JP2000008030A - Chromen composition - Google Patents

Abstract

(57) [Problem] To provide a chromene composition which has a high fading speed, has less coloring at the time of deterioration, and has an excellent balance of photochromic properties. SOLUTION: For example, the following formula: A chromene composition comprising 100 parts by weight of a chromene compound represented by the formula and 10 to 1000 parts by weight of a benzotriazole-based ultraviolet absorber and / or a benzophenone-based ultraviolet absorber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an excellent color fading which changes into a colored form upon irradiation with light including ultraviolet rays such as sunlight or light from a mercury lamp, has a high color density, and the change is reversible. The present invention relates to a chromene composition which exhibits a speed and has less coloring upon deterioration, and has an excellent balance of photochromic properties.

[0002]

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

[0003] PCT Patent Application Publication WO94 / 22
No. 850 discloses a chromene compound represented by the following formula (A).

[0004]

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This chromene compound has a high color density and
Although it shows a fast fading speed, it has a drawback that it is colored when deteriorated.

Further, US Pat. No. 4,989,089 discloses a chromene compound represented by the following formula (B).

[0007]

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This chromene compound has little coloring during deterioration and exhibits photochromic properties at around room temperature (20 to 30 ° C.), but has a low color fading speed when placed in a dark place after being irradiated with ultraviolet rays. When a mixed color is toned by combination with a photochromic compound having another color such as flugimide and spirooxazine,
Hue changes when fading.

Further, PCT Patent Application Publication WO95
No./16215 includes the following formula (C)

[0010]

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Wherein R7 is an aminocarbonyl group or an alkoxycarbonyl group, R8 and R9 are hydrogen, an alkyl group, a substituted or unsubstituted phenyl group or an alkoxy group, and k is 0-3. , B and B ′ are a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted adamantylidene group, or a substituted or unsubstituted norbornylidene group.) Are disclosed. This compound improved the fading speed as compared with the compound described in the above-mentioned U.S. Pat. No. 4,989,089, but could not completely prevent a hue change at the time of fading from a mixed color state. Furthermore, the coloring at the time of deterioration is larger than the coloring at the time of deterioration of the compound (B).

Further, “photochromism” (“Photoc
hromism '' Brown, GH (Ed), John Wiley & Sons, New Yo
rk, 1971) shows a chromene compound represented by the following formula (D).

[0013]

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Although this compound has a low initial coloring and a fast fading rate, it has a low color density and is not practical.

As described above, when each chromene compound is used alone, it is not satisfactory in terms of color density, color fading speed and coloring at the time of deterioration.

[0016]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a chromene composition having a sufficient color-forming density, a high fading speed, little coloring upon deterioration, and an excellent balance of photochromic properties. is there.

[0017]

DISCLOSURE OF THE INVENTION The present invention has been proposed to achieve the above-mentioned object, and a specific chromene compound having a high coloring sensitivity and a high fading speed is mixed with an ultraviolet absorber in a certain range. The present invention has been completed based on the knowledge of the present inventors that a chromene composition having a sufficient coloring density, a high fading speed, and suppressed coloring during deterioration can be obtained.

That is, the present invention provides: (A) the following general formula (1)

[0019]

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[Wherein R ¹ is the following formula (2)

[0021]

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(Wherein R ⁵ and R ⁶ are hydrogen atoms which may be different from each other, substituted or unsubstituted carbon atoms having 1 to 10 carbon atoms)
, A substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms or a heterocyclic group. Or a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and a nitrogen atom bonded to a naphthopyran ring, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring as the heterocyclic group Is a fused heterocyclic group condensed, R ² and R ³ are a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or an alkyl group which may be different from each other; ⁴ is a substituent, n is an integer of 0 to 4 representing the number of R ⁴ , and when n is 2 or more, R ⁴ may be the same or different. A chromene compound represented by the following formula: 100 parts by weight and (B) an ultraviolet absorber: 10 to 1000 parts by weight.

Another aspect of the present invention is a polymerizable composition containing a polymerizable monomer and the chromene composition, and a cured product obtained by polymerizing the polymerizable composition.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention includes a chromene compound represented by the above general formula (1) (hereinafter also referred to as component (A)).

In the general formula (1), R ¹ is the same as the general formula (2),

[0026]

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(Wherein R ⁵ and R ⁶ are hydrogen atoms which may be different from each other, substituted or unsubstituted carbon atoms having 1 to 10 carbon atoms)
, A substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms or a heterocyclic group. Or a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and a nitrogen atom bonded to a naphthopyran ring, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring as the heterocyclic group Is a condensed heterocyclic group condensed.

The substituents R ⁵ and R ⁶ in the above formula (2) are a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms or As the heterocyclic group, a known group is used without any limitation. As these alkyl groups, aromatic hydrocarbon groups or heterocyclic groups, methyl group, ethyl group, isopropyl group,
An alkyl group having 1 to 4 carbon atoms such as an n-butyl group: an aromatic hydrocarbon group such as a benzene ring and a naphthalene ring; and a heterocyclic group such as a furyl group, a thienyl group, and a benzothienyl group are preferable. The substituents R ⁵ and R ⁶ may be the same or different.

Examples of the substituent of the alkyl group, aromatic hydrocarbon group or heterocyclic group include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a hydroxy group and a cyano group.

Specific examples of the group represented by the above formula (2) include an amino group, a methylamino group, an ethylamino group,
Propylamino group, isopropylamino group, dimethylamino group, diethylamino group, dipropylamino group, methylethylamino group, 2-hydroxyethylamino group, di (hydroxyethyl) amino group, di (cyanomethyl) amino group, diphenylamino group And the like.

In the general formula (1), a substituted or unsubstituted heterocyclic group or a heterocyclic group represented by R ¹ having a nitrogen atom as a hetero atom and bonding the nitrogen atom to a naphthopyran ring In a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed, the number of carbon atoms constituting the heterocyclic group is preferably 2 to 10, and preferably 2 to 6 carbon atoms. is there. A hetero atom may be present in the ring in addition to the nitrogen atom bonded to the naphthopyran ring, and the hetero atom is not particularly limited, but an oxygen atom,
Sulfur and nitrogen are preferred. Examples of the aromatic hydrocarbon ring or aromatic hetero ring bonded to the heterocyclic group include an aromatic hydrocarbon ring and an aromatic hetero ring having 6 to 10 carbon atoms. As these, a benzene ring, a thiophene ring, and a furan ring are preferable. The heterocyclic group may be substituted with at least one hydrogen atom, and the substituent is not particularly limited as long as it is a known substituent, but may be an alkyl group, an aromatic hydrocarbon group, Halogen atoms are preferred.

A substituted or unsubstituted heterocyclic group having the nitrogen atom represented by the substituent R ¹ as a heteroatom and the nitrogen atom bonded to a naphthopyran ring, or an aromatic hydrocarbon ring or The alkyl group which is a substituent of the condensed heterocyclic group in which the aromatic heterocyclic ring is condensed is not particularly limited, but is generally an alkyl group having 1 to 10, 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 aromatic hydrocarbon group is not particularly limited, but generally has 6 to 14, preferably 6 carbon atoms.
To 10 aromatic hydrocarbon groups. Specific examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

The halogen atom is not particularly limited, but is generally a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine or bromine atom.

A substituted or unsubstituted heterocyclic ring having the nitrogen atom represented by R ¹ as a heteroatom and bonded to the naphthopyran ring by the nitrogen atom, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring as the heterocyclic group. Specific examples of the condensed heterocyclic group in which the rings are condensed include a pyrrolidinyl group, a piperidino group, a hexamethyleneimino group, a 2,2,6,6-tetramethylpiperidino group, a morpholino group, and a 2,6-dimethylmori Examples include a horno group, an N-methylpiperazinyl group, a thiomorpholino group, an indolyl group, a methylindolyl group, a tetrahydroquinolyl group, and an aziridinyl group.

In the general formula (1), R ² and R ³ may be different from each other, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or an alkyl group. .

The aromatic hydrocarbon group is not particularly limited, but is generally preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of the aromatic hydrocarbon group include a phenyl group, a 2-naphthyl group, and a 1-naphthyl group.

The aromatic heterocyclic group is not particularly limited, but is generally an aromatic heterocyclic group having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. The hetero atom contained in the aromatic heterocyclic group is not particularly limited, but is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and the number is 1 to 3, preferably 1 to 2. When the aromatic heterocyclic group contains a plurality of hetero atoms, the hetero atoms may be the same or different hetero atoms. Further, the aromatic heterocyclic group may be condensed with an aromatic ring. The aromatic ring which may be condensed has 6 carbon atoms.
To 10 aromatic rings, such as a benzene ring and a naphthalene ring. Specific examples of the aromatic heterocyclic group include a furyl group, a thienyl group, a pyrrolyl group, a benzofuryl group, an indole group, a quinolyl group, an isoquinolyl group, a dibenzofuryl group, and a carbazole group.

The alkyl group is not particularly limited, but generally has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl and the like. it can. A methyl group is most preferable in consideration of practical durability.

The aromatic hydrocarbon group and the aromatic heterocyclic group represented by the above substituents R ² and R ³ may have a known substituent, and the type thereof is not particularly limited. ,
Alkyl group, alkoxy group, alkoxyalkoxy group,
An aryloxy group, an alkoxyalkyl group, an aralkyl group, a substituted amino group, a substituted or unsubstituted nitrogen atom having the nitrogen atom as a heteroatom and the aromatic hydrocarbon group or the aromatic heterocyclic group bonded thereto; Examples include substituents such as a heterocyclic group, an acyloxy group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a cyano group, a trifluoromethyl group, a trifluoromethoxy group, and a nitro group. The bonding position and the number of the substituents of the aromatic hydrocarbon group and the aromatic heterocyclic group are not particularly limited, but the number of the substituents is preferably 0 to 4, preferably 0 to 3,
These substituents may be the same or different, and may be combined without any limitation.

The alkyl group which is a substituent of the aromatic hydrocarbon group or the aromatic heterocyclic group represented by the substituents R ² and R ³ is not particularly limited, but generally has 1 to 1 carbon atoms.
It is 0, preferably 1-4 alkyl groups. Specific examples of the alkyl group include a methyl group, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, t-butyl group and the like.

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

The alkoxyalkoxy group is not particularly limited, but generally has 2 to 20, preferably 3 carbon atoms.
To 10 alkoxyalkoxy groups. Specific examples of the alkoxyalkoxy group include a methoxyethoxy group, an ethoxyethoxy group, a methoxypropoxy group,
A methoxybutoxy group and the like can be mentioned.

The aryloxy group is not particularly limited, but is generally an aryloxy group having 6 to 14, preferably 6 to 10 carbon atoms. Specific examples of the aryloxy group include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group.

The alkoxyalkyl group is not particularly limited, but is generally an alkoxyalkyl group having 2 to 10, preferably 2 to 6, carbon atoms. Specific examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a dimethoxymethyl group, a 2,2-dioxacyclopentan-1-yl group and a butoxymethyl group.

The aralkyl group is not particularly limited, but is generally an aralkyl group having 7 to 16, preferably 7 to 10 carbon atoms. Specific examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group.

The acyloxy group is not particularly limited, but is generally an acyloxy group having 1 to 15, preferably 1 to 6 carbon atoms. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, a (meth) acryloyloxy group, and a benzoyloxy group.

The substituted amino group is not particularly limited, but generally includes an amino group having a substituent such as an alkyl group having 1 to 10 carbon atoms and a hydroxy-substituted alkyl group. Specific examples of the substituted amino group include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, a methylethylamino group, and a 2-hydroxyethylamino group. And a di (hydroxyethyl) amino group.

A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom bonded to the aromatic hydrocarbon group or the aromatic heterocyclic group constitutes the heterocyclic group. The number of carbon atoms is preferably 2 to 10, and preferably 2 to 6 carbon atoms. In the ring, a hetero atom may be further present in addition to the nitrogen atom bonded to the aromatic hydrocarbon group or the aromatic heterocyclic group, and the hetero atom is not particularly limited. An atom and a nitrogen atom are preferred.

A specific example of a substituted or unsubstituted heterocyclic group having the above nitrogen atom as a hetero atom and bonded to the above aromatic hydrocarbon group or aromatic heterocyclic group by the nitrogen atom is a pyrrolidinyl group. , Piperidino group, hexamethyleneimino group, 2,2,6,6-tetramethylpiperidino group, morpholino group, 2,6-dimethylmorpholino group, N-methylpiperazinyl group, thiomorpholino group and the like. Can be.

The alkoxycarbonyl group is not particularly limited, but is generally an alkoxycarbonyl group having 1 to 10, preferably 1 to 7 carbon atoms. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an (iso) propoxycarbonyl group, and an (iso, t-) butyroxycarbonyl group.

The aryloxycarbonyl group is not particularly limited, but is generally an aryloxycarbonyl group having 6 to 20, preferably 6 to 10 carbon atoms. Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthoxycarbonyl group,
-Naphthoxycarbonyl group and the like.

The acyl group is not particularly limited, but is generally an acyl group having 1 to 15 carbon atoms, preferably 1 to 7 carbon atoms. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, and a benzoyl group.

The halogen atom is not particularly limited, but is generally a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

R ⁴ in the above general formula (1) is a substituent that is substituted at the 5-, 7, 8-, 9- and 10-positions of the naphthopyran ring, and the introduction of the substituent greatly affects the effect of the present invention. No effect. Examples of the substituent include an alkyl group, an alkoxy group, an aralkyl group, an acyl group, an alkoxycarbonyl group, a substituted amino group, and a substituted or unsubstituted nitrogen atom having a heteroatom bonded to a naphthopyran ring. Examples thereof include a heterocyclic group, an aromatic hydrocarbon group, an acyloxy group, a nitro group, a hydroxy group, and a halogen atom. The aromatic hydrocarbon group is not particularly limited by the number of carbon atoms, but generally is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms. Examples of suitable aromatic hydrocarbon groups include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Other substituents are
The same groups or atoms as those described above for the substituents which the substituted or unsubstituted aromatic hydrocarbon group and aromatic heterocyclic group represented by R ² and R ³ may have may be used.

N is the number of the substituent R ⁴ and is an integer of 0 to 4. The value of n may be 0 to 4, but is preferably 3 or less, and more preferably 2 or less, for convenience of synthesis.

As the component (A) of the present invention, a chromene compound represented by the following formula is particularly suitable for obtaining a chromene composition having characteristics such that it has practically sufficient color-forming sensitivity and a high fading speed. Can be used for

[0058]

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In the formula, R ¹ is the following formula

[0060]

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Wherein R ⁵ and R ⁶ are a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms which may be different from each other, or a substituted or unsubstituted pyrrolidinyl group , A morpholino group, a piperidino group, a thiomorpholino group, an aziridinyl group, a piperazinyl group, a hexamethyleneimino group, an indolyl group or a tetrahydroquinolyl group, and R ² and R ³ are a substituted or unsubstituted phenyl group, a naphthyl group, Furyl, thienyl,
A pyrrolyl group, a benzofuryl group, a benzothienyl group or a methyl group.

Specific examples of preferred chromene compounds in the component (A) of the present invention include: 1) 6-morpholino-3,3-bis (3-fluoro-4)
-Methoxyphenyl) -3H-benzo (f) chromene 2) 6-morpholino-3- (4-methoxyphenyl)-
3- (4-trifluoromethoxyphenyl) -3H-benzo (f) chromene 3) 6-piperidino-3-methyl-3- (2-naphthyl) -3H-benzo (f) chromene 4) 6-piperidino-3 -Methyl-3-phenyl-3H
-Benzo (f) chromene 5) 6-morpholino-3,3-bis (4-methoxyphenyl) -3H-benzo (f) chromene 6) 6-hexamethyleneimino-3-methyl-3- (4
-Methoxyphenyl) -3H-benzo (f) chromene 7) 6-morpholino-3- (2-furyl) -3-methyl-3H-benzo (f) chromene 8) 6-morpholino-3- (2-thienyl) -3-Methyl-3H-benzo (f) chromene 9) 6-morpholino-3- (2-benzofuryl) -3-
And methyl-3H-benzo (f) chromene.

The chromene compound of the component (A) of the present invention can be used singly or in combination of two or more depending on the use.

Known UV absorbers (hereinafter, also referred to as component (B)) can be used without limitation, and particularly preferred are benzotriazole UV absorbers and benzophenone UV absorbers. As the benzotriazole-based ultraviolet absorber, a known compound having a benzotriazole skeleton and having an ultraviolet absorbing ability can be used without any limitation. For example, a benzotriazole-based ultraviolet absorber represented by the following formula (3) is preferable. Can be used for

[0065]

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(Wherein R ¹⁰ and R ¹¹ may be different hydrogen atoms, alkyl groups, aromatic hydrocarbon groups,
An arylalkyl group, and R ¹² is a hydrogen atom or a chlorine atom. In the formula (3), examples of the alkyl group, aromatic hydrocarbon group, alkylaryl group, and arylalkyl group represented by R ¹⁰ and R ¹¹ include a methyl group, a butyl group, a sec-butyl group, and a t-butyl group. , A t-amyl group or other alkyl group having 1 to 10 carbon atoms; a phenyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms such as 1-naphthyl group or 2-naphthyl group; a butylphenyl group, sec-butylphenyl An alkylaryl group having 6 to 20 carbon atoms, such as a group, a t-butylphenyl group, a t-octylphenyl group; a benzyl group, a phenylethyl group,
Examples thereof include an arylalkyl group having 7 to 20 carbon atoms such as α, α-dimethylbenzyl group, and an alkyl group having 1 to 5 carbon atoms, in which R ¹⁰ and R ¹¹ may be different from each other, particularly a methyl group, t -Butyl group, t-amyl group, carbon number 6-1
5 alkylaryl groups, especially methylphenyl groups, t-
A butylphenyl group, a t-octylphenyl group, or an arylalkyl group having 7 to 15 carbon atoms, particularly a benzyl group,
Compounds that are α, α-dimethylbenzyl groups can be suitably used.

As the benzophenone-based ultraviolet absorber, known compounds having a benzophenone skeleton and capable of absorbing ultraviolet light can be used without any limitation. For example, a benzophenone-based ultraviolet absorber represented by the following formula (4) can be suitably used.

[0068]

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(In the formula, R ¹³ and R ¹⁴ are a hydrogen atom, an alkoxy group and an arylalkoxy group which may be different from each other, and R ¹⁵ is a hydrogen atom or a hydroxy group.) In the above formula (4), The alkoxy group represented by R ¹³ and R ¹⁴ is not particularly limited, but is generally an alkoxy group having 1 to 15 carbon atoms. Specific examples of suitable alkoxy groups include a methoxy group, a butoxy group, and an octyloxy group. , Dodecyloxy group and the like.

In the above formula (4), the arylalkoxy groups represented by R ¹³ and R ¹⁴ are not particularly limited, but are generally arylalkoxy groups having 7 to 20 carbon atoms. And a benzyloxy group.

The preferred UV absorbers are shown below.

Examples of the benzotriazole ultraviolet absorber include (1) 2- (5-methyl-2-hydroxyphenyl) benzotriazole (trade name: Tinuvin P: manufactured by Nippon Ciba Geigy Co., Ltd.), (2) 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole (trade name: Tinuvin 2
34, Nippon Ciba Geigy Co., Ltd.), (3) 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole (trade name: Tinuvin 320, manufactured by Nippon Ciba Geigy Corporation), (4) 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole (trade name) : Tinuvin 326, manufactured by Nippon Ciba Geigy Co., Ltd.), (5) 2- (3,5-di-t)
-Butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (trade name: Tinuvin 327, manufactured by Nippon Ciba Geigy Co., Ltd.), (6) 2- (3,5-di-t-amyl-2-hydroxyphenyl) ) Benzotriazole (trade name: Tinuvin 328, manufactured by Nippon Ciba Geigy Co., Ltd.), (7) 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole (trade name: Tinuvin 329, Nippon Ciba Geigy) Co., Ltd.).

Examples of the benzophenone-based ultraviolet absorber include: (1) 2-hydroxy-4-methoxybenzophenone (trade name: Sumisorb 110, manufactured by Sumitomo Chemical Co., Ltd.) (2) 2-hydroxy-4-octyloxy Benzophenone (trade name: Sumisorb 130, manufactured by Sumitomo Chemical Co., Ltd.) (3) Bis (2-hydroxy-4-methoxy) benzophenone (trade name: Ubinal D-49, BASF Corporation)
(4) 2-Hydroxybenzophenone (trade name: Ubinal 400, manufactured by BASF Corporation) (5) Bis (2,4-dihydroxy) benzophenone (trade name: Ubinal D50, manufactured by BASF Corporation) (6) 2,4-dihydroxybenzophenone (trade name:
(7) 2-Hydroxy-4-dodecyloxybenzophenone (trade name: Chemisorb 13, manufactured by Chemipro Kasei Co., Ltd.) (8) 4-Benzyloxy-2-hydroxybenzophenone (Trade name: Chemisorb 15, manufactured by Chemipro Kasei Co., Ltd.) (9) 2,2'-dihydroxy-4-methoxybenzophenone (trade name: Chemisorb 111, manufactured by Chemipro Kasei Co., Ltd.).

In the present invention, the amount of the component (B) is 10 to 1000 parts by weight, preferably 10 to 700 parts by weight, more preferably 20 to 500 parts by weight, based on 100 parts by weight of the component (A). . If the amount is less than 10 parts by weight, the effect of suppressing the coloring at the time of deterioration is small.
When the amount is more than 00 parts by weight, the effect of suppressing the coloring of the composition of the present invention at the time of deterioration becomes large, but the coloring density becomes insufficient.

The chromene composition of the present invention is well soluble in common organic solvents such as toluene, chloroform, tetrahydrofuran and the like. When the chromene composition of the present invention is dissolved in such a solvent, it is almost colorless and transparent, or has some initial coloring. When this is irradiated with sunlight or ultraviolet light,
It rapidly changes to a color or an intermediate color, and exhibits a good reversible photochromic action that quickly returns to its original colorless state when light is blocked. The photochromic action of the chromene composition of the present invention exhibits similar properties even in a solid polymer matrix. The target polymer solid matrix may be any one in which the chromene compound represented by the general formula (1) of the present invention is uniformly dispersed, and optically preferable, for example, polymethyl acrylate, polyacrylic acid Examples include thermoplastic resins such as ethyl, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane, and polycarbonate.

Further, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) Polyhydric acrylic acid and polyhydric methacrylate compounds such as propane and 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, epoxy amber Diallyl acid, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl jig Call carbonate, polyvalent allyl compounds such as trimethylolpropane triallyl carbonate; 1,2-bis (methacryloyl thio) ethane, bis (2-acryloylthioethyl) ether, 1,4
Polyvalent thioacrylic acid and polyvalent thiomethacrylate compounds such as bis (methacryloylthiomethyl) benzene; glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4
Glycidyloxy methacrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3
-Glycidyloxy-2-hydroxypropyloxy)
Acrylic ester compounds such as -2-hydroxypropyl acrylate and methacrylic ester compounds; and thermosetting resins obtained by polymerizing radically polymerizable polyfunctional monomers such as divinylbenzene.

Further, these monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride; methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, etc. Acrylic acid and methacrylic acid ester compounds; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate; styrene, chlorostyrene, Copolymers with radically polymerizable monofunctional monomers such as vinyl compounds such as methylstyrene, vinylnaphthalene, α-methylstyrene dimer, and bromostyrene are exemplified.

The method for dispersing the chromene composition of the present invention in the polymer solid matrix is not particularly limited, and a general method can be used. For example, kneading the thermoplastic resin and the chromene composition in a molten state,
A method of dispersing in a resin, or a method of dissolving the chromene composition in the polymerizable monomer, adding a polymerization catalyst, polymerizing with heat or light, and dispersing the resin in the resin, or a method in which the thermoplastic resin and thermosetting For example, a method in which a chromene composition is dyed on the surface of a conductive resin to disperse the resin in the resin. Among them, from the viewpoint of easy operation, as a method for dispersing the chromene composition in the polymer, a method in which these are mixed and dispersed in a polymerizable monomer and then polymerized is preferable.

The polymerizable monomer is not particularly limited.
One or more known polymerizable monomers may be used as a mixture, but a radical polymerizable monomer is preferable in order to avoid a decrease in photochromic performance due to a polymerizable group remaining after polymerization. Examples of the radical polymerizable monomer include a polymerizable monomer having a polymerizable group such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group, and an acryloyl group may be used to obtain good photochromic performance. Alternatively, a polymerizable monomer having a methacryloyl group is most preferable. Specifically, the radical polymerizable monomer exemplified in the description of the polymer composed of the above-mentioned radical polymerizable polyfunctional monomer or the copolymer of each of the above monomers and the radical polymerizable monofunctional monomer is used. The same as the dimer can be mentioned.

When preparing the photochromic polymerizable composition by mixing the chromene composition of the present invention and the above-mentioned polymerizable monomer, the mixing ratio of the chromene composition and the polymerizable monomer is determined according to the present invention. There is no particular limitation as long as the chromene composition of the present invention can be uniformly dissolved, but in order to make the photochromic performance of the obtained cured product practical, the polymerizable monomer 10 is usually used.
The amount is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight based on 0 part by weight.

To the chromene composition of the present invention, various stabilizers and additives such as an antioxidant, an ultraviolet stabilizer, a dye, a pigment, an anti-coloring agent, an antistatic agent and a fluorescent dye are added as required. May be. For example, hindered amine light stabilizers, hindered phenol light stabilizers, sulfur-based antioxidants and the like can be suitably used as the ultraviolet light stabilizer. The amount of the UV stabilizer used is not particularly limited, but is usually selected from the range of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the chromene composition.

The polymerization method is not particularly limited, and a known curing method can be employed. The polymerization can be carried out by using various radical polymerization initiators such as peroxides and azo compounds, or by irradiating ultraviolet rays, α-rays, β-rays, γ-rays or the like, or in combination with both. To illustrate a typical polymerization method, between a mold held by an elastomer gasket or a spacer, a radical polymerization initiator,
After injecting the photochromic composition of the present invention and a polymerizable composition comprising a polymerizable monomer and polymerizing in a heating furnace,
Detachable casting polymerization can be employed.

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, and the like. Diallyl peroxide such as acetyl peroxide; t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate, t-butylperoxyiso Peroxyesters such as butyrate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate; percarbonates such as diisopropylperoxycarbonate and di-sec-butylperoxydicarbonate;
Azo compounds such as azobisisobutyronitrile and the like can be mentioned. Among them, t-butyl peroxyneodecanate, t-butylperoxyneodecanate / t-butylperoxyneodecanate
A combination of butylperoxyisobutyrate and t-butylperoxyneodecanate / 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate is preferred in terms of polymerization efficiency and hardness of the cured product.

The chromene composition of the present invention can be widely used as a photochromic material. For example, various memory materials in place of silver salt photosensitive materials, copying materials, photosensitive materials for printing, memory materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for lasers, It can be used as various storage materials such as a holographic photosensitive material. In addition, the photochromic material using the chromene composition of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material, a light meter, a decoration, and the like. For example, when used in a photochromic lens, there is no particular limitation as long as uniform light control performance can be obtained, and specifically, a polymer film obtained by uniformly dispersing the photochromic material of the present invention. Or a method of sandwiching the chromene compound of the present invention in the polymerizable monomer and polymerizing it by a predetermined method, or dissolving this compound in, for example, silicone oil. 150-2
There is a method in which the surface of the lens is impregnated at 00 ° C. for 10 to 60 minutes, and the surface is further coated with a curable substance to form a photochromic lens. Further, there is a method in which the above-mentioned polymer film is applied to a lens surface, and the surface is coated with a curable substance to form a photochromic lens.

[0085]

Industrial Applicability The chromene composition of the present invention has an excellent photochromic property having a sufficient color density, exhibiting excellent fading speed, and having little coloring upon deterioration. For example, a photochromic lens using the chromene composition of the present invention reaches a dark color density quickly when it goes outdoors, and rapidly fades when it comes back indoors from outdoors,
Furthermore, even when used for a long period of time, there is little coloring due to deterioration and good durability is exhibited.

[0086]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. “Parts” in the examples is “parts by weight”. The abbreviations of the compounds used in Examples and Comparative Examples are described below.

1. (A) Component AC1) 6-morpholino-3,3-bis (3-fluoro-4-methoxyphenyl) -3H-benzo (f) chromene AC2) 6-morpholino-3- (4-methoxyphenyl) -3- (4-trifluoromethoxyphenyl) -3
H-Benzo (f) chromene AC3) 6-Piperidino-3-methyl-3- (2-naphthyl) -3H-benzo (f) chromene AC4) 6-Hexamethyleneimino-3-methyl-3-
(4-methoxyphenyl) -3H-benzo (f) chromene 2. (B) component BT1) 2- (5-methyl-2-hydroxyphenyl)
Benzotriazole (trade name: Tinuvin P: manufactured by Ciba-Geigy Japan KK), BT2) 2- [2-hydroxy-3,5-bis (α, α)
-Dimethylbenzyl) phenyl] -2H-benzotriazole (trade name: Tinuvin 234, manufactured by Nippon Ciba Geigy Co., Ltd.), BT3) 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole ( Product Name: Tinuvin 3
20, BT4) 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole (trade name: Tinuvin 326, Nippon Ciba Geigy Co., Ltd.) BT5) 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole (trade name: Tinuvin 3)
28, Nippon Ciba Geigy Co., Ltd.), a benzophenone-based ultraviolet absorber BP1) 2-hydroxy-4-methoxybenzophenone (trade name: Sumisorb 110, manufactured by Sumitomo Chemical Co., Ltd.) BP2) 2-hydroxy-4-octyl Oxybenzophenone (trade name: Sumisorb 130, manufactured by Sumitomo Chemical Co., Ltd.) BP3) Bis (2-hydroxy-4-methoxy) benzophenone (trade name: Ubinal D-49, BASF)
BP4) 2-Hydroxy-4-dodecyloxybenzophenone (trade name: Chemisorb 13, Chemipro Kasei Co., Ltd.)
2). Other chromene compounds C1) Spiro (norbornane-2,2 '-(2H) benzo (h) chromene) C2) 5-Methoxycarbonyl-6-methyl-2,2-
3. diphenyl-2H-benzo (h) chromene C3) 3,3-diphenyl-3H-benzo (f) chromene Radical polymerizable monomer 3PG: tripropylene glycol dimethacrylate (trade name: NK ester 3PG, Shin-Nakamura Chemical Co., Ltd.)
3G: Triethylene glycol dimethacrylate (trade name: NK ester 3G, manufactured by Shin Nakamura Chemical Co., Ltd.) 4G: Tetraethylene glycol dimethacrylate (trade name: NK ester 4G, manufactured by Shin Nakamura Chemical Co., Ltd.) BPE-100N: 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (trade name: NK ester BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.) MS: α-methylstyrene MSD: α-methylstyrene 4. Dimer HEMA: 2-hydroxyethyl methacrylate BzMA: benzyl methacrylate GMA: glycidyl methacrylate Radical polymerization initiator Perbutyl ND: t-butyl peroxy neodecaneate (trade name: Perbutyl ND, manufactured by NOF Corporation) Perocta O: 1,1,3,3-tetramethylbutyl peroxy-2-ethyl Hexanate (trade name: Perocta O, manufactured by NOF CORPORATION) Example 1 A chromene composition composed of 100 parts of AC1 and 120 parts of BT1 was mixed with 70 parts of 4G, 15 parts of 3G, and 1 part of GMA1.
AC1 is 0.04% by weight based on 0 parts and 5 parts of HEMA.
And mixed well. This mixture was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. In the polymerization, the temperature was gradually increased from 30 ° C. to 90 ° C. over 18 hours using an air furnace, and the temperature was maintained at 90 ° C. for 2 hours. After the completion of the polymerization, the polymer was removed from the glass mold of the mold.

A xenon lamp L-2480 (300 W) manufactured by Hamamatsu Photonics was added to the obtained polymer (thickness: 2 mm).
SHL-100 was passed through an aeromass filter (manufactured by Corning) at 20 ° C. ± 1 ° C., and the beam intensity at the polymer surface was 365 nm = 2.4 mW / cm ² , 245 nm = 24 μm.
The color was developed by irradiation at 120 W / cm ² for 120 seconds, and the photochromic properties were measured. The photochromic properties were expressed as follows.

Maximum absorption wavelength (λmax): λmax after color development of this polymer was determined using a spectrophotometer (Instant Multi-Channel Photo Detector MCPD1000) manufactured by Otsuka Electronics Co., Ltd.

Coloring density (−) = ε (120) −ε (0) · ε (120): Absorbance at the maximum absorption wavelength of this polymer after irradiation for 120 seconds under the above conditions.

.Epsilon. (0): absorbance of the unirradiated polymer at the same wavelength as the maximum absorption wavelength when irradiated with light.

Initial coloring (−) = ε (0) Fading rate [t1 / 2 (min.)] = After irradiating for 120 seconds, the absorbance of this polymer is 1 / (ε (120) −ε (0)].
The time it takes to drop to 2.

The following test was conducted as a method of accelerating the deterioration.
After irradiating the obtained polymer with sunlight for 30 minutes to develop a color,
A cycle of fading under fluorescent light for one hour was performed three times a day for a total of ten days.

As a method for evaluating the photochromic property before and after deterioration, the color density of the previous order was evaluated before and after the deterioration, and the initial color density (T0) and the color density (T30) 10 days after the promotion experiment were measured. The durability was expressed as follows.

Durability (%) = (T0 / T30) × 100 Further, the color difference before and after the deterioration was measured by a color difference meter (SM-4) manufactured by Suga Test Instruments, and the color before the deterioration was measured. The degree was represented by YI (0), the degree of coloring after deterioration was represented by YI (10), and the change in coloring due to deterioration was represented by ΔYI.

Color change degree (ΔYI) = YI (10) −YI (0) Table 1 shows the results.

Examples 2 to 22 The same procedures as in Example 1 were carried out except that the composition of the chromene compound was as shown in Table 1. The results are shown in Table 1.

Comparative Examples 1 to 9 The same procedures as in Example 1 were carried out except that the chromene compound was changed as shown in Table 1. The results are shown in Table 1.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

Examples 23 to 24 The procedure of Example 1 was repeated, except that the polymerizable monomer and the polymerization initiator were changed as shown in Table 2. The results are shown in Table 2.

[0103]

[Table 4]

The chromene compositions of the present invention were prepared according to Comparative Examples 1 to 6.
Although the color density is slightly reduced as compared with the above, the color density is sufficient, the coloration at the time of deterioration is reduced, the fading speed is high, and the photochromic characteristics are well balanced.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J011 AC04 PA35 PA36 PB25 PB40 PC02 PC08 QA03 QA06 QA08 QA12 QA13 QA19 QA20 QA34 QA37 QA40 QA43 SA22 SA26 SA36 SA78 UA01 WA01 WA10

Claims (3)

[Claims] (A) The following general formula (1): [Wherein R ¹ is the following formula (2): (Wherein, R ⁵ and R ⁶ may be different hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 10 carbon atoms, or A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and a nitrogen atom bonded to a naphthopyran ring, or an aromatic hydrocarbon as the heterocyclic group A fused heterocyclic group in which a ring or an aromatic heterocyclic ring is fused, wherein R ² and R ³ may be different from each other, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or an alkyl group, R ⁴ is a substituted radical, n represents the number of R ⁴ 0 to 4
And when n is 2 or more, R ⁴ may be the same or different groups. A chromene compound represented by the formula: 10
Chromene composition comprising 0 parts by weight and (B) an ultraviolet absorber: 10 to 1000 parts by weight 2. A polymerizable composition comprising 100 parts by weight of a polymerizable monomer and 0.001 to 1 part by weight of the chromene composition according to claim 1. 3. A cured product obtained by polymerizing the polymerizable composition according to claim 2.