., Ltd. is used.
b) LS-2000 and LS-2001 (both are trade names).

The hindered phenol antioxidant suitable as an ultraviolet stabilizer is specifically exemplified as follows.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

(However, the above formulas (h), (h), (h),
In (sa), (si), (su) and (se), R ¹ , R ² , R
³ , R ⁴ and R ⁵ are alkyl groups. )

The above (h), (g), (h), (h),
In (S), (S) and (S), the alkyl group is not particularly limited to the number of carbon atoms, but is generally preferably in the range of 1 to 20 for reasons such as easy availability of these compounds. .

The following are specific examples of the sulfur-based antioxidants suitable as ultraviolet stabilizers.

Embedded image

Embedded image

(However, in the above formulas (so) and (ta), R ¹
And R ² are alkyl groups. )

In the above (so) and (ta), the alkyl group is not particularly limited to the number of carbon atoms, but is generally preferably in the range of 1 to 20 for reasons such as easy availability of these compounds. .

The mixing ratio of the above-mentioned spirooxazine compound and ultraviolet stabilizer is 100
The ultraviolet stabilizer is used in an amount of 0.01 to 10,000 based on parts by weight.
It is preferably in the range of 0 parts by weight. When the amount of the ultraviolet stabilizer is less than 0.01 part by weight, the effect of improving the photochromic repetition durability may hardly be recognized. On the other hand, when the amount exceeds 10,000 parts by weight, the after-mentioned When dispersed in a copolymer of 2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane, molding tends to be difficult. From the viewpoint of the photochromic property of the obtained photochromic composition, the UV stabilizer is more preferably in the range of 50 to 600 parts by weight.

In the photochromic composition of the present invention, the mixture of the above-mentioned spirooxazine compound and the ultraviolet stabilizer is 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane (hereinafter simply referred to as B
MDBP). BM
The DBP copolymer has a high refractive index and a low Abbe number,
It is also excellent in impact strength, dyeability and surface hardness, and is an excellent copolymer as an optical lens.

As a monomer copolymerized with BMDBP, a monomer copolymerizable with BMDBP can be employed without any limitation. When obtaining an objective optical lens in the present invention, the following monomers are preferred from the viewpoint of optical characteristics.

For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride; methyl acrylate,
Acrylic acid and methacrylic acid ester compounds such as methyl methacrylate, benzyl methacrylate, phenyl methacrylate and 2-hydroxyethyl methacrylate; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; methylthioacrylate, benzylthioacrylate, benzylthio Radical polymerizable monofunctional monomers such as thioacrylic acid and thiomethacrylate compounds such as methacrylate; vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene and bromostyrene.

Also, polyacrylic acid and polyhydric methacrylic acid such as ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, etc. Ester compounds: diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate, etc. Allyl compound; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ate Le, 1,4-bis (methacryloyl thio methyl) polyhydric thio acrylate and polyhydric thio methacrylic acid ester compounds such as benzene, it may be mentioned radical polymerizable polyfunctional monomer such as divinylbenzene.

The copolymerization ratio of the above-mentioned BMDBP and the monomer copolymerizable therewith is adopted from a wide range, but is excellent in high refractive index and low Abbe number, impact strength, dyeability and surface hardness. BMDBP is 10 to obtain
Preferably, the amount is 80% by weight, and the amount of monomers copolymerizable therewith is in the range of 20 to 90% by weight.

The blending amounts of the spirooxazine compound and the UV stabilizer dispersed in the above-mentioned BMDBP copolymer are as follows:
The total amount of the spirooxazine compound and the ultraviolet stabilizer is 0.001 to 100 parts by weight based on 100 parts by weight of the BMDBP copolymer.
20 parts by weight, preferably 0.1 to 10 parts by weight.

Dispersion of a mixture of a spirooxazine compound and an ultraviolet stabilizer in a copolymer of BMDBP is carried out by the method of BMDBP.
A method is generally employed in which BP, a monomer copolymerizable therewith, a spirooxazine compound and an ultraviolet stabilizer are mixed and then polymerized.

In the present invention, in order to develop various intermediate colors such as gray, amber, brown and the like, which are preferred colors as a photochromic lens, the above-mentioned spirooxazine compound has the following formula

Embedded image

It is preferable to mix a chromene derivative represented by the formula (wherein R ₅ is a hydrogen atom or an alkoxy group).

Specific examples of chromene derivatives that can be suitably used in the present invention are as follows.

(1) Spiro [norbornane-2,2'-
[2H] benzo [h] chromene]

(2) 7-methoxyspiro [norbornane-2,2 '-[2H] benzo [h] chromene]

(3) 7-ethoxyspiro [norbornane-2,2 '-[2H] benzo [h] chromene]

(4) 7-propoxyspiro [norbornane-2,2 '-[2H] benzo [h] chromene]

In the present invention, the mixing ratio of the above-mentioned spirooxazine compound and chromene derivative can be arbitrarily selected according to the desired color tone. However, in order to adjust the color tone to brown, gray, amber or the like, generally, The chromene derivative is preferably used in an amount of 1 to 5,000 parts by weight, preferably 5 to 500 parts by weight, more preferably 10 to 300 parts by weight, based on 100 parts by weight of the spirooxazine compound.

[0059]

As described above, the photochromic composition of the present invention changes from colorless to colored by light including ultraviolet rays such as sunlight or light from a mercury lamp, and the change is reversible and excellent durability. Shows sex. Further, according to the present invention, by using a spirooxazine compound and a chromene derivative together, various intermediate colors such as gray, brown, and amber can be easily obtained.

Therefore, the photochromic composition of the present invention has excellent properties as a photochromic lens,
It can also be used as a material for optical filter materials, display materials, light meters, decorations, and the like.

[0061]

The present invention will be described in more detail with reference to the following examples. However, needless to say, the present invention is not limited to these examples. "Part" in the examples
Is "parts by weight".

The ultraviolet stabilizer used in the examples is a compound represented by the following formula.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image-Sumilizer TP-D (trade name: manufactured by Sumitomo _{Chemical) (H 25 C 12 SCH 2} CH 2 COOCH 2) 4 C

First, a production example of a spirooxazine compound represented by the general formula [I] used in each example will be described. The method for producing the spirooxazine compound represented by the general formula (I) is not particularly limited, and may be obtained by any synthesis method. However, typical methods that are generally preferably employed are as follows: The following production examples also followed this method.

A typical production method is represented by the following general formula [II]

Embedded image

(R ₂₁ and R ₂₂ are the same or different alkyl groups, and they may be combined to form a cyclohexane ring, R ₂₃ is an alkyl group, and R ₂₄ is , A hydrogen atom or a halogen atom.) And a compound of the formula [III]

Embedded image

In this method, a nitroso compound is reacted.

The reaction between the compound represented by the general formula [II] and the compound represented by the formula [III] can be carried out as follows. That is, the reaction ratio of these two compounds is adopted from a wide range, but is generally from 1:10 to 1:10.
It is selected from the range of 10: 1 (molar ratio). The reaction temperature is usually preferably from 0 to 200 ° C., and as the solvent, an organic solvent such as methyl alcohol, ethyl alcohol,
N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene and the like are used.

Production Example 1

Embedded image

1.73 g (0.01 mol)

Embedded image

1.74 g (0.01 mol) was dissolved in 100 ml of ethyl alcohol and refluxed for 2 hours. After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel to obtain 1.8 g of a spirooxazine compound represented by the following formula.

Embedded image

The elemental analysis value of this compound was C 76.5.
8%, H 5.78%, N 12.75%, O 4.8
9%, C 76.59 relative to C ₂₁ H ₁₉ N ₃ O
%, H 5.78%, N 12.77%, O 4.86
%.

Further, when the proton nuclear magnetic resonance spectrum was measured, a spectrum of 10H based on a proton of a quinoline ring, a proton of an indoline ring and a proton of an oxazine ring was found around δ 6.58 to 9.10 ppm, δ 3.2
Around ₃ ppm based on> N—CH ₃ bond protons
The H spectrum showed a 6H spectrum at around δ 1.35 ppm based on the proton of the methyl group.

Further, when ¹³ C-nuclear magnetic resonance spectrum was measured, a spectrum based on the carbons of the benzene ring, quinoline ring and oxazine ring of indoline was found at about δ100 to 160 ppm, a spectrum based on spiro carbon was found near δ99 ppm, and a spectrum was found near δ20 to 30 ppm. Shows the spectrum based on the carbon of the methyl group.

[0074] The measured infrared absorption spectrum (IR), C = N bond near 1620 cm ^-1, 148
0 cm ^-1 aromatic C-H bonds in the vicinity of, the spectral absorption of ether bond appeared around 1250 cm ^-1.

From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (1). This corresponds to the compound of (1) among those specifically exemplified as spirooxazine compounds in the above-mentioned "Means for Solving the Problems".

Production Examples 2 to 5 Spirooxazine compounds shown in Table 1 were synthesized in the same manner as in Production Example 1. The obtained product was subjected to a structural analysis using the same structure confirming means as in Production Example 1, and as a result, Table 1 was obtained.
Was confirmed to be a compound represented by the structural formula shown in Table 1.

[Table 1]

The compound 2 obtained in Production Example 2 corresponds to a mixture of the compounds (2) and (4) among those specifically exemplified as spirooxazine compounds in the above “Means for Solving the Problems”. Compound 3 obtained in Example 3 corresponds to the exemplified compound of (7), and compound 4 obtained in Production Example 4.
Corresponds to the exemplified compound of (9), and the compound 5 obtained in Production Example 5 also corresponds to a mixture of the compounds of (8) and (10).

Table 2 shows chromene derivatives used in the following examples.

[Table 2]

Examples 1 to 19 2,2-bis- (4-methacryloyloxyethoxy-
Spirooxazine compound (1) is added to a composition consisting of 60 parts of 3,5-dibromophenyl) propane and 40 parts of styrene.
And 0.2 parts of each of the various UV stabilizers shown in Table 3.
And 1 part of perbutyl ND as a radical polymerization initiator were added and mixed well.

The mixture was poured into a mold composed of a gasket composed of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was carried out using an air furnace at 30 ° C. to 90 ° C. over 18 hours, gradually increasing the temperature, and maintaining the temperature at 90 ° C. for 2 hours. After the polymerization was completed, the mold was taken out of the air furnace, and after standing to cool, the polymer was removed from the glass of the mold.

The obtained molded product was subjected to a xenon long life fade meter FAL-25AX manufactured by Suga Test Instruments Co., Ltd.
-The fatigue life was measured by HC.

For the fatigue life (T _1/2 ), the absorbance at the maximum absorption wavelength based on the spirooxazine compound is initially (T ₀ )
The time required for the absorbance to fall to one half of the absorbance was expressed.
However, the absorbances at T ₀ and T _1/2 are values obtained by subtracting the absorbance of the unirradiated film at the maximum absorption wavelength.
The absorbance of ₀ was measured 60 seconds after light irradiation.

The results are shown in Table 3.

The results are shown in Table 3 as Comparative Example 1, except that no ultraviolet stabilizer was used.

[Table 3]

Examples 20 to 38 The same procedures as in Example 1 were carried out except that the spirooxazine compound used in Example 1 was changed to the spirooxazine compound (3) obtained in Production Example 3. The results are shown in Table 4.

The results are shown in Table 4 as Comparative Example 2, except that no ultraviolet stabilizer was used.

[Table 4]

Examples 39 to 54 The procedures of Examples 1, 7, 10 and 18 were the same as in Examples 1, 7, 10 and 18 except that the amount of the ultraviolet stabilizer was changed. Table 5 shows the results.

[Table 5]

Examples 55 to 74 In Example 1, two or three ultraviolet stabilizers were added to 100 parts of the spirooxazine compound, respectively.
All the procedures were the same as in Example 1, except for the combination of 00 parts. The results are shown in Table 6.

[Table 6]

Examples 75 to 82 The same procedures as in Examples 57 and 66 were carried out except that the composition ratio of the ultraviolet stabilizer was changed. The results are shown in Table 7.

[Table 7]

Examples 83 to 85 The same procedures as in Example 1 were carried out except that the spirooxazine compound was changed to the spirooxazine compound obtained in Production Examples 2, 4 and 5. The results are shown in Table 8.

[Table 8]

Examples 86 to 104 In Example 1, 0.3 part of the spirooxazine compound (1), 0.2 part of the chromene derivative (2) and 0.5 parts of the ultraviolet stabilizer shown in Table 9 of Production Example 1 were used. The same procedures as in Example 1 were carried out except for the addition of parts. Further, a change in color tone was visually observed.

The fatigue life (T _1/2 ) is the time required for the absorbance at the maximum absorption wavelength based on each of the spirooxazine compound and the chromene derivative to fall to の of the initial (T ₀ ) absorbance. It was expressed by. Where T
The absorbance at ₀ and T _1/2 is a value obtained by subtracting the absorbance of the unirradiated film at the maximum absorption wavelength based on each compound, and the absorbance at T ₀ is 60% after light irradiation.
It was measured after a lapse of seconds.

Table 9 shows the results. In Table 9, the color tone at T _1/2 is the color tone of the chromene derivative at T _1/2 .

The same procedure as above was carried out except that no ultraviolet stabilizer was used, and the results are shown in Table 9 as Comparative Example 3.

[Table 9]

Examples 105 to 123 The mixing ratios of the spirooxazine compound and the chromene derivative used in Example 86 were 0.25 parts and 0.1%, respectively.
Example 86 was repeated except that the amount was changed to 5 parts and the ultraviolet stabilizer was changed to 0.75 part. The results are shown in Table 10.

The same procedure as described above was carried out except that no ultraviolet stabilizer was used.
It was also described in.

[Table 10]

Examples 124 to 142 The spirooxazine compound and the chromene derivative used in Example 86 were replaced by 0.25 part of the spirooxazine compound (3) and 0.2 part of the chromene derivative (1) of Production Example 3, respectively.
The same procedure as in Example 86 was carried out, except that the parts were changed to 5 parts. The results are shown in Table 11.

The same procedure as described above was conducted except that the ultraviolet stabilizer was not used.
It was also described in.

[Table 11]

Examples 143 to 161 In Example 124, the chromene derivative (2) was added.
Spirooxazine compound (3) and chromene derivative (2)
Of 0.5 part, 0.25 part and 0.1 part, respectively.
Example 124 was repeated except that the amount was 25 parts and the ultraviolet stabilizer was 1.0 part. The results are shown in Table 12.

The same procedure as described above was carried out except that no ultraviolet stabilizer was used.
It was also described in.

[Table 12]

Examples 162 to 177 In Examples 86, 92, 95 and 103, except that the added amount of the ultraviolet stabilizer was changed.
Same as 2, 95 and 103. The results are shown in Table 13.

[Table 13] (Part 1)

[Table 13] (Part 2)

Examples 178 to 197 In Example 86, the total amount of the spirooxazine compound and the chromene derivative was 100 parts, and
All the procedures were the same as in Example 86, except that 100 parts of each of the species or three were combined. The results are shown in Table 14.

[Table 14] (Part 1)

[Table 14] (Part 2)

[Table 14] (Part 3)

Examples 198 to 205 All of Examples 180 and 189 were the same as Examples 180 and 189 except that the composition ratio of the ultraviolet stabilizer was changed. The results are shown in Table 15.

[Table 15]

Examples 206 to 208 In Example 86, the spirooxazine compound (2)
Same as Example 86 except that (4) and (5), the chromene derivatives (1) and (2) were combined and 100 parts of an ultraviolet stabilizer was added to the total of 100 parts of the spirooxazine compound and the chromene derivative I made it. The results are shown in Table 16.

[Table 16]

Reference Example The spirooxazine compounds produced in Production Examples 1 to 5 were dissolved and dispersed in poly (methyl methacrylate) using benzene, and cast films were prepared on slide glasses (11.2 × 3.7 cm). The concentration of the compound contained in the film was adjusted to 1.0 × 10 ⁻⁴ mol / g, and the thickness was adjusted to 0.1 mm. To this photochromic film, a mercury lamp SHL-
100 at 35 ± 1 ° C. for a distance of 10 cm for 60 seconds,
The film was developed and the photochromic properties were measured. The photochromic properties were expressed as follows. The results are shown in Table 17.

Maximum absorption wavelength (λ _max ): Spectrophotometer 220A manufactured by Hitachi, Ltd.
_max (unit: nm) was determined. ε (60): Absorbance at the maximum absorption wavelength after 60 seconds of light irradiation of the film under the above conditions. ε (0): absorbance of the unirradiated film at the maximum absorption wavelength upon light irradiation.

[Table 17]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinsuke Tanaka 1-1, Mikage-cho, Tokuyama-shi, Yamaguchi Prefecture Inside Tokuyama Soda Co., Ltd. Inventor Satoshi Kubota 2329-2 Ina, Ina-gun, Nagano Pref.

Claims (2)

(57) [Claims] (1) The following formula: (However, R ₁ and R ₂ are the same or different alkyl groups, respectively, may be combined to form a cyclohexane ring, R ₃ is an alkyl group, R ₄ is hydrogen A mixture of 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane is 100% by weight of a mixture of the spirooxazine compound represented by the formula (2): A photochromic composition which is added in an amount of 0.001 to 20 parts by weight based on parts. (1) The following formula: (However, R ₁ and R ₂ are the same or different alkyl groups, respectively, may be combined to form a cyclohexane ring, R ₃ is an alkyl group, R ₄ is hydrogen (2) a spirooxazine compound represented by the following formula: (Where R ₅ is a hydrogen atom or an alkoxy group) a mixture of (3) an ultraviolet stabilizer (provided that the spirooxazine compound 100 of (1) is used)
The chromene derivative of (2) is 1 to 5,0 parts by weight based on parts by weight.
0.001 to 20 parts by weight based on 100 parts by weight of a copolymer of 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane.
A photochromic composition formulated by weight.