JPH0820768A - Photochromic composition - Google Patents

Abstract

PURPOSE:To obtain a photochromic composition which undergoes no change in hue for a long time by combining a new spirooxazine compound with a chromene compound. CONSTITUTION:This composition comprises 100 pts.wt. sprio-oxazine compound represented by the formula [wherein the rings alpha and beta are each a hydrocarbon aromatic ring or an unsaturated heterocyclic ring which may have the same or different substituents; R<4> is alkylene or (A-B-A)m (wherein A is an alkylene; B is oxygen, carbonyl, COO, OCO, or an arylene; and (m) is an integer of 1-3); R<1> is an alkyl, cycloalkyl, aryl or alkoxycarbonylalkyl; R<2> and R<3> may be the same or different alkyl groups and are cycloalkyl or alkoxyalkyl groups, provided that they may be combined with each other to form a ring; and (n) is an integer of 1-4] and 1-1000 pts.wt. chromene compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic composition having various color tones such as gray, brown and amber and having excellent durability against repeated coloring and decoloring.

[0002]

2. Description of the Related Art Photochromism is a phenomenon that has been attracting attention for several years, and when a compound is irradiated with light including ultraviolet rays such as sunlight or the light of a mercury lamp, the color of the compound rapidly changes and the irradiation of light is prevented. It is a reversible action that returns to the original color when stopped and placed in the dark. A compound having this property is called a photochromic compound, and various compounds have been synthesized conventionally, but no special commonality is recognized in the structure.

A chromene compound is known as a photochromic compound. The color tone of the chromene compound is orange to yellow. On the other hand, spirooxazine compounds are also well known as photochromic compounds, and the color tone of this compound is red to blue.

When these compounds are used alone, the desired color tone may not be obtained in some cases. In particular, when used as a photochromic lens, color tones such as gray, brown and amber are preferred, but these color tones cannot be obtained by the above compounds alone. Therefore, as a result of mixing the above-mentioned chromene compound and spirooxazine compound, the present inventors succeeded in developing various mixed colors such as gray, brown and amber.

[0005]

However, it has been found that the mixed color of these two types of photochromic compounds exhibits excellent reversible durability, but the color tone gradually changes with long-term use. Regarding the cause of this, as a result of examination by the present inventors, it was revealed that the repeated durability of coloration-fading of the above-mentioned spirooxazine compound is inferior to the durability of the chromene compound, so that a change in color tone occurs due to long-term use. It was

Therefore, the present inventors considered that if the spirooxazine compound is made to have a coloring-fading repeating durability that is almost the same as that of the chromene compound, a mixture which does not change its color tone over a long period of time can be obtained. . Therefore, there has been a demand for the development of a photochromic composition comprising a spirooxazine compound and a chromene compound, which have comparable durability.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above problems. As a result, they have found that the above problems can be solved by combining a novel spirooxazine compound found by the present inventors with a chromene compound, and completed the present invention.

That is, the present invention is

(A) The following general formula (1)

[0010]

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[Wherein the α ring and the β ring are a hydrocarbon aromatic ring or an unsaturated heterocyclic ring which may have the same or different substituents, and R ⁴ is an alkylene group or-(AB-- A) _m − (where A is an alkylene group, B is an oxygen atom, a carbonyl group, —COO—, —OCO— or an arylene group, and m is an integer of 1 to 3) and R ¹ Is an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonylalkyl group, R ² and R ³ are the same or different alkyl groups, cycloalkyl groups or alkoxyalkyl groups, and R ² and R ³ are the same. And may form a ring, and n is an integer of 1 to 4].
100 parts by weight and (B) chromene compound 1-1000
A photochromic composition comprising 0 parts by weight.

The component (A) of the photochromic composition in the present invention is a spirooxazine compound represented by the above general formula (1).

The α-ring and β-ring in the above general formula (1) are hydrocarbon aromatic rings or heteroaromatic rings, and specific examples thereof include benzene ring, naphthalene ring, phenanthrene ring and the like. Aromatic ring consisting of 1 monocyclic ring or 2 to 4 condensed rings thereof; nitrogen-containing heterocyclic ring such as pyrrole ring, pyridine ring, quinoline ring, isoquinoline ring, piperidyl ring; oxygen-containing ring such as furan ring and benzofuran ring Heterocycles: 5-membered rings containing oxygen, sulfur, nitrogen atoms such as sulfur-containing heterocycles such as thiophene ring and benzothiophene ring,
A 6-membered ring or an unsaturated heterocycle in which a benzene ring or a cyclohexene ring is condensed therewith can be mentioned.

R ² and R ^{3 in} the general formula (1) are the same or different alkyl groups, cycloalkyl groups and alkoxyalkyl groups. The alkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t-butyl group.

The cycloalkyl group is not particularly limited, but generally has 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group,
Examples thereof include a cyclohexyl group, a norbornyl group, and an adamantyl group.

The above alkoxyalkyl group is not particularly limited, but generally has 2 to 20 carbon atoms,
It is preferably 2 to 8. Specific examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group and a methoxybutyl group. Also, R ² and R ³ may be taken together to form a ring. The spiro ring composed of a spiro atom, R ² and R ³ is not particularly limited, but generally has 3 to 15 carbon atoms, preferably 3 to 10 carbon atoms. Further, the spiro ring may contain an oxygen atom derived from an alkoxyalkyl group. Specific examples of the spiro ring include a cyclopropyl ring, a cyclopentyl ring, a cyclohexyl ring, a bicyclononane ring, an adamantyl ring and a tetrahydropyranyl ring.

When the α ring and β are substituted, the substituents are a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group,
Examples thereof include an aralkoxy group, an aryloxy group, an acyloxy group, an optionally substituted amino group, a nitro group, a cyano group, a halogenoalkyl group or an alkoxycarbonyl group, and one or more of these substituents are included. Can be Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

The above alkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 carbon atoms.
Through 4. When the alkyl group is specifically exemplified,
Examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group.

The cycloalkyl group is not particularly limited, but generally has 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group,
Examples thereof include a cyclohexyl group, a norbornyl group, and an adamantyl group.

The above aralkyl group is not particularly limited, but generally has 7 to 20 carbon atoms, preferably 7 to 15 carbon atoms. Specific examples of the aralkyl group include a benzyl group, a phenethyl group and a (2-naphthyl) methyl group.

The above aryl group is not particularly limited, but generally has 6 to 20 carbon atoms, preferably 6 carbon atoms.
Through 14 Specific examples of the aryl group include a phenyl group, a naphthyl group and a tolyl group.

The above-mentioned alkoxy group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

The above-mentioned aralkoxy group is not particularly limited, but generally has 7 to 20 carbon atoms, preferably 7 to 15 carbon atoms. Specific examples of the aralkoxy group include a benzyloxy group, a phenethyloxy group,
An example is a (2-naphthyl) methyloxy group.

The aryloxy group is not particularly limited, but generally has 6 to 20, preferably 6 to 14 carbon atoms. Specific examples of the aryloxy group include a phenoxy group and a 2-naphthyloxy group.

The acyloxy group is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the acyloxy group include a formyloxy group, an acetoxy group, a benzoyloxy group, and a (meth) acryloyloxy group.

The above alkoxyalkyl group is not particularly limited, but generally has 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. Specific examples of the alkoxyalkyl group include a methoxymethyl group, a methoxyethyl group and an ethoxyethyl group.

The halogen atom in the above halogenoalkyl group is fluorine, chlorine, bromine or the like, and the alkyl group preferably has 1 to 4 carbon atoms. Specific examples of the halogenoalkyl group include a trifluoromethyl group, a trichloromethyl group and a tribromomethyl group.

As the above-mentioned alkoxycarbonyl group,
It is not particularly limited, but generally has 2 to 20 carbon atoms,
It is preferably 2 to 12. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group and a butoxycarbonyl group.

The above-mentioned amino group which may have a substituent is not particularly limited, but generally includes an amino group having a substituent such as an alkyl group having 0 to 10 carbon atoms and a hetero atom-containing alkyl group. However, these substituents may form a ring together. Specific examples of the amino group include amino group, methylamino group, ethylamino group, propylamino group, isopropylamino group, dimethylamino group, diethylamino group, methylethylamino group, 2-hydroxyethylamino group, di ( 2-hydroxyethyl) amino group, piperidinyl group, morpholinyl group, N-methylpiperazinyl group, thiomorpholinyl group,
Examples thereof include an aziridinyl group and a pyrrolidinyl group.

R ^{4 in the} above general formula (1) is an alkylene group or — (ABAA) _m — (where A is an alkylene group, B is an oxygen atom, a carbonyl group, —COO—, —OCO). -Or an arylene group, and m is an integer of 1 to 3).

The alkylene group for R ⁴ is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and an n-butylene group.

A in R ⁴ can be used without any limitation as long as it is an alkylene group, but it generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the alkylene group include methylene group, ethylene group, n
-A propylene group and n-butylene group can be mentioned. B in R ⁴ is an oxygen atom, a carbonyl group, or -CO.
It is an O-, -OCO- or arylene group. The arylene group is not particularly limited, but generally has 6 to 20, preferably 6 to 14 carbon atoms.
Specific examples of the arylene group, a phenylene group,
A naphthylene group can be mentioned.

If R ^{1 in the} above general formula (1) is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an alkoxycarbonylalkyl group, known substituents can be used without any limitation. The alkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t-butyl group.

The cycloalkyl group is not particularly limited, but generally has 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group,
Examples thereof include a cyclohexyl group, a norbornyl group, and an adamantyl group. The aryl group is not particularly limited, but generally has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group and a tolyl group. The above-mentioned alkoxycarbonylalkyl group is not particularly limited, but generally has 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms. Specific examples of the alkoxycarbonylalkyl group include a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a propoxycarbonylmethyl group, and a methoxycarbonylethyl group.

The compound represented by the above-mentioned general formula (1) of the present invention generally exists as a colorless or pale yellow solid or viscous liquid at room temperature and atmospheric pressure, and has the following (a) to (d).
It can be confirmed by such means.

(A) Proton nuclear magnetic resonance spectrum ( ¹
The type and number of protons present in the molecule can be known by measuring (H-NMR). That is,
Spectra based on aromatic protons and oxazine ring protons around δ 6.5-9 ppm, δ 1.0
A spectrum based on the protons of the alkyl group and the alkylene group appears at around 2.5 ppm, and a spectrum based on the protons of the nitrogen-bonded carbon and the sulfur-bonded carbon near δ2.5 to 4.5 ppm. Further, the number of protons of each bonding group can be known by comparing the respective spectrum intensities relatively.

(B) The weight ratio of carbon, hydrogen, nitrogen, sulfur and halogen can be determined by elemental analysis. Furthermore, the sum of the weight ratios of the recognized elements is 100.
It is possible to calculate the weight ratio of oxygen by subtracting from. Therefore, the composition of the corresponding product can be determined.

(C) ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
It is possible to know the type of carbon present in the molecule by measuring -NMR). Approximately 20 to 50 ppm, spectra based on primary and secondary carbons, δ110
A spectrum based on carbon of an aromatic hydrocarbon group or an unsaturated heterocyclic group appears at about 150 ppm, a spectrum based on spiro carbon near δ100 ppm, and a spectrum based on carbonyl carbon near δ170 ppm.

(D) By measuring the infrared absorption spectrum (IR), the kind of functional group present in the molecule can be known. Representative absorption, C = N bond near 1620 cm ^-1, spectral absorption of the aromatic C-H bonds appears at around 1480 cm ^-1.

The method for producing the compound represented by the general formula (1) of the present invention is not particularly limited and may be obtained by any synthetic method. A typical method that is generally adopted is described below.

The following general formula (2)

[0042]

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(Wherein the α-ring is a hydrocarbon aromatic ring which may have a substituent or an unsaturated heterocycle, and R ⁴ is a linear or branched alkylene group or-(AB- A) _m − (where A is an alkylene group, B is an oxygen atom, a carbonyl group, —COO—, —OCO— or an arylene group, and m is an integer of 1 to 3) and R ¹ Is an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonylalkyl group, R ² and R ³ are the same or different alkyl groups, cycloalkyl groups or alkoxyalkyl groups, and R ² and R ³ are the same. To form a ring, and n is an integer of 1 to 4] and a general formula (3)

[0044]

[Chemical 4]

The method is to react a nitroso compound represented by (wherein β ring is a hydrocarbon aromatic ring optionally having a substituent or an unsaturated heterocycle).

The reaction between the compound represented by the general formula (2) and the compound represented by the general formula (3) is carried out as follows. The reaction ratio of these two compounds is adopted from a wide range, but generally 1:10 to 10: 1.
It is selected from the range of (molar ratio). The reaction temperature is usually 0
The temperature is preferably ˜200 ° C. As the solvent, organic solvents such as methyl alcohol, ethyl alcohol, N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene and toluene are used.

When an amino group which may have a substituent is introduced into the β ring, when the compounds represented by the general formulas (2) and (3) are reacted, the corresponding amino compounds are simultaneously reacted. I'll do it. At this time, the molar ratio of the amino compound to the compound represented by the general formula (3) is 1: 1 to 10 :.
1, preferably from 2: 1 to 6: 1.

The spirooxazine compound represented by the above general formula (1) of the present invention is well soluble in general organic solvents such as toluene, chloroform and tetrahydrofuran. When the spirooxazine compound represented by the general formula (1) is dissolved in such a solvent, the solution is generally almost colorless and transparent, and when it is exposed to sunlight or ultraviolet rays, it rapidly develops color, and when it is shielded from light, the original It exhibits a good reversible photochromic effect that returns to colorless.

The component (B) of the photochromic composition in the present invention is a chromene compound. As the chromene compound, a known compound having a chromene skeleton and having photochromic properties can be adopted without any limitation. In the present invention, the chromene compound represented by the following formula (4) is particularly preferably used because it has excellent photochromic properties.

[0050]

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(Provided that R ¹ , R ² , R ³ and R ⁴ are the same or different hydrogen atoms, hydrocarbon groups, substituted amino groups or saturated heterocyclic groups, and R ³ and R ⁴ together are May form a ring,

[0052]

[Chemical 6]

The group represented by is an optionally substituted aromatic hydrocarbon group or unsaturated heterocyclic group. )

Specific examples of the spirooxazine compound and chromene compound that can be preferably used in the present invention include the following compounds. Spirooxazine compound: (1) 1- (methylthio) ethyl-3,3-dimethylspiro [indole-2 (2H), 3 '-[3,2-a]
[1,4] naphthodioxane] (2) 6 "-morpholino-8" -methoxy-1 '-[2
-(Phenylthio) ethyl] -6'-fluoro-7'-
Methyl dispiro [cyclohexane-1,3 '-[3H]
Indole-2 ', 3 "-[3,2-a] [1,4] naphthoxazine" (3) 6 "-morpholino-1'-(phenylthio) ethyl-6'-fluorodisspiro [cyclohexane-1,
3 '-[3H] indole-2'(2'H), 3 "-
[3,2-a] [1,4] naphthoxazine] (4) 1- (cyclohexylthio) ethyl-6-fluoro-7-methyl 3,3-dimethylspiro [indole-
2 (2H), 3 '-[3H] pyrido [4,3-f] [1,
4] benzoxazine] (5) 1 '-[(3-methylthiopropionyloxy)
Ethyl] dispiro [tetrahydropyranyl-4,3'-
[3H] -7-azaindole-2 ', 2 "-[3H]
Pyrido [2,3-h] [1,4] benzoxazine] (6) 6'-thiomorpholino-1-[(1-naphthylthio) ethyl] -3,3,4,5-tetramethyl-6-tri Fluoromethyl spiro [indole-2,3 '-[3
H] pyrido [3,4-f] [1,4] benzoxazine] (7) 1- [2- (3-methylthio) propionyl]-
3,3-Dimethylspiro [pyrido [3,4-f] indole-2,3'-pyrido [4,3-e] [1,4] oxazine] (8) 9'-methoxy-1- (3- Methylthiopropion-2-yl) -3,3-dimethylspiro [pyrido [3,
4-f] indole-2,2 '-[2,3-a] [1,
4] naphthooxazine] (9) 1 '-[8- (methylthio) octyl] disspiro [cyclohexane-1,3'-[3H] dibenzo [e,
g] indole-2 ', 2 "-[3H] N-phenylpyrrolino [4,5-e] [1,4] oxazine]

Chromene compound: (1) Spiro [norbornane-2,2 '-[2H] benzo [h] chromene] (2) Spiro [bicyclo [3.3.1] nonane-9,
2 '-[2H] benzo [f] chromene] (3) 7'-methoxyspiro [bicyclo [3.3.1]]
Nonane-9,2 '-[2H] benzo [f] chromene] (4) 7'-methoxyspiro [norbornane-2,2'
-[2H] benzo [h] chromene] (5) 2,2-dimethyl-7-octoxy [2H] benzo [h] chromene (6) Spiro [2-bicyclo [3.3.1] nonene-
9,2 '-[2H] benzo [f] chromene] (7) 4'-methylspiro [bicyclo [3.3.1] nonane-9,2' [2H] benzo [f] chromene] (8) 3'-methyl spiro [norbornane-2,2'-
[2H] benzo [f] chromene] (9) spiro [tricyclo [3.3.1.13,7] decane-2,2 '-[2H] benzo [h] chromene] (10) 4'-piperidinospiro [ Bicyclo [3.3.
1] Nonane-9,2 '-[2H] benzo [h] chromene] (11) 2,2-Dimethyl-6-octadecyl [2H]
Benzo- [h] chromene (12) Spiro [norborinane-2,2 '-[2H] naphtho [1,2-h] chromene] (13) 2,2-Dimethyl-7- [ethylthiogexyl] oxy [ 2H] benzo [h] chromene (14) 6-chloro-2,2-dimethyl-7- [dipropylphosphonohexyl] oxy [2H] benzo [h] chromene (15) 2,2-dimethyl [2H] pyrido [2,3-h]
Chromene (16) 7-methoxy-2,2-dimethyl [2H] benzo [h] chromene (17) 7- [Diethylaminooctyl] -2,2-dimethyl [2H] benzo [h] chromene

In the present invention, the mixing ratio of the above-mentioned spirooxazine compound and chromene compound can be arbitrarily selected according to the intended color tone, but in order to adjust to gray, brown, amber or the like, spiro Chromene compounds 1 to 100 relative to 100 parts by weight of the oxazine compound
It is suitable that the amount is 00 parts by weight, preferably 5 to 2000 parts by weight.

The photochromic composition of the present invention can be made into a photochromic fluid which can be used for applications such as decoration by dispersing it in an organic solvent. Further, by dispersing the photochromic composition of the present invention in a polymer such as a thermoplastic resin or a thermosetting resin, a molded product such as photochromic glass or photochromic lens can be obtained.

The thermoplastic resin may be any one as long as it can uniformly disperse the spirooxazine compound and the chromene compound. Optically, for example, polymethyl acrylate, ethyl polyacrylate, polymethyl methacrylate, poly Examples thereof include ethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane, and polycarbonate.

The dispersion of the photochromic composition of the present invention in the thermoplastic resin is carried out by synthesizing the thermoplastic resin, that is, by carrying out the polymerization in the presence of the photochromic composition, or by using the thermoplastic resin and the photochromic composition. A method of melt-kneading at a temperature not lower than the melting temperature of the thermoplastic resin can be mentioned.

As the thermosetting resin, known ones can be used without any limitation as long as they can uniformly disperse the spirooxazine compound and the chromene compound. In particular, the following general formulas (5), (6) and (7)
The use of a radically polymerizable monomer represented by, or a combination of these monomers with another radically polymerizable monomer copolymerizable with the monomer is a dark color density of the photochromic compound. It is preferable because a high fading speed can be obtained and the reversible durability of the photochromic action can be improved. Further, it is suitable because a photochromic resin having practical physical properties such as good transparency, surface hardness, and heat resistance can be obtained. The following general formulas (5), (6) and (7)
Two or more compounds represented by may be used in combination.

[0061]

[Chemical 7]

[Wherein R ⁵ is a hydrogen atom or a methyl group, R ⁶ is an alkylene group having 1 to 4 carbon atoms, or

[0063]

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(Wherein k is an integer of 0 to 5) and n is an integer of 1 to 20].

In the general formula (5), the alkylene group having 1 to 4 carbon atoms represented by R ⁶ is a methylene group, an ethylene group,
Examples thereof include a propylene group, a butylene group, a trimethylene group and a tetramethylene group.

[0066]

[Chemical 9]

(Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸ is an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, or a carbon atom which may be substituted with a halogen atom). An aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms which may be substituted with a halogen atom).

In the above general formula (6), the alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group represented by R ⁸ is a methyl group, an ethyl group, a propyl group, a butyl group or a hydroxyethyl group. , A hydroxypropyl group and the like, and the aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom may be exemplified by a phenyl group, a naphthyl group, a chlorophenyl group, a tribromophenyl group and the like. Examples of the aralkyl group having 7 to 10 carbon atoms which may be substituted with a halogen atom include benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, trichlorobenzyl group and tribromobenzyl group. You can

[0069]

[Chemical 10]

(Provided that R ⁹ and R ¹² are the same or different hydrogen atoms or methyl groups, and R ¹⁰ and R ¹¹ are the same or different C 1 -substituted carbon groups. ~ 4 alkylene group, or

[0071]

[Chemical 11]

And m and n are 0 or 1 respectively). The alkylene group represented by R ¹⁰ and R ¹¹ in the above formula (7) is a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, a tetramethylene group, or a group in which these groups are substituted with a hydroxyl group. Can be illustrated.

Specific examples of the compounds represented by the above general formulas (5), (6) and (7) include methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate and n-butyl methacrylate. , T-butyl methacrylate, t-butyl methacrylate tribromophenyl methacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, bisphenol A dimethacrylate, 2 ,
Examples thereof include acrylic and methacrylic acid ester compounds such as 2-bis (4-methacryloyloxyethoxyphenyl) propane.

Further, glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4
-Glycidyloxybutyl methacrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3- (glycidyloxy-2-hydroxy) There may be mentioned acrylate compounds such as propyloxy) -2-hydroxypropyl acrylate or methacrylate compounds.

The other radical-polymerizable monomer copolymerizable with these compounds is not particularly limited as long as it is copolymerizable with the monomer, and examples thereof include styrene and chloro. Styrene, α-methylstyrene, α-
Aromatic vinyl compounds such as methylstyrene dimer, vinylnaphthalene, isopropenylnaphthalene, bromostyrene, divinylbenzene and the like can be mentioned.

For the dispersion of the photochromic composition in the thermosetting resin described above, a method in which the raw material monomer of the thermosetting resin and the photochromic composition are mixed and then polymerized is generally adopted. The polymerization method for obtaining the polymer is not particularly limited, and a known polymerization method can be adopted. The polymerization can be initiated by using radical polymerization initiators such as various peroxides and azo compounds. To exemplify a typical polymerization method, a polymerizable monomer, a radical polymerization initiator and the photochromic composition of the present invention are injected between molds held by an elastomer gasket or a spacer and polymerized in a heating furnace. Later, detached cast polymerization can be employed. Further, in the case of obtaining a photochromic polymer having a polarizing property, a polymerizable monomer, a radical polymerization initiator and the photochromic composition of the present invention are injected between molds which also hold a polarizing film with an elastomer gasket or a spacer. Then, cast polymerization may be employed in which the polymer is polymerized in a heating furnace and then removed.

The radical polymerization initiator is not particularly limited and known ones can be used. Typical examples thereof include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, Diacyl peroxides such as acetyl peroxide; peroxyesters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate and t-butylperoxybenzoate; diisopropyl Examples thereof include percarbonates such as peroxydicarbonate and di-sec-butyl peroxydicarbonate; and azo compounds such as azobisisobutyronitrile. These radical polymerization initiators can be used alone or in combination of two or more.

The amount of the radical polymerization initiator used varies depending on the polymerization conditions, the type of the initiator, and the composition of the above-mentioned monomers,
Generally, the polymerizable monomer 10
A range of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, relative to 0 parts by weight is suitable.

Among the polymerization conditions, the temperature particularly affects the properties of the obtained photochromic resin. This temperature condition cannot be unconditionally limited because it is influenced by the type and amount of the initiator and the type of the monomer, but generally the polymerization is started at a relatively low temperature, the temperature is slowly raised, and the polymerization is performed. It is preferable to perform a so-called taper type two-stage polymerization in which curing is performed at a high temperature at the end. Since the polymerization time also depends on various factors like the temperature, it is preferable to determine the optimum time in advance according to these conditions, but generally 2 to 40
It is preferable to select the conditions so that the polymerization is completed in time.
The amount of the photochromic composition of the present invention dispersed in such a polymer is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the polymer. At the time of the polymerization, release agents, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, various stabilizers such as fragrances, additives are selected as necessary. Can be used.

By incorporating an ultraviolet stabilizer into the composition of the present invention, the durability of photochromic property can be further improved. As the ultraviolet stabilizer, known ultraviolet stabilizers added to various plastics can be used without any limitation. In the present invention, considering the improvement of durability of the photochromic compound, among various ultraviolet stabilizers, singlet oxygen quencher, hindered amine light stabilizer, hindered phenol antioxidant, and sulfur-based antioxidant are preferably used. To be done. The amount of the ultraviolet stabilizer compounded is preferably in the range of 0.1 to 10000 parts by weight, and more preferably in the range of 1 to 1000 parts by weight, based on 100 parts by weight of the total amount of the spirooxazine compound and the chromene compound. Is more preferable.

[0081]

INDUSTRIAL APPLICABILITY The photochromic composition of the present invention changes from a colorless state to a colored or darkened state by light containing ultraviolet rays such as sunlight or light of a mercury lamp, and the change is reversible and excellent dimming property. Indicates. Furthermore, the present invention has succeeded in obtaining an intermediate color having excellent durability against repeated coloring / decoloring and having little change in color tone by combining a novel spirooxazine compound with a chromene compound. Therefore, the photochromic composition of the present invention can be used in a wide range of fields, such as various recording memory materials replacing silver salt photosensitive materials, copying materials, printing photoreceptors, recording materials for cathode ray piping, and photosensitive materials for lasers. It can be used as various recording materials. In addition, the photochromic composition of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material, a photometer, and decoration.

[0082]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The compounds used in the examples below are: Spirooxazine compound

Production Example 1

[0084]

[Chemical 12]

2.33 g (0.01 mol),

[0086]

[Chemical 13]

1.73 g (0.01 mol) was dissolved in 50 ml of ethyl alcohol and refluxed for 2 hours. After the reaction,
The solvent was removed and the product was purified by chromatography on silica gel to obtain 2.1 g (yield 54%) of a spirooxazine compound (A) represented by the following formula. A: 1- (methylthio) ethyl-3,3-dimethylspiro [indole-2 (2H), 3 '-[3,2-a]
[1,4] naphthodioxane]

[0088]

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The elemental analysis value of this compound is C74.05.
%, H6.20%, N7.38%, S8.12%, O4.2
5%, C74.19% against CHNOS, H
It was in very good agreement with 6.23%, N7.21%, S8.25%, and O4.12%. In addition, when the proton nuclear magnetic resonance spectrum was measured, a spectrum of 11H based on a proton of the naphthalene ring, a proton of the indoline ring and a proton of the oxazine ring was measured at δ of about 6.8 to 8.5 ppm, δ
> N-CH bond and -S- in the vicinity of 2.5 to 4.5 ppm.
7H spectrum based on CH-bonded protons, δ1.
A spectrum of 6H based on the proton of the methyl group of the indoline ring was shown at around 2 to 2.3 ppm.

Further, the ¹³ C-nuclear magnetic resonance spectrum was measured. As a result, a spectrum based on carbons of benzene ring, naphthalene ring and oxazine ring of indoline around δ 110 to 150 ppm, a spectrum based on spiro carbon near δ 100 ppm, and a thioether around δ 30 ppm. The carbon-based spectrum of is shown. The measured infrared absorption spectrum (IR), C = N bond near 1620 cm ^-1, spectral absorption of the aromatic C-H bonds appeared around 1485cm ^-1. From the above results, it was confirmed that the isolated product was the compound represented by the structural formula (A).

Production Example 2

[0092]

[Chemical 15]

3.67 g (0.01 mol),

[0094]

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2.03 g (0.01 mol) and 4.35 g (0.05 mol) of morpholine were dissolved in 50 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 2.0 g of a spirooxazine compound (B) represented by the following formula. B: 6 "-morpholino-8" -methoxy-1 '-[2-
(Phenylthio) ethyl] -6'-fluoro-7'-methyldisspiro [cyclohexane-1,3 '-[3H] indole-2', 3 "-[3,2-a] [1,4] naphthoxazine]

[0096]

[Chemical 17]

The elemental analysis value of this compound is C71.72.
%, H6.20%, N6.51%, S4.99%, O7.6
2%, F 2.96%, C for CHNOSF
71.56%, H6.32%, N6.59%, S5.03
%, O 7.53% F 2.98%. Also, when the proton nuclear magnetic resonance spectrum was measured,
Protons of the naphthalene ring near δ 6.8-8.5 ppm,
12H spectrum based on proton of indoline ring, proton of oxazine ring, proton of thiophenyl, δ
> N-CH bond, -S-CH around 2.5-4.5 ppm
15H spectrum based on bound protons, morpholine ring protons and methoxy group protons, δ1.2
A spectrum of 13 H based on the proton of the cyclohexyl ring bound to the indoline ring and the proton of the methyl group bound to the benzene ring was shown at about 2.3 ppm.

Further, the ¹³ C-nuclear magnetic resonance spectrum was measured. As a result, a spectrum based on carbons of the benzene ring, naphthalene ring and oxazine ring of indoline around δ 110 to 150 ppm, a spectrum based on spiro carbon near δ 100 ppm, and a thioether around δ 30 ppm. The spectrum based on carbon is shown. The measured infrared absorption spectrum (IR), C = N bond near 1620 cm ^-1, spectral absorption of the aromatic C-H bonds appeared around 1485cm ^-1. From the above results, it was confirmed that the isolated product was the compound represented by the structural formula (B).

Production Examples 3 to 9 The spirooxazine compounds shown below were synthesized in the same manner as in Production Examples 1 and 2, and the structure was analyzed using the same means for confirming the structure as in Production Example 1. Among the spirooxazine compounds described below, the compounds C, D, and E were produced by the same method as in Production Example 1, and the compound F was produced by the same method as in Production Example 2. C: 1- (cyclohexylthio) ethyl-6-fluoro-7-methyl 3,3-dimethylspiro [indole-2
(2H), 3 '-[3H] pyrido [4,3-f] [1,
4] Benzoxazine]

[0100]

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D: 1 '-[(3-methylthiopropionyloxy) ethyl] disspiro [tetrahydropyranyl-
4,3 '-[3H] -7-azaindole-2', 2 "-
[3H] pyrido [2,3-h] [1,4] benzoxazine]

[0102]

[Chemical 19]

E: 9'-methoxy-1- (3-methylthiopropion-2-yl) -3,3-dimethylspiro [pyrido [3,4-f] indole-2,2 '-[2,3]
-A] [1,4] naphthoxazine]

[0104]

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F: 1 '-(phenylthio) ethyl-6'
-Fluorodisspiro [cyclohexane-1,3 '-[3
H] indole-2 '(2'H), 3 "-[3,2-a]
[1,4] naphthoxazine]

[0106]

[Chemical 21]

G:

[0108]

[Chemical formula 22]

H:

[0110]

[Chemical formula 23]

I:

[0112]

[Chemical formula 24]

Chromene Compounds The following compounds were used. A: Spiro [norbornane-2,2 '-[2H] benzo [h] chromene] B: Spiro [bicyclo [3.3.1] nonane-9,2'-
[2H] benzo [f] chromene] C: 7'-methoxyspiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [f] chromene] D: 7'-methoxyspiro [norbornane -2,2'-
[2H] benzo [h] chromene] E: 2,2-dimethyl-7-octoxy [2H] benzo [h] chromene F: Spiro [2-bicyclo [3.3.1] nonene-9,
2 '-[2H] benzo [f] chromene]

Radical Polymerizable Monomer The following compounds were used. A: Glycidyl methacrylate B: α-methylstyrene C: α-Methylstyrene dimer D: Triethylene glycol dimethacrylate E: Tetraethylene glycol dimethacrylate F: 2-Hydroxyethyl methacrylate G: 2,2-Bis (4-methacryloyl) Oxyethoxyphenyl) propane H: n-butyl methacrylate

Example 1 65 parts by weight of tetraethylene glycol dimethacrylate, 15 parts by weight of triethylene glycol dimethacrylate, 9 parts by weight of glycidyl methacrylate, 2 parts by weight of 2-hydroxyethyl methacrylate, 8 parts by weight of α-methylstyrene, α-methyl. 1- (methylthio) ethyl-3,3-dimethylspiro [indole-2 (2H), 3 '-[3,2-a] was added as a spirooxazine compound to each radical-polymerizable monomer of 1 part by weight of styrene dimer. ]
[1,4] naphthodioxane] 0.08 part by weight, and 7'-methoxyspiro [bicyclo [3.3.
1] Nonane-9,2 '-[2H] benzo [f] chromene] 0.04 part by weight was added and mixed well. In this mixed solution, t-butylperoxy-2 was used as a radical polymerization initiator.
-Ethyl hexanate 0.5 part by weight was added and mixed well, and the resulting mixture was poured into a mold composed of a glass plate and a gasket composed of ethylene-vinyl acetate copolymer, and cast polymerization was carried out. went. Polymerization is carried out using an air oven at 30 ° C.
To 90 ° C. over a period of 18 hours, the temperature was gradually raised, and the temperature was maintained at 90 ° C. for 2 hours. After completion of the polymerization, the mold was taken out of the air furnace, allowed to cool, and then the polymer was removed from the glass plate of the mold.

The resulting photochromic polymer (thickness 2
mm), xenon lamp L-24 made by Hamamatsu Photonics
80 (300 W) SHL-100 was passed through an aeromass filter (manufactured by Corning) at 20 ° C. ± 1 ° C., the beam intensity on the polymer surface was 365 nm = 2.4 mW / cm ² , 24.
Color was developed by irradiation at 5 nm = 24 μW / cm ² for 30 seconds. [epsilon] (30)-[epsilon] (0) was calculated and used as the color density. Here, ε (30) is obtained by irradiating light for 30 seconds under the above conditions,
It is the absorbance at the maximum absorption wavelength of the photochromic compound at the time of color development, and ε (0) is the absorbance at the same wavelength as that at the time of color development before irradiation with light.

Then, the durability was measured by a xenon fade meter FA-25AX-HC manufactured by Suga Test Instruments Co., Ltd. Durability, after irradiating the polymer to the xenon fade meter, develop the color of the polymer by the above method, the absorbance at the maximum absorption wavelength based on the color development of the photochromic compound at that time, the absorbance in the color before irradiation of the fade meter It is expressed as the time until it becomes 1/2 of the. In Table 1, it is represented by T _1/2 (hr).

Further, the change in color tone of the photochromic polymer was visually observed. The change in color tone was compared between before the fade meter irradiation and after irradiation with the spirooxazine compound for T _1/2 hours. The results are shown in Table 1.

Examples 2 to 23 Example 1 except that the spirooxazine compound, the chromene compound and the polymerizable monomer shown in Example 1 were changed in kind and polymerization was carried out by a known means according to the monomer. Same as. The results are shown in Table 1.

Comparative Examples 1 and 2 As a spirooxazine compound, J: 1-methoxyethyl-3,3-dimethylspiro [indole-2 (2H), 3 '-[3,2-a] [1,4]
Naphthoxazine]

[0121]

[Chemical 25]

Example 1 and Example 1 except that
The same procedure as in 1 was performed. The results are shown in Table 1.

[0123]

[Table 1]

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[Procedure amendment]

[Submission date] August 12, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

When the α-ring and the β-ring are substituted, the substituents are halogen atom, alkyl group, cycloalkyl group, aralkyl group, aryl group, alkoxy group, aralkoxy group, aryloxy group, acyloxy group,
An amino group which may have a substituent, a nitro group, a cyano group,
There may be mentioned a halogenoalkyl group or an alkoxycarbonyl group, and the number of these substituents may be 1 or 2 or more. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

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[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0092

[Correction method] Change

[Correction content]

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[Chemical 15]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0096

[Correction method] Change

[Correction content]

[0096]

[Chemical 17]

Claims (1)

[Claims] 1. (A) The following general formula (1): [However, the α ring and the β ring are a hydrocarbon aromatic ring or an unsaturated heterocycle which may have the same or different substituents, and R ⁴ is an alkylene group or — (ABA) _m -(Wherein A is an alkylene group, B is an oxygen atom, a carbonyl group, -COO-, -OCO- or an arylene group, and m is an integer of 1 to 3), and R ¹ is alkyl. Group, a cycloalkyl group, an aryl group, an alkoxycarbonylalkyl group, R ² and R ³ are the same or different alkyl groups,
A cycloalkyl group or an alkoxyalkyl group,
R2 and R3 may be joined together to form a ring, and n is an integer of 1 to 4] 100 parts by weight of the spirooxazine compound and (B) the chromene compound 1 to 1000
A photochromic composition comprising 0 parts by weight.