JPH03121188A - Photochromic composition - Google Patents

Abstract

PURPOSE:To obtain the title composition undergoing little change in color even when used over a long period of time by mixing chromene (derivative), a fulgide or fulgimide compound, and an ultraviolet stabilizer each in a specified amount. CONSTITUTION:The title composition consists of 100 pts.wt. chromene (derivative) (e.g. a compound of formula I), 0.01-10,000 pts.wt. fulgide or fulgimide compound (e.g. a compound of formula II), and 0.01-10,000 pts.wt. ultraviolet stabilizer (e.g. a compound of formula III).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photochromic composition that exhibits little change in color tone even after long-term use.

(Prior art) Photochromism is a phenomenon that has attracted attention over the past few years.When a certain compound is irradiated with light containing ultraviolet rays, such as sunlight or mercury lamp light, the color changes immediately, and when the compound is irradiated with light, it immediately changes color. This is a reversible effect that returns to the original color when you stop using it and leave it in a dark place. Compounds having this property are called photochromic compounds, and compounds with various structures have been synthesized and proposed, but no particular common skeleton has been recognized in their structures.

Chromene or its derivatives are known as photochromic compounds. The color tone of chromene or its derivatives is orange to yellow. On the other hand, fulgide compounds or fulgimide compounds are also well known as photochromic compounds, and the color tone of these compounds is orange to blue.

When each of these compounds is used alone, the 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 by the above-mentioned compounds alone. Therefore, the present inventors mixed the above-described chromene or its derivative with a fulgide compound or a fulgimide compound, and as a result, succeeded in developing various mixed colors including gray, amber, and brown.

(Problem to be Solved by the Invention) However, it has been found that the color tone of a mixture of these two types of photochromic compounds gradually changes over a long period of time. As a result of our investigation into the cause of this, we found that the above-mentioned fulgide compound or fulgimide compound has a shorter durability of repeated coloring and decoloring than chromene or its derivatives. It was found that this is because the fulgimide compound produces less color.

Therefore, the present inventors believe that if the repeated coloring and decoloring durability of the fulgide compound or fulgimide compound can be increased to almost the same level as that of chromene or its derivatives, then the photochromic material will not change in color tone over a long period of time. It was assumed that a mixture of compounds would be obtained. Then, we conducted extensive research in order to improve the durability of the fulgide compound or fulgimide compound over repeated color development and decolorization.

(Means for Solving the Problem) As a result, by combining a fulgide compound or a fulgimide compound with an ultraviolet stabilizer, the durability of the photochromic properties of these compounds can be improved, and furthermore, chromene or its derivatives can also be made durable by the ultraviolet stabilizer. The present inventors have discovered that the properties of these two types of compounds are improved, and that the durability of these two types of compounds is approximately the same, leading to the completion of the present invention.

That is, the present invention provides: (a) 100 parts by weight of chromene or its derivative; (b) fulgide compound or fulgimide compound 0.0
1 to 10,000 parts by weight and (c) ultraviolet stabilizer 0.01 to 10,000
It is a photochromic composition characterized in that it consists of parts by weight.

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

7 The group to be substituted is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group. Specific examples of aromatic hydrocarbon groups include divalent groups derived from one benzene ring or 2 to 4 condensed rings thereof, such as a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. In addition, in the above aromatic hydrocarbon group, hydroxyl group, nitro group, cyano group, fluoroalkyl group, substituted amine group, halogen atom, alkyl group, alkoxy is an alkylene group or +ORz+1v- (however, R8 is an alkylene group, n is a positive integer), and R3 and R1° are each a substituted aromatic hydrocarbon group substituted with one or more heterocyclic groups such as the same or different arthienyl group, furyl group, or pyrrolyl group. can be mentioned.

The group includes oxygen, sulfur, a 5-membered ring containing a nitrogen atom, and a 6-membered ring.
Examples include a membered ring or a heterocyclic group in which a benzene ring is fused to the membered ring. Specifically, they are derived from nitrogen-containing heterocycles such as a pyridine ring, quinoline ring, and virol ring; oxygen-containing heterocycles such as a furan ring and benzofuran ring; and sulfur-containing heterocycles such as a thiophene ring and benzothiophene ring. Examples include divalent heterocyclic groups.

Furthermore, substituted unsaturated heterocyclic groups in which these unsaturated heterocyclic groups are substituted with the substituents described in the description of the aromatic hydrocarbon group described above are also employed without any limitations in the present invention.

Furthermore, during the above-mentioned ritual (All and CB), R4°R,
, R, and R7 are the same or different hydrogen atoms, alkyl groups, aralkyl groups, aryl groups, or substituted amine groups, respectively. The above alkyl group is not particularly limited, but -C has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
6 is preferable. The alkylene group in the aralkyl group generally has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. More specific examples of these alkyl groups and aralkyl groups include methyl, ethyl, propyl, methyl, benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups. Further, as the aryl group, for example, a phenyl group, tolyl group, xylyl group, naphthyl group, etc. are suitable.

Furthermore, during the above-mentioned rituals (A) and (B), R4°Rs,
The substituted amino group represented by Rh and R7 has 3 carbon atoms.
~6 alkylene group; -C)l! (jlOcll□-
10Z CIl zOcHzctl□--C)12cII□oc
Oxyalkylene group having 3 to 6 carbon atoms such as o2coz-CH20(cI+□), -, -CH2SCII□
CL CHzS (cHz) 3G+I□C1l□
CH having 3 to 6 carbon atoms, such as SCH□C112-.

Azoalkylene groups having 3 to 6 carbon atoms, such as CII□CI□NCII□C11□-, are preferably employed.

In the group represented by RI Zs RI 3, one of R92 and RI3 is a hydrogen atom and the other is an alkyl group, or each represents the same or different alkyl group. The alkyl group is not particularly limited, but specifically, the same groups as the above-mentioned examples of the alkyl group can be employed. Furthermore, R14 is a bornylidene group such as a tetramethylene group or a pentamethylene group, or a bicyclo(
3,3,1) 9-nonylidene group, adamantylidene group. Specific examples of the substituent include, for example, hydroxy group; substituted amino groups such as methylamino group and diethylamino group; alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, and tart-butoxy group; benzyloxy group Aralkoxy groups having 7 to 15 carbon atoms such as phenoxy groups and 1-naphthoxy groups; Lower alkyl groups having 1 to 4 carbon atoms such as methyl groups, ethyl groups, and t-butyl groups. Group; halogen atom such as fluorine, chlorine, oxaline; cyano group; carboxyl group; alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl group; halogen-substituted alkyl group having 1 or 2 carbon atoms such as trifluoromethyl group Nitro group; Aryl group such as phenyl group and tolyl group; Aralkyl group such as benzyl group, phenylethyl group and phenylpropyl group;
These substituents are not only included as one substituent, but may also be included as a polysubstituted product having two or more substituents, and furthermore, the substituents in the polysubstituted product may be of the same type. There is no problem even if they are different types, and the positions of the substituents can be changed depending on the purpose or use.

Among the above-mentioned chromenes or derivatives thereof, fused rings having the above-mentioned or more condensed rings are preferable because the coloring density is high. Among these, compounds in which a ring is condensed at the 7.8-position of a chromene derivative are more preferred. Further, in the above formula (B), a compound in which a ring is condensed to the 5th and 6th positions of a chromene derivative is also suitably used.

Component (b) of the photochromink composition of the present invention is a fulgide compound or a fulgimide compound. As the fulgide compound, a compound having a structure represented by the following formula and having photochromic properties is employed without any restriction. Further, the fulgimide compound has a structure represented by the following formula, a monovalent hydrocarbon group which may have a substituent, or a monovalent compound, and has photochromic properties, and can be employed without any restriction.

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

mantylidene group is an oxygen atom, Basic N-R.

Base N A+ 8+ (Ih)-(Bz sweat R:+
Group>N Ai A4 or a group; h-s, -R, is shown.

Divalent unsaturated heterocyclic group in formula (I) above, the aromatic hydrocarbon group has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms; Examples of rings forming a hydrogen ring include a benzene ring, a naphthalene ring, and a phenanthrene ring.

Further, as the unsaturated heterocyclic group, a 5- or 6-membered monocyclic heterocyclic group containing at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom, or a benzene ring or a cyclo - A fused heterocyclic group in which a xene ring is fused is shown.

Examples of the rings forming such a heterocyclic group include nitrogen-containing heterocycles such as virole ring, pyridine ring, quinoline ring, and isoquinoline ring; oxygen-containing heterocycles such as furan ring, benzofuran ring, and biran ring; thiophene ring; Examples include sulfur-containing heterocycles such as benzothiophene rings.

Heterocyclic groups may have at most 5, preferably up to 3 substituents.

The hydrogenated group or unsaturated heterocyclic group may contain at most 5, preferably up to 3 substituents. Examples of such substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl groups; cyano groups; nitro groups; amino groups; carboxyl groups; methylamino groups; alkyl groups having 1 to 4 carbon atoms such as diethylamino groups; Amino group;
Lower alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, and t-butyl group; halogenated lower alkyl groups having 1 to 3 halogen atoms such as trifluoromethyl group and 2-chloroethyl group; Lower alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, and L-butoxy; aryl groups having 6 to 10 carbon atoms, such as phenyl, naphthyl, and tolyl; phenoxy, 1-naphthoxy, etc. Aryloxy group having 6 to 14 carbon atoms; aralkyl group having 7 to 15 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group; aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group, phenylpropoxy group; Examples include alkylthio groups of numbers 1 to 4. These substituents may be the same or different, and their positions are not particularly limited.

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

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

A 5- or 6-membered monocyclic heterocycle containing one elementary atom or a fused heterocycle in which a benzene ring or a cyclohexene ring is fused to this heterocycle is preferred. It is also a preferred embodiment that these benzene rings, monocyclic heterocycles, or fused heterocycles contain one or two of the above-mentioned substituents.

R1 in formula (I) above is a monovalent hydrocarbon group or a monovalent heterocyclic group, each of which may have a substituent.

The hydrocarbon group for R1 may be an aliphatic, alicyclic, or aromatic hydrocarbon group, and specific examples include a hydrocarbon group having 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. 2o, preferably 1 to 6 alkyl groups; aryl groups having 6 to 14 carbon atoms such as phenyl, tolyl, xylyl, and naphthyl groups; carbon atoms such as benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups An aralkyl group having 1 to 10 alkylene groups, preferably 1 to 4 alkylene groups is suitable.

Further, as the heterocyclic group for R8, at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom is selected from 1 to 3.
A 5- or 6-membered monocyclic heterocyclic group, preferably 1 or 2, or a fused heterocyclic group in which benzene is fused thereto is preferred. In addition to the examples of unsaturated heterocyclic groups explained in the above definitions, saturated heterocyclic groups such as saturated piperidine ring, piperazine ring, morpholine ring, pyrrolidine ring, indoline ring, and chroman ring can be mentioned.

There is no particular problem even if the hydrocarbon group or heterocyclic group of R1 described above has a substituent. Examples of such substituents include the same substituents as those described above, preferably containing at most 5, preferably 3, for the hydrocarbon group or heterocyclic group.

The above R+ is preferably a halogen atom, a C1-C4 alkoxy group, or a C1-20 alkyl group optionally substituted with a phenyl group; substituted with a halogen atom or a C1-4 alkoxy group or a 5-membered or 61-ring monocyclic heterocyclic group containing 1 to 3, especially 1 nitrogen atom, carbon atom, and sulfur atom; It is a fused heterocyclic group in which a benzene ring is fused to a ring group, especially a monocyclic heterocyclic group.

Furthermore, the above R is particularly preferable, having 1 to 6 carbon atoms.
an alkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

In the above formula (1) in the present invention, it means a lupolnylidene group or an adamantylidene group. Here, the norbornylidene group is represented by the following formula, and the adamantylidene group is represented by the following formula.

\ / The above formula shows the skeletal structure of a norbornylidene group and an adamantylidene group, both of which have no substituents. In these norbornylidene groups or adamantylidene groups, the hydrogen atom of the above formula may be substituted with a substituent, and the number thereof may be one or more. When a substituent is present, its type, number and position are arbitrarily selected depending on the purpose and use. Moreover, when it has a plurality of substituents, they may be the same substituent or different types of substituents.

Substituents for the norbornylidene group or adamantylidene group include, for example, a hydroxy group; an alkylamino group having 1 to 4 carbon atoms such as a methylamino group and a diethylamino group; a methoxy group, an ethoxy group, a tert-butoxy group, etc. Alkoxy group having 1 to 4 carbon atoms; aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group; phenoxy group, 1
-Aryloxy group having 6 to 14 carbon atoms such as naphthoxy group; 1 to 4 carbon atoms such as methyl group, ethyl group, t-butyl group, etc.
Lower alkyl group: halogen atom such as fluorine, chlorine, oxaline; cyano group; carboxyl group; alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl; halogen substitution having 1 or 2 carbon atoms such as trifluoromethyl group Alkyl groups; nitro groups; aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl groups; aralkyl groups having 7 to 9 carbon atoms such as phenylethyl and phenylpropyl groups; and the like.

Preferred examples of these substituents include halogen atoms, hydroxy groups, alkyl groups having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
an alkoxy group having 2 to 10 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or an aralkyl group having 6 to 1 carbon atoms
0 aryl group.

In the above-mentioned ritual (1) of the present invention, X is an oxygen atom (-0-), a group>N-R2, a group>N-ArB+
8. -A4 or group>l'l represents A3-Ra.

Also, in -ritual (1),
N A3 Ra or group N-, -a, -(Az)-(Bz)r R3((
R1 is 1 to 3 atoms selected from the group consisting of a halogen atom, a cyano group, and a nitro group, or an optionally substituted alkyl group having 1 to 10 carbon atoms. ) is more preferable from the viewpoint of the durability of the photochromic properties of the resulting compound.

X in the general formula (1) is the above-mentioned group>N-AI-B "(^2+-r-(B z )r R
In s, when R3 is a naphthyl group or a naphthylalkyl group, and when it is a group; NA, -A,
Naphthyl group and imide group (〉N-
It is preferable that the number of atoms in the main chain sandwiched between the two groups is from 3 to 7 because a compound with excellent durability of photochromic action can be obtained.

Next, Rz, R3, Ra, A1, A in the above X
The definitions of t, A, , Aa, B+, Bz, m and n will be explained in detail.

R2 represents a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group include a methyl group, ethyl group, propyl group, n-1so- or tert-butyl group, pentyl group, hexyl group, and octyl group. , decyl group, etc. Among these, those having 1 to 20 carbon atoms, and more preferably those having 1 to 10 carbon atoms. Examples of the aryl group include those having 6 to 10 carbon atoms, such as phenyl, tolyl, and naphthyl groups.

At, Az and A may be the same or different from each other and can be an alkylene group, an alkyritene group, a cycloalkylene group or an alkylcycloalkane-diyl group.

Specific examples of these include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, trimethylene group, tetramethylene group or 2,2-dimethyltrimethylene group; ethylidene group;
Alkylidene group having 2 to 10 carbon atoms such as propylidene group or isopropylidene group; cycloalkylene group having 3 to 10 carbon atoms such as cyclohexylene group; 2-methylcyclohexane-α, ■-diyl group (-CIl□be◇) , 4
-Methylcyclohexane-α,1-diyl group and cycloalkanediyl group. As A1 and A2, in particular, an alkylene group having 1 to 6 carbon atoms, an alkylidene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms,
An alkylcycloalkane-diyl group having 6 to 7 carbon atoms is preferred.

B, and B! may be the same or different and are selected from the following seven bonding groups.

ooo o.

0 1 or -NHC- m and n each independently represent 0 or 1,
When it represents 0, -02)r or +Bz)r means a bond. Furthermore, when m is O, n also represents 0.

R3 represents an alkyl group, a naphthyl group, or a naphthylalkyl group, each of which may have a substituent. Although the number of carbon atoms in the above alkyl group is not particularly limited, it is preferably 1 to 10, and the number of carbon atoms in the alkyl group of the naphthylalkyl group is preferably 1 to 4.

The above-mentioned substituents are 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; Naphthyl group or naphthylalkyl group is halogen atom, cyano group, nitro group, carbon number 1
It may be substituted with 1 to 3 atoms or groups selected from the group consisting of 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.

As the alkyl group represented by R1 above, the same alkyl group as exemplified for R2 above can be used. Further, examples of the naphthyl alkyl group include a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, a naphthylbutyl group, and the like.

A4 represents a naphthyl group which may have a substituent.

The type of substituent is not particularly limited, but the naphthyl group includes a halogen atom, an aano 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: Further, R4 represents a halogen atom, a cyano group or a nitro group.

In the above definitions of R2 and A4, examples of the halogen atom include fluorine, chlorine, and bromine.

The third component of the photochromic composition of the present invention is a UV stabilizer.

As the UV stabilizer, any known UV stabilizer added to various plastics can be used without any limitations. In the present invention, considering the improvement in the durability of both chromene or its derivative and the fulgide compound or fulgide compound, among various UV stabilizers, - heavy ring oxygen quencher,
Hindered amine light stabilizers (including light stabilizers having a hindered amine structure and a hindered phenol structure in the molecule), hindered phenol antioxidants, and sulfur-based antioxidants are preferably used.

Among these, - light stabilizers having a hindered amine structure and a hindered phenol structure in the molecule are most preferred, followed by other hindered amine light stabilizers, - heavy ring oxygen quenchers, and hindered phenol antioxidants. It has almost the same effect.

Furthermore, by combining two or more of the above-mentioned UV stabilizers, even better effects can be obtained than when used alone. Among these, a combination of two types in which - a light stabilizer having a hindered amine structure and a hindered phenol structure in the molecule is added with another hindered amine light stabilizer, a hindered phenol antioxidant, or - a heavy ring oxygen quencher is preferred. .

Furthermore, the best results can be obtained with a combination of three types in which - a light stabilizer having a hindered amine structure and a hindered phenol structure in the molecule, another hindered amine light stabilizer and a heavy ring oxygen quencher.

Singlet oxygen quenchers preferably used in the present invention include complexes of Ni'' and organic ligands, cobalt (111
)-1 lis-di-n-butyldithiocarbamate, iron (
Examples include I[[)-diisopropyldithiocarbamate and cobalt(II)-diisopropyldithiocarbamate. Among these -heavycyclic oxygen quenchers, a complex of NiZ+ and an organic ligand is particularly preferred.

Specific examples of such complexes are as follows.

[2,2-thiobis(4-(1,1,3,3-tetramethylbutyl)phenolado)butylamine)nickel, nickel-bis[0-ethyl(3,5-di-tert-butyl-4-hydroxybenzyl)]phosphonate, (1) Bis(2,2'-thiobis-4-(1,1,3,3-tetramethylbutyl)phenolad) nickel, UV-Chek AM105, U from Ferro Corporation
Mention may be made of the Ni complexes commercially available under the trade names V-Chek M126 and U-Chek AM205.

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

Nickel-dibutyldithiocarbamate, (ke) CCz&)lszN4)- (Ko) 7 (vinegar) R'' 3 R' (However, the above formulas (o), (force), (ki), (ri).

(ke), (ko), (su), (shi) and (su), R'
R"R'R', R6, R
R9RIOR11, R eyes, RI3. R”, R”l R”
and R'7 are alkyl groups, R3 and R11 are hydrogen atoms or alkyl groups, RI8 is a benzoyl group, acryloyl group or methacryloyl group, and m and n are positive integers. ) Above (e), (power), (ki), (ri), (ke).

In (c), (s), (c) and (s), the number of carbon atoms in the alkyl group is not particularly limited, but is generally in the range of 1 to 12 for reasons such as the ease of obtaining these compounds. It is preferable that there be.

Furthermore, as a hindered amine light stabilizer, Sumireep (Sun+1sorb) LS manufactured by Sumitomo Chemical Co., Ltd.
2000 and LS-2001 (both are trade names).

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

1? ' 1 6 (d) (te) (nu) (ne) and ()), R1, R1, R4, R%R6, R
? and R8 are an alkyl group, R3 is hydrogen or an alkyl group, R11 is a hydrogen atom, an alkyl group, or an acryloyl group, and n is a positive integer. ) The above (C), (S), (Yu), (C), (T).

(te), ()), (su), (d), (nu), (
In (6) and (2), the number of carbon atoms in the alkyl group is not particularly limited, but is generally preferably in the range of 1 to 20 for reasons such as ease of obtaining these compounds.

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

CHzCHtCOOR’ (c) ()) CHzGHZCOOR” (However, the above formulas (C), (S), (Yu), (C).

(ツ), (te), ()), 　ke), (d), (nu).

(R' 5GHzC)ItCOOCHt)*C(hi) (e) (However, in the above formulas (c), (hi), ()), (f) and (e), the total I R"l R', R 'l R' and R7 are alkyl groups, and R3 is a hydrogen atom or an alkyl group.) In the above (c), (h), ()), (e) and (e), as the alkyl group, Although the number of carbon atoms is not particularly limited, it is generally 1 to 2 carbon atoms due to the ease of obtaining these compounds.
A range of 0 is preferable.

The above-mentioned blending ratio of chromene or its derivative, fulgide compound or fulgimide compound, and ultraviolet stabilizer is based on 100 parts by weight of chromene or its derivative,
fulgide compound or fulgimide compound is 0.01 to 10
000 parts by weight, and the UV stabilizer is 0.01-100 parts by weight.
00 parts by weight.

If the amount of the UV stabilizer is less than 0.01 parts by weight, little improvement in the repeat durability of photochromic properties will be observed, and if it exceeds 10,000 parts by weight, the photochromic composition may be dispersed in the resin described below. This is not preferable because molding of the resin becomes difficult when In particular, from the viewpoint of photochromic properties of the resulting photochromic composition, the amount of the ultraviolet stabilizer is preferably in the range of 50 to 400 parts by weight.

The blending ratio of the fulgide compound or fulgimide compound may be determined depending on the desired color tone of the photochromic composition, but generally when a good mixed color is expected by mixing with chromene or its derivatives, 0.05 ~20
It is preferable to select from a range of 0 parts by weight.

The photochromic composition of the present invention can satisfactorily exhibit the desired photochromic function as described above by being uniformly dispersed in various polymer matrices. The synthetic resin constituting the polymer matrix used in which the photochromic composition of the present invention is dispersed may be any synthetic resin as long as it can uniformly disperse chromene or its derivative and the fulgide compound or fulgimide compound, and may be optically Preferably, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate 1, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly(2-hydroxyethyl methacrylate), polydimethylsiloxane, polycarbonate. Polymers such as poly (allyl diglycol carbonate), or polymers formed by copolymerizing the monomers forming these polymers with each other or with other monomers are preferably used. The amount of the photochromic composition of the present invention to be dispersed in such a resin is from o, ooi to 10 parts by weight, preferably from 0.1 to 10 parts by weight, based on 100 parts by weight of the resin.

The photochromic composition of the present invention is particularly suitable for use in photochromic lenses. The method for producing the photochromine lens is not particularly limited as long as it provides uniform light control performance, and specific examples include the above-mentioned chromene or its derivative, fulgide compound or fulgimide compound, and ultraviolet stabilizer. There is a method of sandwiching a polymer film made of a uniformly dispersed material into a lens. Alternatively, there is a method in which the photochromic composition is dispersed in silicone oil and impregnated onto the lens surface at, for example, 200° C. for 15 minutes, and then the surface is coated with a curable substance to form a photochromic lens. Also,
Another method is to apply the above polymer film to the lens surface and coat the surface with a curable substance to make a photochromic lens.

(Effects) As explained above, the photochromink composition of the present invention has the following effects, especially by uniformly dispersing it in various resins:
It changes from colorless to colored or darkly colored when exposed to ultraviolet light such as sunlight or light from a mercury lamp, and this change is reversible and has excellent dimming properties. Moreover, the present invention
By using chromene or a derivative thereof, a fulgide compound or a fulgimide compound, and an ultraviolet stabilizer,
It is easy to obtain a mixed color, and the color tone of the mixed color changes little even after long-term use (and it has also succeeded in dramatically improving the repeat durability of photochromic properties without reducing the color density). be.

Therefore, the photochromic composition of the present invention can be used in a wide range of fields, such as various recording memory materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, etc. It can be used as a variety of recording materials. In addition, the photochromic composition of the present invention can also be used as a material for photochromic lenses, optical filter materials, display materials, photometers, decorations, and the like.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Note that "parts" in the examples are "parts by weight."

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

・Cyasorb UV 1084
(Product name: Manufactured by American Cyanamid Company) Irgastab 2002 (Product name: Manufactured by Ciba Kaigyi Company) ・Ylex BC (Product name: Manufactured by DuPont Company) UV-Chek (hek) MIO (Product name: Ferro Corporation) H Chimassorb 4 (Product name: Ciba Geigy) C1 (2 C(cH3)3 Cyasorb 6 (Product name: American Cyanamid) UV-Hek M105 (Product name: Manufactured by Ferro Corporation) - Tinuvin (Product name: Manufactured by Ciba Geigy) - Tinuvin ■ 4 (Product name: Manufactured by Ciba Geigy) - Tinuvin 622 (Product name: Manufactured by Ciba Geigy) ) ・Sanol 5-11 (Product name: Manufactured by Nisankyo Co., Ltd.) CH3 ■ ・Sanol LS-74 (Product name: Manufactured by Sankyo Co., Ltd.) ・Mark (ARK) A-82 (Product name: Manufactured by Near Deca Argus Co., Ltd.) ・Mark ( ARK ) A-87 (Product name: Made by Neardeka Argus Co., Ltd.) ・Mark (ARK) 0-50 (Product name: Made by Neardeca Argus Co., Ltd.) C (cH3)! ・Sumilizer 0M (Product name: Made by Sumima Kagaku Co., Ltd.) ・Sumilizer 88M-3 ・Sanol LS-2626 (Product name: manufactured by Nisankyo Co., Ltd.) C) 13 ・Sumilizer A (Product name: Manufactured by Sumima Kagaku Co., Ltd.) ・Irganox ■ (Product name: Manufactured by Ciba Geigy Co., Ltd.) (Product name Sumilizer -20 (Product name: Made by Niadeka Argus) - Mark ARK 0-30 Irganox 45 (Product name: Made by Ciba-Geigy) - Antioxidant PM-12 (Product name: Made by S Company) CI.

l3 CH.

L (Product name: Made by Adeka Argus) ・Mark (ARK AO-330 (Product name: Made by Neardeka Argus) ・Mark (ARK 0-23 (Product name: Made by Adeka Argus) ・Sumilizer P-D (Product) Name: Made by Sumitomo Chemical) (H sH:+v CHzCHzCOOCIaH:++ ・A chromanone compound of Sumilizer MB (product name: Sumima Kagaku Co., Ltd.) was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to make a chromanol compound.This chromanol compound was 7.47 ml.
15 g with 4.5 g of anhydrous copper sulfate in a stream of carbon dioxide.
The mixture was heated at 0-160° C. for 10 minutes and the brown viscous liquid was purified by chromatography on silica gel to obtain 6.3 g of a chromene derivative of the following formula.

Production example 1 1-hydroxy-2-acetonaphthone 10g (0.05
41Iof) and Norcamphor 6.6g (0.06m
ol) and 8 g of pyrrolidine (0,113010
A solution was prepared by dissolving 1) in 300 cc of toluene. The mixture was boiled for 10 hours and the water was separated.

After the reaction was completed, toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized from acetone. The elemental analysis value of this compound is C86, 93%, ■46.8
9%, 06.18%, which is the calculated value for CtqH+sO CB7.02%, H6,87%, 0
It was extremely consistent with 6.12%.Also, when proton nuclear magnetic resonance spectrum was measured, it was 67.2-8.3%.
<6H peak based on the naphthalene ring proton near pps+, <2H peak based on the alkene proton near 65.6-6.1 ppm, δ1.2-2.5 pp
10H based on the proton of norbornylidene group near m
showed a broad peak. Furthermore, when we measured the 13C-nuclear magnetic resonance spectrum, we found that there was a peak based on the carbon of the norbornylidene group in the vicinity of 627 to 52 ppm, and a peak at δ110 to 52 ppm.
A peak based on the carbon of the naphthalene ring appears near tsoppm, and a peak based on the carbon of the alkene appears near 680 to 110 ppm+.

From the above results, it was confirmed that the isolated product was a compound represented by the above structural formula (1).

Production example 2 1-acetyl-2-naphthol 10 g (0,054
mol ) and bicyclo(3,3,13 nonan-9-one 8.29 g (0.06 mol) and morpholine 8.7
A solution was prepared by dissolving 0.1 g (0°10 mol) in 300 cc of toluene. The mixture was boiled for 5 hours and the water was separated. After the reaction was completed, toluene was removed under reduced pressure, and the remaining chromanone compound was recrystallized from acetone. Next, this chromanone compound was dissolved in methanol 200
cc and added lithium aluminum hydride to obtain a chromanol compound. 6.49 g of this chromanol compound was heated with anhydrous copper sulfate in a stream of carbon dioxide at 170-180°C for 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel to obtain the chromene derivative 5. 8g was obtained.

The elemental analysis values of this compound are C86,81%, H7,6
2%, 05.57%, which is the calculated value for cz + L□0 C 86.9Q%, H7, 59%, 05.5
2%. In addition, when proton nuclear magnetic resonance spectrum was measured, it was found to be 67.2 to 8.3 ppm.
Nearby is a <6H peak based on the proton of the naphthalene ring,
66.0-7. A peak of <2) (based on the alkene proton) was shown near Oppm, and a broad peak of 14H based on the broton of the bicyclo(3,3,i)9-nonylidene group was shown around 61.2 to 2.5 ppm.

Furthermore, when the 13C-nuclear magnetic resonance spectrum was measured, bicyclo(3,3°1)
Peak based on carbon of 9-nonylidene group, δ110~
A peak based on the carbon of the naphthalene ring appears around 160 ppm, and a peak based on the carbon of the alkene appears around 680 to 110 ppm. From the above results, the isolated product is
It was confirmed that the compound was represented by the above structural formula (2).

Production Example 3 A chromanone compound represented by the following formula was added dropwise into a solution of 3.06 g over about 1 hour. After the addition was completed, the ether solution was stirred for another 2 hours at room temperature, the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, the ether was removed under reduced pressure, and the chromanone The chromanol compound was then heated at 200° C. for about 10 minutes with anhydrous copper sulfate in a stream of carbon dioxide, and a brown viscous liquid was chromatographed on silica gel,
2.47 g of a chromene derivative of the following formula was obtained.

was dissolved in 50 cc of anhydrous ether, the solution was cooled to 0°C, and the freshly prepared Grignard reagent CHsMgJ (0,012 mol) was dissolved in 50 cc of anhydrous ether. %
7. This compound was confirmed to be a compound represented by the above structural formula (3) by measurement of vector and 11C-nuclear magnetic resonance spectra.

Production example 4 1-acetyl-2-naphthol 10 g (0,054
mol) and norcamphor 6,6 g (0,06
mol) and morpholine 8.7 g (0,10+wol
) was dissolved in 300 cc of toluene, boiled for 15 hours, and water was separated. After the reaction, toluene was removed under reduced pressure, and the remaining product was recrystallized with acetone to obtain compound 7 represented by the following formula. .53g was obtained.

Next, the generated chromanone compound was converted into a chromanol compound in the same manner as in Production Example 3, and after dehydration reaction, separation and purification, a chromene derivative 5.84 of the following formula was obtained.
I got g.

Next, 7.53 g of this compound was added to 100 cc of methanol.
6.95 g of a chromanone compound represented by the following formula was obtained by dissolving it in the solution and reacting it with methyl iodide.

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

Production Example 5 10 g (0,0318 mol) of 5-n-octyloxy-1-hydroxy-2acetonaphthone, 2.77 g (0,0477 mol) of acetone, and 1.13 g (0,0159 mol) of pyrrolidine were mixed with 10 g of toluene.
A solution was prepared in 01I11. 1 of this mixture
It was boiled for 0 hours and the water was separated. After the reaction was completed, toluene was removed under reduced pressure, the remaining chromanone compound was dissolved in 100 mf of methanol, and sodium borohydride was gradually added to form a chromanol compound.

By heating 6.0 g of this chromanol compound with 4.0 g of anhydrous copper sulfate at 150 to 160°C for 10 minutes in a carbon dioxide stream and purifying the brown viscous liquid by chromatography on silica gel, the following formula 3.8 g of chromene derivative was obtained.

It was confirmed that the compound was

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

As a result of structural analysis of the obtained product using the same structural confirmation method as in Production Example 1, it was confirmed that it was a compound represented by the structural formula shown in Table 1.

Similarly to Production Example 1, elemental analysis, proton nuclear magnetic resonance spectrum, and 13c-nuclear magnetic resonance spectrum revealed that this compound was shown to have the above structural formula (5).Production Example 15 3-Thienylethylidene-2 of the following formula -3.4 g (0.01 mol) of adamantylidene succinic anhydride and 17.8 g (0.01 mol) of glycine-methyl ester of the following formula:
02 mol) NlbCHzCOCIh 1 was dissolved in toluene and heated at 50° C. for 2 hours under a nitrogen atmosphere. After the reaction, the solvent was removed, the solution was dissolved in acetyl chloride, and the mixture was refluxed for 1 hour for cyclization. The obtained compound was rearranged to the following fulgimide compound (1) by refluxing it in 0-dichlorobenzene for 6 hours. The compound was purified by chromatography on silica gel using benzene and ether as eluent and was obtained as pale yellow needles from chloroform and hexane in 27% yield. The elemental analysis values of this compound are C66, 78%, H6
,09%, N 3.36%, 015.8%, 37
．． 96%, which is the calculated value for Cz, HzsOaNS, C67.15%, H6,08%, N
3.41%, OL5.6%.

There was an extremely good agreement of 37.79%. In addition, when proton nuclear magnetic resonance spectra were measured, the results were 67.0 to 8.
Based on aromatic protons near 0 ppm+
2H peak at 62.7 ppm; <3H peak based on the proton of the C-CH3 bond; peak of 14H peak based on protons of adamantylidene group at .2 to 2.5 ppm.

63-5 ppm with 1-5 rearranged protons and ≧N-C
A 3H peak based on 3t-bond is shown.

Furthermore, 13Q-nuclear magnetic resonance spectrum (+3cm NMR
When measured, there was a peak of M at around 627 to 70 pps at the carbon of the adamantylidene group and the carbon of the methylene chain.
A peak based on the methyl group] carbon at around δ15.6 ppm, a peak based on the carbon of the thiophene ring around δ110-160 ppn+ (1:"-'l, δ160-170 ppm
Nearby, a peak based on carbon of C=0 bond appears.

From the above results, it was confirmed that the isolated product was fulgimide compound α9 represented by the following structural formula.

was dissolved in tetrahydrofuran, and 1 part of metallic potassium was added to the solution.
g was reacted at room temperature to obtain 3 g of imido potash having the following formula.

Production Example 16 Fulgimide compound of the following formula 3.4 g (0.01 mo
l) This and 1.2 g of bromoacetonitrile (0
,01 mol) BrCHzCN in dimethylformamide, the following fulgimide compound 0ω was obtained. The compound was purified by chromatography on silica gel using chloroform and hexane as eluent and was obtained as pale yellow crystals from hexane in 57% yield. The elemental analysis values of this compound are C69, 81%, H5, 80%,
N 7.44%, 08.50%, 38.46%, calculated values for CzzHzNzOz3: C 69.84%, H5,82%, N 7.41%
, 08.47%, and 38.47%. In addition, when the proton nuclear magnetic resonance spectrum was measured, there was a <2H peak based on the proton of the thiophene ring around 67.0 to 7.5 ppm, and a <2H peak at 64.5 ppm.
Nearby ≧N -C)l Based on the proton of zCN bond <
2H peak, <IH peak based on 1.5 translocated protons near 63.7 ppm, <3H peak based on 10113 bonded protons near δ2.7pprrl,
-C1t, - bond proton and 14 protons based on adamantylidene group near δ1.3~2,5 pptn
A peak of H was shown.

Furthermore, lIC-nuclear magnetic resonance spectrum (+3c-NMR
) was measured, and a peak based on the carbon of the adamantylidene group was found around δ27 to 70 ppm, and a peak at 615.6 ppm was found.
Based on the carbon of the methyl group in the vicinity (Heake, 6110-16
A peak based on the carbon of the thiophene ring near 0 ppm, 6
A peak based on carbon of C═O bond appears near 160 to 170 ppm.

From the above results, it was confirmed that the isolated product was fulgimide compound 06) shown by the following structural formula.

Example 1 100 parts of benzene, 10 parts of polymethyl methacrylate, the chromene derivative obtained in Production Example 1, the fulgimide compound obtained in Production Example 58, and 0.2 parts and 0.0 parts of Cyasorb UV 1084 as an ultraviolet stabilizer, respectively. .2 parts and 0.4 parts were added, dissolved, and placed on a slide glass (11, 2 parts).
A cast film was made on a 3.7cm x 3.7cm The thickness was adjusted to 0.1 m111. The fatigue life of this photochromic film was measured using a xenon long life fade meter FAL-25AX-HC manufactured by Suga Test Instruments Co., Ltd.

In addition, changes in color tone were visually observed. Fatigue life (T
, 7□) is expressed as the time required for the absorbance at the maximum absorption wavelength based on each compound to decrease to 1/2 of the initial absorbance (To) for chromene or a chromene derivative and a fulgide compound or a fulgimide compound. However, the absorbance of To and T1/2 is the value obtained by subtracting the absorbance of the unirradiated film at the maximum absorption wavelength based on each compound, and the absorbance of To is the value obtained by subtracting the absorbance of the unirradiated film at the maximum absorption wavelength based on each compound.
Measurement was taken after seconds had elapsed.

The results are shown in Table 3. In Table 3, the color tone at TI/2 is the color tone at TI/□ of chromene or a chromene derivative.

Examples 2 to 32 The same procedures as in Example 1 were carried out except that the type of ultraviolet stabilizer used was changed.

The results are shown in Table 3.

Comparative Example 1 The same procedure as in Example 1 was carried out except that no ultraviolet stabilizer was used. The results are shown in Table 3.

Example 33 The blending ratios of the chromene derivative and fulgimide compound used in Example 1 were changed to 0.5 part and 0.1 part, respectively, and the ultraviolet stabilizer (Syasorb UV1084) was changed to 0.5 part and 0.1 part, respectively.
The procedure was the same as in Example 1 except that the amount was changed to 6 parts. 4th result
Shown in the table.

Examples 34 to 64 The same procedure as Example 33 was carried out except that the ultraviolet stabilizer was changed. The results are shown in Table 4.

Comparative Example 2 The same procedures as in Example 33 were carried out except that no ultraviolet stabilizer was used. The results are shown in Table 4.

Example 65 The same procedure as Example 1 was carried out except that the chromene derivative and fulgimide compound used in Example 1 were changed to the chromene derivative of Production Example 2 and the fulgimide compound of Production Example 57, respectively. The results are shown in Table 5.

Examples 66-96 The same procedure as Example 65 was carried out except that the ultraviolet stabilizer was changed. The results are shown in Table 5.

Comparative Example 3 The same procedure as in Example 65 was carried out except that no ultraviolet stabilizer was used. The results are shown in Table 5.

Example 97 In Example 1, the fulgimide compound of Production Example 57 was added, and the respective blending ratios of the chromene derivative, the fulgimide compound of Production Example 57, and the fulgimide compound of Production Example 58 were adjusted to 0.2 part, 0.05 part, and 0. The procedure was the same as in Example 1 except that the UV stabilizer was changed to 0.05 part and 0.3 part. The results are shown in Table 6.

Examples 97 to 128 The same procedure as Example 97 was carried out except that the ultraviolet stabilizer was changed. The results are shown in Table 6.

Comparative Example 4 The same procedure as in Example 97 was carried out except that no ultraviolet stabilizer was used. The results are shown in Table 6.

Examples 129 to 144 All Examples 1, 7.13 and 1 except that the amount of UV stabilizer added was changed in Examples 1, 7.13 and 18.
Same as 8. The results are shown in Table 7.

Examples 145 to 164 Examples 1.7.13 and 8, except that 100 parts by weight of each of two or three types of ultraviolet stabilizers were combined with a total of 100 parts by weight of the chromene derivative and the fulgimide compound. Everything was the same as in Example 1. The results are shown in Table 8.

Examples 165 to 172 In Examples 146 and 155, everything was the same as in Examples 146 and 155 except that the composition ratio of the ultraviolet stabilizer was changed. The results are shown in Table 9.

Examples 173 to 214 In Example 155, Production Example 3 was used as the chromene derivative.
The procedure of Example 155 was repeated, except that the compounds of Examples 15 to 14 were optionally combined with the fulgide compound or the compounds of Production Examples 15 to 56 as the fulgide compound. The results are shown in Table 10.

Reference Example I 100 parts of benzene, 10 parts of polymethyl methacrylate, and 0.2 parts of the chromene derivative obtained in Production Example 1 were added and dissolved to form a cast film on a slide glass (11.2 x 3.7 cm). The thickness was adjusted to 0.1 mm. This photochromic film was irradiated with a mercury lamp 5HL-100 manufactured by Toshiba ■ at 25°C±1°C at a distance of 10 cm for 60 seconds to develop color, and the photochromic properties were measured. The photochromic properties were expressed as follows. The results are shown in Table 11.

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

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

Reference Examples 2 to 14 All procedures were carried out in the same manner as in Reference Example 1, except that the chromene derivative in Reference Example 1 was changed to the chromene derivative obtained in Production Examples 2 to 14. The results are shown in Table 11.

Table 11

Claims (1)

[Claims] (1) (a) 100 parts by weight of chromene or its derivative (b
) fulgide compound or fulgimide compound 0.01-10
000 parts by weight and (c) 0.01 to 10,000 parts by weight of an ultraviolet stabilizer.