JP3047434B2 - Photochromic molding - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photochromic molded article having excellent photochromic action durability.

(Prior art) Photochromism is a phenomenon that has been attracting attention for the past several years. When a compound is irradiated with light containing ultraviolet light 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 compounds having various structures have been conventionally synthesized and proposed, but no special common skeleton is recognized in the structure.

As the photochromic compound, a spiropyran compound, a spirooxazine compound, a thionin compound, a viologen compound, a fulgide or fulgimide compound, an azobenzene compound, a dithizone metal compound, and chromene or a derivative thereof are known.

When each of these compounds is used alone, a desired color tone may not be obtained. In particular, when used as a photochromic lens, color tones such as gray, amber, and brown are preferred, but these color tones cannot be obtained with the above compounds alone. In order to obtain these colors, chromene or a derivative thereof having a color tone of yellow to orange, a viologen compound or a dithizone metal compound and a spiropyran compound having a color tone of red to blue, a spirooxazine compound, a thionin compound, fulgide or It is conceivable to mix a flugimide compound and an azobenzene compound.

(Problems to be Solved by the Invention) However, it has been found that the color tone of the mixture of the plurality of photochromic compounds gradually changes over time. As a result of an investigation by the present inventors regarding the cause, the fatigue life of the various photochromic compounds described above is different from each other, and when a photochromic compound having a different fatigue life is used in combination, the photochromic compound having the shorter fatigue life is used first. It was found that the color was not developed any more.

Therefore, the present inventors have proposed a photochromic compound mixture that does not cause a color change over a long period of time if the durability of a photochromic compound having a short fatigue life can be extended to be substantially the same as that of a photochromic compound having a long fatigue life. Thought that it could be obtained. Then, intensive studies were carried out to improve the durability of photochromic compounds having a short fatigue life.

(Means for Solving the Problems) As a result, it has been found that, when the photochromic compound is dispersed in the polymer, the compound existing more inside than on the surface has good repetition durability. Therefore, a photochromic compound having relatively short durability is present inside the polymer, and a photochromic compound having relatively excellent durability is present on the surface of the polymer.
The inventors have succeeded in adjusting the durability of various photochromic compounds to the same degree, and have come to propose the present invention.

That is, the present invention provides a photochromic molded article containing a photochromic compound having a different fatigue life, wherein a photochromic compound having a long fatigue life is present on a surface layer of a polymer containing a photochromic compound having a short fatigue life dispersed therein. Body.

In the present invention, known photochromic compounds are employed without any limitation. For example, spiropyran compounds,
Spirooxazine compounds, thionine compounds, viologen compounds, fulgide or fulgimide compounds, azobenzene compounds, dithizone metal compounds, and chromene derivatives may be mentioned.

When using the photochromic molded article of the present invention as a photochromic lens, gray, amber, brown or the like color tone is required, in order to prepare these color tones, chromene or a derivative thereof whose color tone is yellow to orange, It is preferable to combine a viologen compound or a dithizone metal compound with a spiropyran compound, a spirooxazine compound, a thionin compound, a fulgide or fulgimide compound, and an azobenzene compound whose color tone is red to blue.

Among them, photochromic properties such as coloring density, fading rate and fatigue life, and the combination of a spirooxazine compound and chromene or a derivative thereof, and a fulgide or fulgimide compound and chromene or A combination with a derivative thereof is suitably employed in the present invention.

A spirooxazine compound which is a photochromic compound suitably used in the present invention is represented by the following formula [I].

In the above general formula (I), Is an aromatic hydrocarbon group or an unsaturated heterocyclic group which may be substituted, respectively. Specific examples of the aromatic hydrocarbon group include a divalent group derived from one benzene ring such as a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring or a fused ring of 2 to 4 benzene rings. Further, the above aromatic hydrocarbon group may be substituted with a substituent. Examples of such substituents are fluorine,
Halogen atoms such as chlorine, bromine and iodine; hydroxyl groups; cyano groups; nitro groups; amino groups;
Methylamino group; having 1 to 4 carbon atoms such as diethylamino group
Alkylamino group; methyl group, ethyl group; lower alkyl group having 1 to 4 carbon atoms such as propyl group and t-butyl group; halogen having 1 to 3 halogen atoms such as trifluoromethyl group and 2-chloroethyl group. Lower alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, t-butoxy group; aryl group having 6 to 10 carbon atoms such as phenyl group, naphthyl group and tolyl group; phenoxy group, 1 An aryloxy group having 6 to 14 carbon atoms such as a naphthoxy group; an aralkyl group having 7 to 15 carbon atoms such as a benzyl group, a phenylethyl group and a phenylpropyl group; and a 7 to 15 carbon atom such as a benzyloxy group and a phenylpropoxy group.
And an alkylthio group having 1 to 4 carbon atoms. These substituents may be the same or different, and the position is not particularly limited.

In the above general formula (I), Examples of the optionally substituted unsaturated heterocyclic group represented by are a 5-membered ring and a 6-membered ring containing an oxygen, sulfur, or nitrogen atom, or a heterocyclic group in which a benzene ring or a cyclohexane ring is condensed. Specifically, it is derived from a nitrogen-containing heterocycle such as a pyridine ring, a quinoline ring, a pyrrole ring, or an indole ring; an oxygen-containing heterocycle such as a furan ring or a benzofuran ring; or a sulfur-containing heterocycle such as a thiophene ring or a benzothiophene ring. And a divalent heterocyclic group represented by the formula: In particular, in the case of a bicyclic fused heterocycle of a benzene ring and a 5- or 6-membered heterocycle, a high color density can be obtained.

As the substituent of the unsaturated heterocyclic group, the substituent of the aromatic hydrocarbon group described above is employed without any limitation.

Next, in the general formula [I], Is It is.

Here, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different, respectively, a hydrogen atom, a halogen atom, a hydrocarbon group,
An alkoxy group, a cyano group, a halogenoalkyl group, an amino group, a substituted amino group or an alkoxycarbonyl group,
At least one of R ₄ and R ₅ is a cyano group, a halogenoalkyl group or an alkoxycarbonyl group, Is an optionally substituted aromatic hydrocarbon group or an unsaturated heterocyclic group.

Examples of the halogen atom include fluorine, chlorine, and bromine.

Examples of the hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group. Among them, the alkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
It is preferably from 4 to 4. More specific examples of the alkyl group include a methyl group, an ethyl group, and an isopropyl group. Further, the aryl group preferably has 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. The aralkyl group preferably has 7 to 14 carbon atoms. Specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, and a naphthylmethyl group.

Next, the alkoxy group is not particularly limited, but generally preferably has 1 to 10 carbon atoms, and preferably 1 to 4 carbon atoms. Specific examples include a methoxy group, an ethoxy group, and an isopropoxy group. it can.

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. Specifically, a trifluoromethyl group,
Trichloromethyl group, tribromomethyl group and the like.

An amino group or a substituted amino group has the general formula Indicated by R ₁₁ and R ₁₂ are preferably the same or different hydrogen atoms and hydrocarbon groups, respectively. As the hydrocarbon group, the same groups as those described for R _{4 to} R ₁₀ are preferably used. Furthermore, the substituted amino group has the general formula In the case shown by R ₁₃ is an alkylene group such as a tetramethylene group or a pentamethylene group; --CH ₂ OCH ₂ CH _2- , --CH ₂ CH ₂ OCH ₂ CH _2- , --CH ₂ O (CH _{2 3}
An oxyalkylene group such as —CH ₂ SCH ₂ CH ₂ —, —CH ₂ S (C
Thioalkylene groups such as H _{2 3} and —CH ₂ CH ₂ SCH ₂ CH ₂ —; And the like.

The alkoxycarbonyl group is not particularly limited, but generally has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More specific examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

In the general formula [I], at least one of R ₄ and R ₅ must be a cyano group, a halogenoalkyl group or an alkoxycarbonyl group. By selecting these groups, the spirooxazine compound used in the present invention exhibits a good photochromic action even in a high temperature range.

next Is an aromatic hydrocarbon group or an unsaturated heterocyclic group which may be substituted. These groups are already The groups described for are employed without any limitation.

Is the general formula [I] And the spirooxazine compound used in the present invention exhibits a good photochromic action even at a high temperature range.

Next, in the general formula [I], But When R ₁ and R ₂ are a hydrogen atom or an alkyl group, R ₁ and R ₂ may form a ring together,
R ₃ is an alkoxycarbonylalkyl group, When R ₁ and R ₂ are a hydrogen atom or an alkyl group, at least one of which is an alkyl group having 2 or more carbon atoms,
Or they may together form a ring,
R ₃ is a hydrogen atom, a hydrocarbon group, an alkoxycarbonylalkyl group or a cyanoalkyl group.

The alkyl group is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the above alkyl group include a methyl group, an ethyl group, and an isopropyl group. Also, R ₁ and R ₂
When they together form a ring, they are not particularly limited, but generally a cycloalkyl ring having 5 to 10 carbon atoms, a bicycloalkyl ring, and a tricycloalkyl ring are preferred.
When these are exemplified more specifically, a cyclopentyl ring,
Examples include a divalent group derived from a cyclohexyl ring, a cycloheptyl ring, a norbornane ring, an adamantane ring, or a bicyclo [3.3.1] nonane ring. These R ₁ and R ₂ are
In either case, it is preferable that one is an alkyl group having 1 or more carbon atoms and the other is an alkyl group having 2 or more carbon atoms, or that these are together forming a ring in a high-temperature region. It is suitable for indicating

In the general formula [I], the hydrocarbon group represented by R ₃ is not particularly limited, and the groups described in R _{4 to} R ₁₀ are employed.

The alkoxy group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. The alkylene group in the alkoxycarbonylalkyl group is not particularly limited, but generally has 1 to 10, preferably 1 to 4 carbon atoms. More specific examples of the alkoxycarbonylalkyl group include a methoxycarbonylmethyl group, a methoxycarbonylethyl group, a methoxycarbonylpropyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, an ethoxycarbonylbutyl group, and a butoxycarbonylethyl group.

The cyanoalkyl group is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the cyanoalkyl group include a cyanomethyl group, a cyanoethyl group, and a cyanopropyl group.

Next, chromene or a derivative thereof suitably used in combination with the above-mentioned spirooxazine compound is the compound described below.

Chromene has the formula It is a compound shown by these. Further, as the chromene derivative, the compound having the above chromene skeleton is employed without any limitation. In the present invention, a chromene derivative represented by the following formula [II] is preferably used because it has excellent photochromic properties.

In the above general formula (II), An aromatic hydrocarbon group and an unsaturated heterocyclic group represented by
Of the spirooxazine compound represented by the general formula (I) The group described for is employed. Further, the substituents of these aromatic hydrocarbon group and unsaturated heterocyclic group are the same as those in the above general formula [I]. The substituents of the aromatic hydrocarbon group and the unsaturated heterocyclic group represented by are adopted without any limitation.

In addition, -R ⁵ -SR ⁶ , [However, R ⁵ is an alkylene group or 0-R ⁸ _n (however, R ⁸
Is an alkylene group, and n is a positive integer. R ⁶ and R ⁷ are the same or different alkyl groups, and X is -N <, -P <, It is. ] May be substituted one or more times.
The carbon number of the alkyl group and the alkylene group is preferably in the range of 6 to 20, and _n of 0-R ⁸ n
Is preferably an integer such that the total number of carbon atoms is 6 to 20.

Next, in the general formula [II], the hydrocarbon group and the substituted amino group represented by R ¹ , R ² , R ³ and R ⁴ correspond to R ₄ to R _{4 of the} spirooxazine compound represented by the general formula [I]. similar hydrocarbon groups and substituted amino groups as described for R ₁₀ is employed.

Further, in the general formula [II], R ¹ and R ² may form a ring together, and the ring in this case is the same as R ₁ and R ₂ in the general formula [I]. The rings described are employed without any restrictions.

Among the above-mentioned chromenes or derivatives thereof, in the general formula (II), Is preferably a condensed ring of two or more rings because of high color density. Among them, compounds in which a ring is condensed at positions 7 and 8 of the chromene skeleton are more preferable. Further, in the general formula (II),
When R ¹ and R ² form a ring, the chromene skeleton
Compounds in which a ring is fused at the 5- or 6-position are also preferably used.

Next, fulgide compounds or fulgimide compounds that can be suitably used as a photochromic compound in the present invention in combination with the above-mentioned chromene or a derivative thereof are as follows. The fulgide compound has the following formula: And a compound having photochromic properties is employed without any limitation. The fulgimide compound is represented by the following formula: And a compound having photochromic properties is employed without any limitation.

In the present invention, as the fulgide compound or fulgimide compound, a compound represented by the following formula is generally used.

In the formula Is an aromatic hydrocarbon group or an unsaturated heterocyclic group which may each have a substituent; R ₁₁ is a monovalent hydrocarbon group or a monovalent heterocyclic group which may each have a substituent Is a norbornylidene group or an adamantylidene group, each of which may have a substituent; X ″ is an oxygen atom, a group NR ₁₂ A group N-A ₃ -A ₄ or a group N-A ₃ -R _14.

In the general formula (III), An aromatic hydrocarbon group and an unsaturated heterocyclic group represented by
Of the spirooxazine compound represented by the general formula (I) The group described for is employed. Further, the substituents of these aromatic hydrocarbon group and unsaturated heterocyclic group are the same as those in the above general formula [I]. The substituents of the aromatic hydrocarbon group and the unsaturated heterocyclic group represented by are adopted without any limitation.

the above Is an atom or group selected from the group consisting of a halogen atom, a nitro group, a cyano group, an amino group, an alkylthio group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. Is preferably a divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group which may be substituted in each case by at least one of the above.

Also, Is an aryl group having 6 to 14 carbon atoms which may be substituted in each case by 1 to 3 of the above-mentioned substituents, or 5 containing one nitrogen atom, oxygen atom and sulfur atom.
More preferably, it is a membered or 6-membered monocyclic heterocyclic group or a condensed heterocyclic group in which a benzene ring or a cyclohexene ring is condensed to the heterocyclic group.

Further above Is preferably a divalent benzene ring, a 5-membered or 6-membered monocyclic heterocyclic ring containing one heteroatom or a condensed heterocyclic ring in which a benzene ring or a cyclohexene ring is condensed to this heterocyclic ring. . The benzene ring, the monocyclic heterocyclic ring or the condensed heterocyclic ring, which contains one or two substituents described above, is also a preferable embodiment.

R ₁₁ in the general formula [III] is a monovalent hydrocarbon group or a monovalent heterocyclic group which may have a substituent.

As such a hydrocarbon group R ₁₁ similar hydrocarbon groups as described in R ₄ to R ₁₀ of the spirooxazine compound represented by the general formula (I) is employed.

As the heterocyclic group for R ₁₁ , at least one hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom is 1 to
A 5-membered or 6-membered monocyclic heterocyclic group containing three, preferably one or two, or a condensed heterocyclic group obtained by condensing benzene with this is preferred. Specific examples of such a heterocyclic group include:
Said And saturated heterocyclic groups such as saturated piperidine ring, piperazine ring, morpholine ring, pyrrolidine ring, indoline ring, chroman ring and the like.

Hydrocarbon group or heterocyclic group R ₁₁ described above is not particularly permissible may have a substituent. Such a substituent preferably contains at most 5 and preferably up to 3 with respect to the hydrocarbon group or the heterocyclic group. The same substituents as described in can be exemplified.

R ₁₁ is preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a alkoxy group having 1 to 4 carbon atoms or a phenyl group; a halogen atom or an alkoxy group having 1 to 4 carbon atoms. A substituted or unsubstituted aryl group having 6 to 10 carbon atoms; or a 5- or 6-membered monocyclic heterocyclic group containing 1 to 3, especially 1 to 3 nitrogen, carbon and sulfur atoms, or It is a condensed heterocyclic group in which a benzene ring is condensed to the heterocyclic group, particularly a monocyclic heterocyclic group.

More particularly preferred are 1 to the number of carbon atoms as the R ₁₁
An alkyl group having 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

In the general formula (III) of the present invention, Represents a norbornylidene group or an adamantylidene group which may have a substituent. Where the norbornylidene group is The adamantylidene group is represented by the following formula.

The above formula shows a skeleton structure of a norbornylidene group and an adamantylidene group each having no substituent. In these norbornylidene groups or adamantylidene groups, the hydrogen atom of the above formula may be substituted by a substituent, and the number thereof may be one or more. When it has a substituent, its type, number and position are arbitrarily selected depending on the purpose and application. When the compound has a plurality of substituents, the substituents may be the same or different.

Examples of the substituent of the norbornylidene group or the adamantylidene group include a hydroxy group; an alkylamino group having 1 to 4 carbon atoms such as a methylamino group and a diethylamino group; and a carbon atom such as a methoxy group, an ethoxy group and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms; an aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group; an aryloxy group having 6 to 14 carbon atoms such as phenoxy group and 1-naphthoxy group; methyl group, ethyl group and t-butyl A lower alkyl group having 1 to 4 carbon atoms, such as a group; a halogen atom such as fluorine, chlorine, and oxa;
A cyano group; a carboxyl group; an alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl; a halogen-substituted alkyl group having 1 or 2 carbon atoms such as trifluoromethyl group; a nitro group; ~14
An aralkyl group having 7 to 15 carbon atoms, such as a phenylethyl group and a phenylpropyl group, and an alkylthio group having 1 to 4 carbon atoms.

Preferred examples of these substituents include a halogen atom,
Hydroxy group, alkyl group having 1 to 4 carbon atoms, 1 to 1 carbon atom
4 alkoxy groups, alkoxycarbonyl groups having 2 to 10 carbon atoms, aralkyl groups having 7 to 9 carbon atoms or 6 to 10 carbon atoms
Is an aryl group.

X "in the general formula (III) in the present invention, an oxygen atom (-0-), the group N-R _12, group _{N-A 1 -B 1 - (} A 2 m (B 2 n R 13, group N -A ₃ -A ₄ or the group NA ₃ -R ₁₄ is shown.

In the general formula [III], X ″ is a group N—A ₁ —B ₁ — (A _{2 m} (B _{2 nR 13} , a group N—A ₃ —A ₄ or a group N—A ₃ —R ₁₄ , In particular, the group N—A ₃ —R ₄ or the group N—A ₁ —B ₁ — (A _{2 m} (B _{2 n} R ₁₃ (where R ₁₃ is selected from the group consisting of a halogen atom, a cyano group and a nitro group) 1 to 3 atoms or an optionally substituted alkyl group having 1 to 10 carbon atoms) is more preferable from the viewpoint of durability of the photochromic property of the obtained compound.

X ″ in the general formula [III] represents the above-mentioned group N—A ₁ -B _1- (A _{2 m} (B _{2 n} R ₁₃ , wherein R ₁₃ is a naphthyl group or a naphthylalkyl group; If it is N-a ₃ -A _4, to the extent atom number of 3 to 7 backbone sandwiched between the naphthyl group and the imide group represented by R ₁₃ or a ₄ (N-) This is preferable because a compound having excellent photochromic action durability can be obtained.

Next, R ₁₂ , R ₁₃ , R ₁₄ , A ₁ , A ₂ , A ₃ , A
₄ , the definitions of B ₁ , B ₂ , m and n will be described in detail.

R ₁₂ represents a hydrogen atom, an alkyl group or an aryl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-, iso- or tert-butyl group,
Examples thereof include a pentyl group, a hexyl group, an octyl group, and a decyl group. Among them, those having 1 to 20 carbon atoms, and those having 1 to 10 carbon atoms are preferable. Examples of the aryl group include those having 6 to 10 carbon atoms such as a phenyl group, a tolyl group and a naphthyl group.

A ₁ , A ₂ and A ₃ may be the same or different from each other and may be an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group. Specific examples thereof include, for example, an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, a tetramethylene group or a 2,2-dimethyltrimethylene group; an ethylidene group; C2-C10 alkylidene such as propylidene or isopropylidene; C3-C10 cycloalkylene such as cyclohexylene; 2-methylcyclohexane-α, 1-diyl 4-methylcyclohexane-α, 1-diyl group And an alkylcycloalkane-diyl group having 6 to 10 carbon atoms. As A ₁ and A ₂ , particularly those having 1 to 1 carbon atoms
Preferred are an alkylene group having 6 carbon atoms, an alkylidene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, and an alkylcycloalkane-diyl group having 6 to 7 carbon atoms.

B ₁ and B ₂ may be the same as or different from each other, and are selected from the following group of seven bonding groups.

Or m and n each independently represent 0 or 1, and when it represents 0, A _{2 m} or B _{2 n} means a bond. When m is 0, n also represents 0.

R ₁₃ represents an alkyl group, a naphthyl group or a naphthylalkyl group which may have a substituent. The number of carbon atoms of the above alkyl group is not particularly limited, but is preferably 1 to 10, and the alkyl group of the naphthylalkyl group preferably has 1 to 4 carbon atoms.

The substituent of each group described above is not particularly limited, but the alkyl group may be substituted with 1 to 3 atoms or groups selected from the group consisting of a halogen atom, a cyano group, and a nitro group; The naphthyl group or naphthylalkyl group is selected from the group consisting of a halogen atom, a cyano group, a nitro group, an alkylamino group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. Or 1 to 3 atoms or groups. The alkyl group represented by the R _13, can be used the same alkyl groups as those described above for R _12. Examples of the naphthylalkyl group include a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group and a naphthylbutyl group.

A ₄ represents a naphthyl group which may have a substituent.
The type of the substituent is not particularly limited, but the naphthyl group may be a halogen atom, an ano group, a nitro group, an alkylamino group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. It may be substituted with 1 to 3 atoms or groups selected from the group consisting of: R ₁₄ represents a halogen atom, a cyano group or a nitro group.

In the definition of R ₁₃ and A ₄ described above, examples of the halogen atom include fluorine, chlorine and bromine.

The photochromic molded article of the present invention is formed by dispersing a photochromic compound having a short fatigue life in a polymer as described above and dispersing a photochromic compound having a long fatigue life in a polymer surface layer. The point has the largest feature point.

In the present invention, the “fatigue life” is defined as the case where the absorbance at the maximum absorption wavelength of each photochromic compound is reduced to 1/2 of the initial (T ₀ ) absorbance as shown in Examples described later. It is evaluated based on the time required (T _1/2 ). For example, among combinations of various photochromic compounds, in the case of a combination of the above spirooxazine compound and chromene or a derivative thereof, chromene or a derivative thereof is dispersed inside the polymer, and the spirooxazine compound is present on the surface of the polymer. Let it. In the case of a combination of chromene or a derivative thereof and fulgide or a fulgimide compound, fulgide or a fulgimide compound is dispersed in a polymer, and chromene or a derivative thereof is present on the surface of the polymer.

In the present invention, three or more photochromic compounds described above may be used simultaneously. In this case, the photochromic compound having the shortest fatigue life is dispersed in the polymer, and the photochromic compound having the longest fatigue life is used as the polymer surface layer. The photochromic compound having an intermediate fatigue life may be determined depending on the degree of the fatigue life in the inside of the polymer or in the surface layer of the polymer. For example, among the above three photochromic compounds, the fulgide compound has the shortest fatigue life, so that the fulgide compound may be dispersed in the polymer and the spirooxazine compound and the chromene compound may be present on the surface of the polymer. .

In the present invention, the polymer in which the photochromic compound having a short fatigue life is dispersed can be used regardless of a thermoplastic resin or a thermosetting resin.

Any thermoplastic resin may be used as long as it can uniformly disperse a photochromic compound having a short fatigue life.Optically preferred are, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, and polyethyl methacrylate. , Polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane, polycarbonate and the like.

Dispersion of a photochromic compound having a short fatigue life in a thermoplastic resin is performed by synthesizing the thermoplastic resin, that is, a method in which polymerization is performed in the presence of the compound, or the melting temperature of the thermoplastic resin and the compound in the thermoplastic resin. The method of melt-kneading is mentioned above.

Next, as the thermosetting resin, ethylene glycol diacrylate, diethylene glycol dimethacrylate,
Ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2
Poly (acrylic acid) and poly (methacrylic acid ester) compounds such as bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl Polyvalent allyl compounds such as fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ) Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds such as ether and 1,4-bis (methacryloylthiomethyl) benzene; polymers of radically polymerizable polyfunctional monomers such as divinylbenzene: Is each of these monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride; acrylic acid such as methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, and 2-hydroxyethyl methacrylate; 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, methylstyrene, vinyl Copolymers with radically polymerizable polyfunctional monomers such as vinyl compounds such as naphthalene and bromostyrene: ethanedithiol, propanetriol, hexanedithiol, pentaerythritol tetrakis Addition copolymers of polyvalent thiol compounds such as thioglycolate and di (2-mercaptoethyl) ether with the above-mentioned radically polymerizable polyfunctional monomers: diphenylethane diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, etc. An addition polymer of a polyhydric isocyanate compound with a polyhydric alcohol compound such as ethylene glycol, trimethylolpropane, pentaerythritol, and bisphenol A, or the above-mentioned polyhydric thiol compound may be used. These raw material monomers can be used alone or in combination of two or more.

For dispersing the photochromic compound having a short fatigue life in the thermosetting resin described above, a method of mixing the raw material monomer of the thermosetting resin and the photochromic compound having a short fatigue life and then polymerizing the mixture is generally adopted.

The amount of the photochromic compound having a short fatigue life to be dispersed in such a polymer is 0.001 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polymer.

The mode in which the photochromic compound having a long fatigue life is present on the surface layer of the polymer in which the photochromic compound having a short fatigue life is dispersed is not particularly limited. A long photochromic compound is impregnated to form a photochromic compound layer having a long fatigue life near the surface of the polymer.

A resin layer containing a photochromic compound having a long fatigue life dispersed therein is formed on the surface of the polymer.

Is preferably employed.

First, as a method of impregnating the photochromic compound having a long fatigue life on the surface of the polymer, generally, a photochromic compound having a long fatigue life is heated to a melting point or higher, melted, and the polymer is immersed therein for 1 to 60 minutes. A method of impregnating with a photochromic compound having a long fatigue life is used. Further, a method in which a photochromic compound having a long fatigue life is dissolved in a high boiling point inert liquid and a polymer is immersed therein, as disclosed in JP-A-61-501145, can also be employed. Here, as the high boiling point inert liquid,
A silicone oil, a perfluoro oil, or the like is used, and a photochromic compound having a long fatigue life may be dissolved in a high boiling point inert liquid at a concentration of 0.1 to 50% by weight. Further, a photochromic compound having a long fatigue life is dispersed in a commercially available lacquer as shown in JP-A-60-112880, which is applied to a polymer, and is heated at 100 to 250 ° C for 1 to 60.
A method of impregnating the surface by heating for a minute is also employed. At this time, the concentration of the photochromic compound having a long fatigue life in a commercially available lacquer is preferably 0.1 to 50% by weight.

In this way, a photochromic compound having a long fatigue life can be generally impregnated to a depth of about 5 μm from the surface of the polymer.

On the other hand, when a resin layer containing a photochromic compound with a long fatigue life is formed on the surface of the polymer, the resin layer is strongly adhered to the surface of the polymer to be coated, and the photochromic compound with a long fatigue life is uniformly dispersed. Any of the thermoplastic resins and thermosetting resins described above for the polymer can be used without any limitation. In particular, when the photochromic molded article of the present invention is used for an optical material such as an optical lens, a method of forming a coating of a hydrolyzate of an organosilicon compound on the surface of the polymer in order to improve the surface hardness of the polymer is used. A primer used for the purpose of improving the adhesion between the film of the hydrolyzate and the polymer on the silicon compound can be suitably used. Examples of such a primer include an epoxy resin-based primer having two or more epoxy groups in one molecule such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and an alicyclic epoxy resin. Silane-based primers such as Tosprim A, Tosprim B, Tosprim C, Tosprim D, Tosprim E and YP9341 (both manufactured by Toshiba Silicone Co., Ltd .: trade name); Polysol F361, Polysol F341, Polysol
FF-450, Kogum HW-7 (above, manufactured by Showa Polymer Co., Ltd .: trade name), Sebian A517, Sebian A4716, Sebian A4670
1, Sebian A4635, Sebian A4730, Sebian A45000,
Sebian A4171 (all manufactured by Daicel Chemical Industries, Ltd .; trade name), Nicazole FL-3000, Nicazole ME-702, Nicazole FX-201, Nicazole FX-322, Nicazole FX-32
9, Nicazole TS-444, Nicazole TS-501, Nicazole TS-517, Nicazole TS-542, Nissetsu PC-501, Nissetsu PE-115, Nissetsu PE-118, Nissetsu PE-121
(Made by Nippon Carbide Industry Co., Ltd .; trade name). In addition, hydrophilic resins such as polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyacrylonitrile, and cellulose-based natural polymers can also be used as the resin for dispersing the photochromic compound having a long fatigue life.

The amount of the photochromic compound having a long fatigue life to be contained in these resins may be determined according to the coloring density or color tone of the obtained photochromic molded article, and generally, based on 100 parts by weight of the resin, the photochromic compound having a long fatigue life is used. It is preferred that the compound be in the range of 0.001 to 60 parts by weight, particularly 0.1 to 40 parts by weight.

The thickness of the resin layer containing the photochromic compound having a long fatigue life may be determined according to the coloring density or color tone of the obtained photochromic molded product, but is generally 0.5 to 10
The range of μm is preferred.

The mixing ratio of the photochromic compound having a short fatigue life and the photochromic compound having a long fatigue life may be determined according to the desired color tone of the photochromic molded article of the present invention, but fulgide or a fulgimide compound and chromene or a derivative thereof. When used in combination with generally 100 parts by weight of a fulgide compound or a fulgimide compound, chromene or a derivative thereof is in the range of 0.01 to 1000 parts by weight, and when a good mixed color is expected,
It is preferable to select from the range of 0.1 to 10 parts by weight.

Further, when chromene or a derivative thereof and a spirooxazine compound are used in combination, the spirooxazine compound is generally in the range of 0.01 to 10,000 parts by weight with respect to 100 parts by weight of chromene or a derivative thereof, so that a good mixed color is obtained. Is expected, it is preferable to select from the range of 0.05 to 1000 parts by weight.

By incorporating an ultraviolet stabilizer into the photochromic molded article of the present invention, the durability of photochromic properties can be further improved. As the ultraviolet stabilizer, a known ultraviolet stabilizer added to various plastics can be used without any limitation.

In the present invention, considering the improvement in durability of the photochromic compound, among various ultraviolet stabilizers, a singlet oxygen quencher, a hindered amine light stabilizer, a hindered phenol antioxidant, and a sulfur-based antioxidant are preferably used. Is done. More specific examples of these ultraviolet stabilizers include Sheasorb UV1084 and Sheasorb 3346 (all manufactured by American Cyanamid Co.); UV-Cek AM101 and UV-Cek AM105 (all manufactured by Ferro Corporation); Irgas Tab 2002, Tinuvin 765, Tinuvin 144, Chimasorb 94
4, Tinuvin 622, Irganox 1010, Irganox 245
(Above, manufactured by Ciba-Geigy); Rirex NBC (manufactured by DuPont); Sheasorb 3346 (manufactured by American Cyanamid); SANOL LS-1114, SANOL LS-744, SANOL L
S-2626 (above, manufactured by Sankyo Co., Ltd.); Sumilizer GA-8
0, Sumilizer GM, Sumilizer BBM-S, Sumilizer WX
−R, Sumilizer S, Sumilizer BHT, Sumilizer TP−
D, Sumilizer TPL-R, Sumilizer TPS, Sumilizer M
B (above, manufactured by Sumitomo Chemical Co., Ltd.); Mark AO-50, Mark AO-2
0, mark AO-30, mark AO-330, mark AO-23 (above,
Adeka Argus Co .; Antioxidant HPM-12
(Manufactured by SFOS). Each of the above names is a trade name.

The ultraviolet stabilizer, the photochromic compound having a short fatigue life may be simultaneously added and dispersed at the time of dispersing the photochromic compound into the polymer, and the photochromic compound having a long fatigue life may be present in the surface layer of the polymer by the method described above. It may be used at the same time.

The blending ratio of the ultraviolet stabilizer is preferably in the range of 0.01 to 10,000 parts by weight, with respect to 100 parts by weight of the photochromic compound having a long fatigue life and 100 parts by weight of the photochromic compound having a short fatigue life, particularly, the obtained photochromic compound. From the viewpoint of the photochromic property of the molded product, the amount of the ultraviolet stabilizer is preferably in the range of 10 to 500 parts by weight.

Further, in the present invention, for the purpose of further improving the durability of photochromic properties, the surface of the photochromic molded article of the present invention may be coated with a layer made of a hydrolyzate of an effective silicon compound.

(Effects) As described above, the photochromic molded article of the present invention changes from colorless to colored or darkened by light including ultraviolet rays such as sunlight or light from a mercury lamp, and the change is reversible. It shows excellent dimming properties. The present invention has succeeded in easily obtaining various intermediate colors such as gray, brown, and amber by using two or more photochromic compounds in combination.

Therefore, the photochromic molded article of the present invention can be used in a wide range of fields, for example, various recording memory materials, copying materials, photoreceptors for printing, recording materials for cathode ray piping, photosensitive materials for lasers, replacing silver salt photosensitive materials. And various recording materials. In addition, the photochromic molded article of the present invention can be used as a material for photochromic lenses, optical filters, displays, light meters, decorations, and the like.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. “Parts” in the examples is “parts by weight”.

 The symbols in the following examples indicate the following compounds.

・ BMDBP: 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane ・ Cl-St: chlorostyrene ・ TMP-TAC: trimethylolpropane triallyl carbonate ・ BADBP: 2,2-bis ( 4-allyl carbonate ethoxy-3,5-dibromophenyl) propane ・ ADC: allyl diglycol carbonate ・ DAP: diallyl phthalate ・ St: styrene ・ DCIPF: di (2-chloroisopropyl) fumarate ・ EGDMA: ethylene glycol dimethacrylate ・ PETTP : Pentaerythritol tetrakis (β-thiopropionate) ・ DME: Di (2-mercaptoethyl) ether ・ DVB: Divinylbenzene ・ XIC: Xylylene diisocyanate ・ HPA: 3- (2,4-dibromophenoxy) -2- Hydroxypropyl acrylate ・ MMA: Methyl methacrylate ・ DEGDMA: Diethylene glycol Dimethacrylate ・ TBBM: 3,4,5-tribromobenzyl methacrylate ・ HEMA: 2-hydroxyethyl methacrylate ・ BMA: Benzyl methacrylate ・ IPP: Diisopropyl peroxycarbonate ・ Perbutyl ND: t-butyl (manufactured by NOF Corporation) Peroxy-2-hexanate-PVA: polyvinyl alcohol-PHEMA: poly (2-hydroxyethyl methacrylate)-PAN: polyacrylonitrile Production Example 1 1-hydroxy-2-acetonaphthone 10 g (0.054mo
l) with 6.6 g (0.06 mol) of norcamphor and 8 g of pyrrolidine
(0.113 mol) was dissolved in 300 cc of toluene to prepare a solution. The mixture was boiled for 10 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized from acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. Heat 7.47 g of this chromanol compound together with 4.5 g of anhydrous copper sulfate in a stream of carbon dioxide at 150 to 160 ° C. for 10 minutes,
By purifying the brown viscous liquid by chromatography on silica gel, a chromene derivative of the following formula is obtained.
6.3 g were obtained.

Elemental analysis of this compound gave C 86.93% and H 6.89.
% And O 6.18%, which corresponded very well to the calculated values for C ₁₉ H ₁₈ O, C 87.02%, H 6.87%, and O 6.12%. Also, when the proton nuclear magnetic resonance spectrum was measured, a peak of 6H based on the proton of the naphthalene ring at around δ7.2 to 8.3 ppm, a peak of 2H based on the proton of the alkene at around δ5.6 to 6.7 ppm, δ1.2 A broad peak of 10H based on the proton of the norbornylidene group was shown at about 2.5 ppm. When ¹³ C-nuclear magnetic resonance spectrum was further measured, a peak based on the carbon of the norbornylidene group around δ 27 to 52 ppm, a peak based on the carbon of the naphthalene ring around δ 110 to 160 ppm, and a peak based on the carbon of the alkene around δ 80 to 110 ppm Appears. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (1).

Production Example 2 A solution prepared by dissolving 10 g (0.054 mol) of 1-acetyl-2-naphthol, 8.29 g (0.06 mol) of bicyclo [3.3.1] nonan-9-one, and 8.7 g (0.10 mol) of morpholine in 300 cc of toluene was prepared. Prepared. The mixture was boiled for 5 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, and the remaining chromanone compound was recrystallized from acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and lithium aluminum hydride was added to obtain a chromanol compound. This chromanol compound 6.49 g was heated with anhydrous copper sulfate at 170 to 180 ° C. for 10 minutes in a stream of carbon dioxide, and the brown viscous liquid was purified by chromatography on silica gel to obtain 5.8 g of a chromene derivative of the following formula. Was.

The elemental analysis value of this compound was 86.81% for C and 7.62 for H.
% And O 5.57%, which corresponded very well to the calculated values for C ₂₁ H ₂₂ O, C 86.90%, H 7.59% and O 5.52%. Also, when the proton nuclear magnetic resonance spectrum was measured, the peak of 6H based on the proton of the naphthalene ring around δ7.2 to 8.3 ppm, the peak of 2H based on the proton of the alkene around δ6.0 to 7.0 ppm, δ1.2 A broad peak of 14H based on the proton of the bicyclo [3.3.1] 9-nonylidene group was shown at about 2.5 ppm. When further measured ¹³ C-nuclear magnetic resonance spectrum, a peak based on carbon of bicyclo [3.3.1] 9-nonylidene group around δ27 to 55 ppm, a peak based on carbon of naphthalene ring around δ110 to 160 ppm, δ80 to 110 ppm A peak based on the carbon of the alkene appears in the vicinity. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (2).

Production Example 3 3.06 g (0.01 mol) of a chromanone compound represented by the following formula Was dissolved in 50 cc of anhydrous ether, the solution was cooled to 0 ° C., and a freshly prepared Grignard reagent CH ₃ Mgl (0.012 mol) was added dropwise to the solution over 50 minutes in 50 cc of anhydrous ether. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, and the ether was removed under reduced pressure. The compound was changed to a chromanol compound. Then, the chromanol compound was mixed with anhydrous copper sulfate in a stream of carbon dioxide at 200 ° C. for about 1 hour.
After heating for 0 minutes, a brown viscous liquid is generated by chromatography on silica gel, and a chromene derivative of the following formula
2.47 g were obtained.

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

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

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

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

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

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

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

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

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

Production Example 15 3-thienylethylidene-2-adamantylidene succinic anhydride of the following formula: 3.4 g (0.01 mol) And 17.8 g (0.02 mol) of glycine-methyl ester of the following formula Was dissolved in toluene and heated at 50 ° C. for 2 hours under a nitrogen atmosphere. After the reaction, the solvent was removed and dissolved in acetyl chloride,
Refluxed for 1 hour to cyclize. The obtained compound was refluxed in O-dichlorobenzene for 6 hours to rearrange to the following fulgimide compound (15). This compound was purified by chromatography on silica gel using benzene and ether as eluents and was obtained as pale yellow needles from chloroform and hexane in 27% yield. Elemental analysis of this compound showed C 66.78%, H 6.09%,
N 3.36%, O 15.8%, S 7.96%, C ₂₃ H ₂₅ O ₄ NS
67.15%, H 6.08%, N 3.41
%, O 15.6% and S 7.79%. Also,
When the proton nuclear magnetic resonance spectrum was measured, δ7.
2H based on aromatic proton around 0 ~ 8.0ppm
Peak, δ 2.7 ppm, 3H peak based on proton of C-CH ₃ bond, around δ 3.7 ppm 3H peak based on the proton of the methyl group in the bond, δ1.2
14H based on the proton of the adamantylidene group to ~ 2.5 ppm
Peak, protons translocated to 1 to 5 at δ 3 to 5 ppm and N
-CH ₂ - and a peak of 3H based on binding.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C-NMR was measured, and a peak based on the carbon of the adamantylidene group and the carbon of the methylene chain was found at about δ27 to 70 ppm, and a peak based on the carbon of the methyl group was found at about δ15.6 ppm. , Peak at δ110-160ppm based on carbon of thiophene ring, δ160-170pp
A peak based on the carbon of the C ＝ O bond appears near m.

From the above results, it was confirmed that the isolated product was a fulgimide compound (15) represented by the following structural formula.

Production Example 16 3.4 g (0.01 mol) of a fulgimide compound of the following formula In tetrahydrofuran, and add 1 g of metallic potassium
Was reacted at room temperature to obtain 3 g of imidocali of the following formula.

This was reacted with bromoacetonitrile 1.2 g (0.01 mol) BrCH ₂ CN of the following formula in dimethylformamide to obtain the following fulgimide compound (16). This compound was purified by chromatography on silica gel using chloroform and hexane as eluents and was obtained as pale yellow crystals from hexane in 57% yield. Elemental analysis of this compound showed C 69.81%, H 5.80%, N 7.44%, O
8.50%, a S 8.46% C 69.84% is calculated values for _{C 22 H 22 N 2 O 2} S, H 5.82%, N 7.41%, O 8.47
%, S 8.47%. When the proton nuclear magnetic resonance spectrum was measured, δ 7.0 to 7.5 ppm
Near the 2H peak based on the proton of the thiophene ring, δ
2H peak around 4.5 ppm due to N-CH ₂ CN bond proton, 1 due to 1.5 rearranged proton around δ3.7 ppm
H peak, a peak of 3H based on -CH ₃ bond protons near Deruta2.7Ppm, near δ1.3~2.5ppm -CH ₂ - shows a peak of proton based on protons and adamantylidene group bonded 14H Was.

Further, when ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C-NMR) was measured, a peak based on the carbon of the adamantylidene group was found around δ27 to 70 ppm, a peak based on the carbon of the methyl group was found around δ15.6 ppm, and δ110 to 160 ppm. Near the peak based on the carbon of the thiophene ring, and C = O
A peak based on the carbon of the bond appears.

From the above results, it was confirmed that the isolated product was a fulgimide compound (16) represented by the following structural formula.

Production Examples 17 to 34 In the same manner as in Production Examples 15 to 16, fulgide compounds or fulgimide compounds shown in Table 2 were synthesized.

The obtained product was subjected to production analysis using the same means for structure confirmation as in Production Example 15, and as a result, it was confirmed to be a compound represented by the structural formula shown in Table 2.

Production Example 35 Compound of the Following Formula 2.01g (0.0057mol) and the compound of the following formula 1.4 g (0.0057 mol) and 0.41 g (0.0058 mol) of pyrrolidine were dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours.

After the reaction, the solvent was removed, and purification was carried out by chromatography on silica gel to obtain 200 mg of a spirooxazine compound represented by the following formula.

Elemental analysis of this compound gave C 65.12%, H 4.90%,
N 8.51%, O 9.74%, F 11.73%, and C ₂₇ H ₂₄ N ₃ O ₃
C 65.45% is calculated values for _{F 3, H 4.88%, N} 8.4
Very good agreement was reached with 8%, O 9.69% and F 11.50%. When the proton nuclear magnetic resonance spectrum was measured,
A peak of 9H based on a proton of a quinoline ring, a proton of an indoline ring, and a proton of an oxazine ring around δ 6.5 to 9 ppm, and around δ 4 ppm 2H peak based on bond protons, near δ3.7 ppm −
O-CH ₃ peak of 3H based on the binding of protons, δ1.3~2.
A broad peak of 10H based on the cyclohexane ring proton was observed at around 1 ppm. Further, when a ¹⁵ C-nuclear magnetic resonance spectrum was measured, a peak based on carbon of carbonyl at around 170 ppm, a peak based on carbon of benzene ring, quinoline ring and oxazine ring of indoline at around δ100 to 160 ppm, and a trifluoro peak at around δ125 ppm A peak based on a methyl group, a peak based on spiro carbon around δ99 ppm and δ52 ppm, and a peak based on a methyl group and carbon of a methylene chain around δ20 to 50 ppm were shown.

From the results shown above, it was confirmed that the isolated product was the compound represented by the above structural formula (35).

Production Example 36 Compound of the Following Formula 2.0 g (0.0057 mol) of the compound of the following formula 1.4 g (0.0057 mol) and 0.41 g (0.0057 mol) of pyrrolidine were dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours.
After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel to obtain 150 mg of a spirooxazine compound represented by the following formula.

Elemental analysis of this compound gave C 65.23%, H 5.21%,
N 8.56%, O 9.71%, F 11.29%, and C ₂₇ H ₂₆ N ₃ O ₃
C 65.18% is calculated values for _{F 3, H 5.27%, N} 8.4
Very good agreement was reached with 5%, O 9.93% and F 11.46%. When the proton nuclear magnetic resonance spectrum was measured,
A peak based on an aromatic proton around δ 6.5 to 9 ppm, a peak based on a methyl proton of an ethyl group around δ 1.0 ppm, a peak based on a methylene proton of an ethyl group around δ 2 ppm, and an N- peak around δ 3.5 ppm. CH ₂ CH ₂ COOC
And a peak based on protons of the H _3. Also, ¹³ C-NMR
When measured, a peak based on carbonyl carbon around δ170 ppm, an aromatic carbon around δ100 to 160 ppm, a peak based on carbon of oxazine ring and carbon of trifluoromethyl group, a peak based on spiro carbon around δ99 ppm, A peak based on carbon of methylene bonded to nitrogen was shown around δ50 ppm, and a peak based on carbon of methyl group and methylene group bonded to carbon was shown around δ20 to 40 ppm.
From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (36).

Production Example 37 Compound of the Following Formula 2.01g (0.0059mol) and the following compounds 1.02 g (0.0059 mol) and 0.43 g (0.006 mol) of pyrrolidine were dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours.

After the reaction, the solvent was removed, and the residue was purified by chromatography on silica gel to give a spirooxazine compound (400 mg) of the following formula.

Elemental analysis of this compound gave C 81.35%, H 6.60%,
N 7.62%, O 4.43%, calculated values for C ₂₅ H ₂₄ N ₂ O: C 81.49%, H 6.57%, N 7.60%, O 4.34%
Very well matched. Also, when the proton nuclear magnetic resonance spectrum was measured, the peak of 11H, based on the proton of the naphthalene ring, the proton of the indoline ring, and the proton of the oxazine ring, around δ 6.5 to 8.5 ppm, δ 2.8 ppm
Peak of 3H based on the N-CH ₃ bonds of protons in the vicinity,
A broad peak at 10H based on cyclohexane ring protons was shown around δ 1.3 to 2.0 ppm. Further measurement of ¹³ C-nuclear magnetic resonance spectrum, peaks based on carbon of benzene ring, naphthalene ring and oxazine ring of indoline around δ100 to 160 ppm, peaks based on spiro carbon around δ99 ppm and δ56 ppm, around δ20 to 35 ppm Shows the peaks based on the carbons of the cyclohexane group and the methyl group.

From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (37).

Production Example 38 The following compound 2.0g (0.0057mol) and the following compounds 0.98 g (0.0057 mol) and 0.41 g (0.0057 mol) of pyrrolidine were dissolved in 50 ml of ethyl alcohol and heated under reflux for 2 hours.

After the reaction, the solvent was removed, and purification was carried out by chromatography on silica gel to obtain 200 mg of a spirooxazine compound represented by the following formula.

Elemental analysis of this compound gave C 78.66% and H 6.09.
%, N 11.05%, O 4.2%, which are calculated values for C ₂₅ H ₂₃ N ₃ O, C 78.71%, H 6.08%, N 11.02
% And O 4.2%. When the proton nuclear magnetic resonance spectrum was measured, δ 6.5 to 9 ppm
Near 10H peak based on quinoline ring proton, indoline ring proton and oxazine ring proton,
peak of 3H based on the near δ2.7ppm the N-CH ₃ bonds of protons, showed a broad peak 10H based on the protons of the norbornane ring around Deruta1.3～2.5Ppm. Further measurement of ¹³ C-nuclear magnetic resonance spectrum, δ100 ~ δ160pp
Around m, peaks based on carbons of the benzene ring, naphthalene ring and oxazine ring of indoline, δ99 ppm and δ52 ppm
A peak based on spiro carbon in the vicinity and a peak based on carbon in the norbornane ring were shown in the vicinity of δ 27 to 52 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (38).

Production Examples 39 to 55 Spirooxazine compounds shown in Table 3 were synthesized in the same manner as in Production Examples 35 to 38.

The obtained product was subjected to structure analysis using the same means for structure confirmation as in Production Example 35, and as a result, it was confirmed that the product was a compound represented by the structural formula shown in Table 3.

Example 1 70 parts of chlorostyrene, 2,2-bis (3,5-dibromo-4)
-Methacryloyloxyethoxyphenyl) propane 30
To the composition consisting of 0.2 parts of the flugimide compound of Production Example 15, and perbutyl ND as a radical polymerization initiator.
One part was added and mixed well. This 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. for 18 hours, gradually increasing the temperature, and maintaining the temperature at 90 ° C. for 2 hours. After the completion of the polymerization, the mold was taken out of the air furnace, and after standing to cool, the polymer having a thickness of 5 mm was removed from the glass of the mold.

Further, 10 parts of the chromene derivative obtained in Production Example 1 was dispersed in 100 parts of silicone oil, and the surface of the polymer plate obtained above was impregnated at 200 ° C. for 1 hour. Thereafter, the plate was cooled with cold water and washed with methanol and acetone.

The chromene derivative was impregnated to a depth of about 2 μm from the polymer surface. Xenon long life fade meter FAL-15AX manufactured by Suga Test Instruments Co., Ltd.
-The fatigue life was measured by HC.

Further, a change in color tone was visually observed. The fatigue life is defined as the time (T _1/2) required for the chromene derivative and the fulgide compound or the fulgimide compound to decrease the absorbance at the maximum absorption wavelength based on each compound to 1/2 of the initial (T ₀ ) absorbance. ). Where T ₀ and T
Absorbance of _1/2 are both absorbance value minus the molded article unirradiated at the maximum absorption wavelength based on each compound, also, the absorbance of T ₀ is the fatigue life described above after the lapse of 60 seconds after the light irradiation Is the same in other examples and comparative examples. Further, the above-mentioned change in color tone was observed from the surface layer of the obtained photochromic molded article, and was observed at T ₀ and T _1/2 of the photochromic compound in the surface layer. The observation mode of the color tone described above is the same in other examples and comparative examples.

 The results are shown in Table 4.

Examples 2 to 10 In Example 1, the monomers used, chromene derivatives,
Example 1 was repeated except that the type and amount of the flugimide compound were changed, and polymerization was carried out by known means in accordance with the monomer. The results are shown in Table 4.

Comparative Example 1 70 parts of chlorostyrene, 2,2-bis (3,5-dibromo-4)
-Methacryloyloxyethoxyphenyl) propane 30
Part of the chromene derivative of Preparation Example 1 in a composition consisting of
0.2 part of the fulgimide compound of Production Example 15 was added, and 1 part of perbutyl ND as a radical polymerization initiator was further added and mixed well. This 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. for 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.

Evaluation of the photochromic performance of the obtained molded article was performed in the same manner as in Example 1. The results are shown in Table 4.

Example 11 Example 1 was repeated except that 0.3 parts of the chromene derivative obtained in Production Example 1 was added instead of the flugimide compound, and the spirooxazine compound of Production Example 35 was dispersed in silicone oil instead of the chromene derivative. All operations were the same as in Example 1. The results are shown in Table 5.

In addition, the color tone was observed at T ₀ and T _1/2 of the spirooxazine compound.

Examples 12 to 21 In Example 11, the monomers used, chromene derivative,
All examples were conducted except that the type and amount of the spirooxazine compound were changed, and polymerization was carried out by known means according to the monomer.
Same as 11 The results are shown in Table 5.

Example 22 (1) Production of polymer To 100 parts of allyl diglycol carbonate, 3 parts of diisopropyl peroxycarbonate as a radical polymerization initiator and 3 parts of a fulgimide compound of Production Example 25 were added and mixed well. To obtain a polymer having a thickness of 5 mm.

(2) Preparation of primer solution and coating and curing Commercially available primer solution Sebian A46701 (manufactured by Daicel Chemical Industries, Ltd .; trade name) in 111 parts (resin concentration was adjusted to 90% by weight) to prepare the chromene derivative of Production Example 11 0.5 part was added and dissolved with sufficient stirring. This primer solution was filtered through a membrane filter having a pore size of 1 μm, and (1)
Was applied by a dipping method, the pulling speed was adjusted, and the cured primer film thickness was 1 μm.
After application, the coating was dried at 60 ° C. for 1 hour to obtain a photochromic substrate having a good appearance. The evaluation of the photochromic performance was performed in the same manner as in Example 1.

 The results are shown in Table 6.

Examples 23 to 31 The same procedures as in Example 22 were carried out except that the polymers, photochromic compounds and resins used were changed to those shown in Table 6. The results are shown in Table 6.

Example 32 In Example 22, 3 parts of the chromene derivative obtained in Production Example 12 was mixed in place of the fulgimide compound, and the spirooxazine derivative of Production Example 46 was replaced with 0.3% of the chromene derivative.
Example 22 except that 5 parts were added to the primer
Same as. The results are shown in Table 7. The color tone was observed at T ₀ and T _1/2 of the spirooxazine compound.

Examples 33 to 41 The same procedures as in Example 32 were carried out except that the polymers, photochromic compounds and resins used in Example 32 were changed to those shown in Table 7. The results are shown in Table 7.

Continuation of the front page (72) Inventor Junji Momoda 1-1, Mikage-cho, Tokuyama-shi, Yamaguchi Pref.

Claims (1)

(57) [Claims] 1. A photochromic molded article comprising a spirooxazine compound, chromene or a derivative thereof, and a different photochromic compound having a different fatigue life selected from a fulgide or a fulgimide compound, wherein (1). The surface layer of the molded body has a relatively long fatigue life,
(2) The molded article contains a spirooxazine compound and / or chromene or a derivative thereof, and the inner layer of the molded article contains a fulgide or fulgimide compound having a relatively short fatigue life. ). The surface layer of the molded article is composed of a spirooxazine compound having a relatively long fatigue life, and
A photochromic molded body, characterized in that an inner layer of the molded body is formed of one containing chromene or a derivative thereof having a relatively short fatigue life.