JPH0733509B2 - Photochromic composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photochromic composition having good photochromic durability.

(Problems to be Solved by Prior Art and Invention) Photochromism is a phenomenon that has been attracting attention for several years, and when a compound is irradiated with light including ultraviolet rays such as sunlight or light of a mercury lamp, the photochromism is promptly observed. It is a reversible effect that changes color and returns to the original color when the light is stopped and left in the dark. A compound having this property is called a photochromic compound, and various compounds have been conventionally synthesized, but no special commonality is recognized in the structure.

As photochromic compounds, fulgide compounds and fulgimide compounds are known. It is also known to combine an ultraviolet stabilizer with these fulgide compounds or fulgimide compounds in order to improve the repeated durability of the photochromic property of these compounds (JP-A-2006-242242).
64-81884). By combining with a UV stabilizer,
The durability of the fulgide compound or the fulgimide compound is remarkably improved, but further excellent durability is desired for practical use of these compounds.

(Means for Solving the Problems) The inventors of the present invention have conducted diligent research for the purpose of further improving the repeating durability of the photochromic property of the fulgide compound or the fulgimide compound, and as a result, It was found that more excellent durability can be obtained by blending two or more kinds of ultraviolet stabilizers than by increasing the blending amount, and the present invention has been completed.

That is, the present invention is a photochromic composition comprising (a) 100 parts by weight of a fulgide compound or fulgimide compound and (b) a total of 0.01 to 10,000 parts by weight of two or more kinds of ultraviolet stabilizers.

One component of the photochromic composition of the present invention is a fulgide compound or a fulgimide compound. The fulgide compound has the following formula A compound having a structure represented by and having photochromic properties is adopted without any limitation. The fulgimide compound has the following formula A compound having a structure represented by and having photochromic properties is adopted without any limitation.

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

In the ceremony Is a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group R ₁ may be a monovalent hydrocarbon group which may have a substituent, or Monovalent heterocyclic group Is a norbornylidene group or an adamantylidene group which may have a substituent, X is an oxygen atom, a group N—R ₂ group N—A ₁ —B ₁ — (A ₂ m (B ₂ nR ₃ group N -A ₃ shows the -A ₄ or a group N-a ₃ -R _4.

In the general formula [I], The groups are aromatic hydrocarbon groups or unsaturated heterocyclic groups, which may have at most 5, preferably up to 3, substituents. The aromatic hydrocarbon group has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, and examples of the ring forming the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring and a phenanthrene ring. A ring is included.

The unsaturated heterocyclic group is a 5-membered or 6-membered monocyclic heterocyclic group containing at least one heteroatom such as nitrogen atom, oxygen atom and sulfur atom, or a benzene ring or cyclohexene. A fused heterocyclic group in which the ring is fused is shown. Examples of the ring forming the heterocyclic group include nitrogen-containing heterocycles such as pyrrole ring, pyridine ring, quinoline ring and isoquinoline ring; oxygen-containing heterocycles such as furan ring, benzofuran ring and pyran ring; thiophene ring, Examples thereof include sulfur-containing heterocycles such as benzothiophene ring.

As previously mentioned, The aromatic hydrocarbon group or unsaturated heterocyclic group represented by may contain at most 5, preferably up to 3, substituents. Examples of such substituents are halogen atoms such as fluorine, chlorine, bromine and iodine; hydroxyl group; cyano group; nitro group; amino group; carboxyl group; methylamino group; carbon number 1 such as diethylamino group.
~ 4 alkylamino group; lower alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and t-butyl group; 1 to 3 halogen atoms such as trifluoromethyl group and 2-chloroethyl group Halogenated lower alkyl group having; 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, tolyl group; phenoxy group An aryloxy group having 6 to 14 carbon atoms such as 1-naphthoxy group; an aralkyl group having 7 to 15 carbon atoms such as benzyl group, phenylethyl group, and phenylpropyl group; 7 carbon atoms such as benzyloxy group and phenylpropoxy group ~ 15
And an alkoxythio group having 1 to 4 carbon atoms and the like. These substituents may be the same or different and the position is not particularly limited.

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 in each case be substituted by at least one of

Also, above Contains an aryl group having 1 to 14 carbon atoms which may be substituted in each case by 1 to 3 of each of the above-mentioned substituents or one nitrogen atom, oxygen atom and sulfur atom 5
A monocyclic heterocyclic group having a six-membered ring or a six-membered ring or a condensed heterocyclic group in which a benzene ring or a cyclohexene ring is condensed with the heterocyclic group is more preferable.

Further above Is preferably a divalent benzene ring, a 5-membered or 6-membered monocyclic heterocycle containing one heteroatom, or a condensed heterocycle in which a benzene ring or a cyclohexene ring is condensed with this heterocycle. . The benzene ring, monocyclic heterocycle or condensed heterocycle containing one or two of the above-mentioned substituents is also a preferred embodiment.

Each R ₁ in the above general formula [I] is a monovalent hydrocarbon group or a monovalent heterocyclic group which may have a substituent.

The hydrocarbon group of R1 may be any of an aliphatic, alicyclic or aromatic hydrocarbon, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group having 1 to 10 carbon atoms. 20, preferably 1 to 6 alkyl group; phenyl group, tolyl group, xylyl group, aryl group having 6 to 14 carbon atoms such as naphthyl group; benzyl group, phenylethyl group,
1 carbon atom such as phenylpropyl group and phenylbutyl group
Aralkyl groups with -10, preferably 1-4 alkylene groups are suitable.

As the heterocyclic group for R ₁ , at least one heteroatom such as nitrogen atom, oxygen atom and sulfur atom is 1 to 3
A 5-membered or 6-membered monocyclic heterocyclic group containing 1 or 2, preferably 1 or 2, or a condensed heterocyclic group in which benzene is condensed thereto is preferable. Specific examples of such a heterocyclic group include In addition to the examples of the unsaturated heterocyclic group described in the definition of 1, saturated saturated heterocyclic groups such as a piperidine ring, a piperazine ring, a morpholine ring, a prolysine ring, an indoline ring, and a chroman ring can be mentioned.

The hydrocarbon group or heterocyclic group for R ₁ described above may have a substituent, which is not critical. The number of such substituents is at most 5, preferably 3 with respect to the hydrocarbon group or heterocyclic group.
It is preferable to contain up to the above, and specific examples of the substituent include the above. The same substituents as those described above can be exemplified.

Preferred as R ₁ is a halogen atom or a carbon number of 1 to 1.
An alkyl group having 1 to 20 carbon atoms which may be substituted with an alkoxy group having 4 or phenyl groups; an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom or an alkoxy group having 1 to 4 carbon atoms; Or a membered or 6-membered monocyclic heterocyclic group containing 1 to 3, especially 1 nitrogen atom, carbon atom and sulfur atom, or a condensed heterocyclic group in which a benzene ring is condensed to the heterocyclic group, Is a monocyclic heterocyclic group.

Further, particularly preferable as R ₁ is an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

In the above general formula [I] in the present invention, Means a norbornylidene group or an adamantylidene group, each of which may have a substituent. Here, the norbornylidene group is represented by the following formula And the adamantylidene group is represented by the following formula.

The above formulas show the skeleton structures of the norbornylidene group and the adamantylidene group, each of which has no substituent. In these norbornylidene group or adamantylidene group, the hydrogen atom in the above formula may be substituted with 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 it has a plurality of substituents, it may be the same or different.

Examples of the substituent of the above norbornylidene group or adamantylidene group include a hydroxy group; an alkylamino group having 1 to 4 carbon atoms such as a methylamino group and a diethylamino group; a carbon group 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, 1-naphthoxy group; methyl group, ethyl group, t-butyl group A lower alkyl group having 1 to 4 carbon atoms such as a group; a halogen atom such as fluorine, chlorine and iodine;
Cyano group; carboxyl group; alkoxycarbonyl group having 2 to 10 carbon atoms such as ethoxycarbonyl; halogen-substituted alkyl group having 1 or 2 carbon atoms such as trifluoromethyl group; nitro group; 6 carbon atoms such as phenyl group and tolyl group ~Ten
And aryl groups; aralkyl groups having 7 to 9 carbon atoms such as phenylethyl group and phenylpropyl group.

Preferred examples of these substituents include a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms and 1 to 4 carbon atoms.
Is an alkoxy group, a C2-10 alkoxycarbonyl group, a C7-9 aralkyl group, or a C6-10 aryl group.

In the general formula [I] of the present invention, X is an oxygen atom (—O—), a group N—R ₂ , a group N—A ₁ —B ₁ — (A ₂ m (B ₂ nR ₃ , a group N—A ₃ shows the -A ₄ or a group N-a ₃ -R _4.

In the general formula [I], X is a group _{N-A 1 -B 1 - (} A 2 m (B 2 nR 3, group N-A ₃ -A ₄ or a group N-A ₃ -R _4, in particular group N- A ₃ -R ₄ or a group N-A ₁ -B _1- (A ₂ m (B ₂ nR ₃ (wherein R ₃ is 1 to 3 selected from the group consisting of a halogen atom, a cyano group and a nitro group. Atom or optionally substituted carbon number 1
~ 10 alkyl groups. Is more preferable from the viewpoint of durability of photochromic property of the obtained compound.

X in the general formula [I] is the group N-A ₁ -B _1- (A ₂
m (in the case of B ₂ nR ₃ , when R ₃ is a naphthyl group or a naphthylalkyl group, and when it is a group N—A ₃ —A ₄ , a naphthyl group and an imido group represented by R ₃ or R ₄ ( N
It is preferable that the number of main chain atoms sandwiched between (-) and (-) is in the range of 3 to 7 in order to obtain a compound excellent in durability of photochromic action.

Next, in the above X, R ₂ , R ₃ , R ₄ , A ₁ , A ₂ , A ₃ , A ₄ ,
The definitions of B ₁ , B ₂ , m and n will be described in detail.

R ₂ represents a hydrogen atom, an alkyl group or an aryl group,
Examples of the alkyl group include a methyl group, an ethyl group,
Examples thereof include propyl group, n-, iso- or tert-butyl group, pentyl group, hexyl group, octyl group and decyl group. Among them, those having 1 to 20 carbon atoms, and further 1 to 10 carbon atoms. Are preferred. Examples of the aryl group include those having 6 to 10 carbon atoms such as phenyl group, tolyl group and naphthyl group.

A ₁ , A ₂ and A ₃ may be the same as or different from each other and can be an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group. Specific examples of these are, for example,
Methylene group, ethylene group, propylene group, butylene group,
C10 alkylene group such as trimethylene group, tetramethylene group or 2,2-dimethyltrimethylene group; alkylidene group having 2 to 10 carbon atoms such as ethylidene group, propylidene group or isopropylidene group; carbon such as cyclohexylene group Cycloalkylene group of the number 3 to 10; 2-methylcyclohexane-α-, 1-diyl group 4-methylcyclohexane-α, 1-diyl group And an alkylcycloalkane-diyl group having 6 to 10 carbon atoms such as As A ₁ and A ₂ , particularly 1 to ₂ carbon atoms
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 are preferable.

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

Or m and n each independently represent 0 or 1,
When 0 is shown, A ₂ m or B ₂ n means a bond. Further, when m is 0, n is also 0.

R ₃ is an alkyl group which may have a substituent,
A naphthyl group or a naphthylalkyl group is shown. The number of carbon atoms of the above alkyl group is not particularly limited, but it is preferably 1 to 10, and the number of carbon atoms of the alkyl group of the naphthylalkyl group is preferably 1 to 4.

The substituent of each of the above groups 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, and The naphthyl group or naphthylalkyl group is a halogen atom, a cyano group, a nitro group, or a carbon number of 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 R ₃ , the same alkyl groups as those exemplified for R ₂ can be used. Examples of the naphthylalkyl group include naphthylmethyl group, naphthylethyl group, naphthylpropyl group, naphthylbutyl group and the like.

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

In the above definition of R ₃ and A ₄ , the halogen atom may be fluorine, chlorine or bromine.

The second component of the photochromic composition of the present invention is a UV stabilizer. As the ultraviolet stabilizer, known ones which are added to various plastics are used without any limitation. In particular, a singlet oxygen quencher, a hindered amine light stabilizer (including a compound having a hindered amine structure and a hindered phenol structure in one molecule), a hindered phenol antioxidant, and a sulfur-based secondary antioxidant are preferably used. . In the present invention, considering the durability of the fulgide compound or the fulgimide compound, in the combination of two types,
It is preferable to combine a compound having a hindered amine structure and a hindered phenol structure in one molecule with a singlet oxygen quencher and a hindered amine light stabilizer or a hindered phenol antioxidant. Further, when a compound having a hindered amine structure and a hindered phenol structure in one molecule is combined with three types of a singlet enzyme quencher and a hindered amine light stabilizer, the best results are obtained.

As the singlet oxygen quencher preferably used in the present invention, a complex of Ni ²⁺ and an organic ligand, cobalt (III)-
Tris-di-n-butyldithiocarbamate, iron (II
Examples thereof include I) -diisopropyldithiocarbamate and cobalt (II) -diisopropyldithiocarbamate. Among these singlet oxygen quenchers,
A complex of Ni ²⁺ and an organic ligand is particularly preferable. Specific examples of such a complex are as follows.

[2,2-thiobis (4- (1,1,3,3-tetramethylbutyl) phenolato) butylamine) nickel, Nickel-bis [O-ethyl (3,5-di-tert-butyl-4-hydroxybenzyl)] phosphonate, Nickel-dibutyldithiocarbamate, Bis [2,2'-thiobis-4- (1,1,3,3-tetramethylbutyl) phenolato] nickel Other from Ferro Corporation, UV-Chek AM10
5, Ni-complexes marketed under the trade names UV-Chek M126 and UV-Chek AM205 can be mentioned.

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

(C ₂₆ H ₅₂ N ₄ ) m (Co) (However, the above formulas (e), (f), (ki), (ku),
Among (K), (K), (S), (S) and (S), R ¹ , R ² ,
^{R 4, R 5, R 6} , R 7, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16 and R ¹⁷
Is an alkyl group, R ³ and R ⁸ are hydrogen atoms or an alkyl group, R ¹⁸ is a benzoyl group, an acryloyl group or a methacryloyl group, and m and n are positive integers. ) Above (o), (f), (ki), (ku), (ke),
The alkyl group in (ko), (sa), (shi) and (su) is not particularly limited in the number of carbon atoms, but is generally in the range of 1 to 12 for reasons such as easy availability of these compounds. Preferably there is.

Further, as hindered amine light stabilizers, Sumitomo Chemical Co., Ltd. Sumisorb LS-2000 and LS-20
01 (both are trade names) can be mentioned.

Specific examples of the hindered phenol antioxidant suitable as an ultraviolet stabilizer are as follows.

(However, the above formulas (SE), (SO), (TA), (CH),
(Tsu), (te), (to), (na), (d), (nu),
In (n) and (no), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are alkyl groups, R ³ is hydrogen or an alkyl group, and R ¹⁹
Is a hydrogen atom, an alkyl group or an acryloyl group, and n
Is a positive integer. ) Above (se), (so), (ta), (chi), (tsu),
In (te), (to), (na), (d), (nu), (ne) and (no), the alkyl group is not particularly limited in the number of carbons, but generally, the acquisition of these compounds is available. It is preferably in the range of 1 to 20 for reasons such as ease of use.

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

(R ¹ −SCH ₂ CH ₂ COOCH ₂ ) ₄ C (hi) (However, in the above formulas (c), (c), (f), (f) and (e), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are alkyl groups,
R ³ is a hydrogen atom or an alkyl group. ) In the above (c), (c), (f), (f) and (e), the alkyl group is not particularly limited in the number of carbon atoms, but in general, the reason for the easy availability of these compounds, etc. From 1
It is preferably in the range of 20.

The compounding ratio of the fulgide compound or fulgimide compound and the two or more kinds of ultraviolet stabilizers is such that the total of the two or more kinds of ultraviolet stabilizers is 0.01 to 10,000 parts by weight with respect to 100 parts by weight of the fulgide compound or the fulgimide compound. is there. When the amount of UV stabilizer is less than 0.01 parts by weight, the effect of improving the repeating durability of Photochromic Co. is hardly recognized.
If it exceeds 10000 parts by weight, molding of the resin becomes difficult when the fulgide compound or the fulgimide compound is dispersed in the resin described later, which is not preferable. Particularly, from the viewpoint of the photochromic property of the obtained photochromic composition, it is preferable that the total amount of the two or more ultraviolet stabilizers is in the range of 50 to 400 parts by weight.

The amount ratio of each UV stabilizer is arbitrary, but from the viewpoint of photochromic durability, one UV stabilizer is 100 parts by weight, and the other UV stabilizers are each in the range of 30 to 300 parts by weight. It is preferable to select.

The photochromic composition of the present invention can exhibit well the desired photochromic function as described above by being uniformly dispersed in various polymer matrices. As the synthetic resin that constitutes the polymer matrix used by dispersing the photochromic composition in the present invention, any resin that can uniformly disperse the fulgide compound or the fulgimide compound may be used, and it is optically preferable, for example, polyacryl. Methyl acid, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane,
Polymers such as polycarbonate and poly (allyl diglycol carbonate), and polymers obtained by copolymerizing the monomers forming these polymers with each other or with the monomers and other monomers are preferably used. The addition amount of the composition of the present invention dispersed in such a resin is
0.001 to 10 parts by weight relative to 100 parts by weight of the resin, preferably
It is 0.1 to 10 parts by weight.

The photochromic composition of the present invention is particularly preferably used for a photochromic lens. The method for producing the photochromic lens is not particularly limited as long as it is a method capable of obtaining uniform dimming performance, and if it is specifically illustrated, the above-mentioned fulgide compound or fulgimide compound and two or more kinds of ultraviolet stabilizers are uniformly dispersed. There is a method of sandwiching a dispersed polymer film in a lens. Alternatively, the photochromic composition is dispersed in silicone oil,
For example, there is a method in which the lens surface is impregnated at 200 ° C. for 15 minutes, and then the surface is coated with a curable substance to form a photochromic lens. There is also a method in which the above-mentioned polymer film is applied to the lens surface and the surface is coated with a curable substance to form a photochromic lens.

(Effects) As described above, the photochromic composition of the present invention is particularly dispersed by uniformly dispersing it in various resins.
It changes from colorless to colored or dark color by the light including the mode light or the light including ultraviolet rays such as the light of a mercury lamp, and the change is reversible and has an excellent dimming property.

In addition, the present invention improves the repeated durability of photochromic properties by using a fulgide compound or a fulgimide compound in combination with two or more kinds of UV stabilizers, as compared with the case of using a single kind of UV stabilizer. It was successful.

Therefore, the photochromic composition of the present invention can be used in a wide range of fields, for example, various recording memory materials replacing silver salt photosensitive materials, copying materials, printing photoreceptors, cathode ray tube recording materials, laser photosensitive materials, and the like. It can also be used as various recording materials.

(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. In addition, "part" in an Example is a "weight part."

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

・ Cyasorb UV1084 (Product name: American Cyanamid) Irgastab 2002 (trade name: manufactured by Ciba Kaiggy) ・ Rylex NBC (Product name: DuPont) ・ UV-Chek AM101 (Product name: Ferro Corporation) ・ UV-Chek AM105 (Product name: Ferro Corporation) ・ Tinuvin 765 (Product name: Ciba Geigy) ・ Tinuvin 144 (Product name: Ciba Geigy) ・ Chimassorb 944 (Product name: Ciba Geigy) ・ Cyasorb 3346 (Product name: American Cyanamid) ・ Tinuvin 622 (trade name: manufactured by Ciba Geigy) Sanor LS-1114 (Product name: Sankyosha) ・ Sanol LS-744 (Product name: Sankyosha) ・ MARK LA-82 (Product name: ADEKA ARGUS) ・ MARK LA-87 (Product name: ADEKA ARGUS) ・ Sanol LS-2626 (Product name: Sankyo Co., Ltd.) ・ Sumilyzer GA-80 (Product name: Sumitomo Chemical Co., Ltd.) ・ Irganox 1010 (Product name: Ciba Geigy) ・ MARK AO-50 (Product name: ADEKA ARGUS) ・ Sumilyzer GM (Product name: Sumitomo Chemical Co., Ltd.) ・ Sumilyzer BBM-S (Product name: Sumitomo Chemical Co., Ltd.) ・ Sumilyzer WX-R (Product name: Sumitomo Chemical Co., Ltd.) ・ Sumilyzer S (Product name: Sumitomo Chemical Co., Ltd.) ・ Sumilyzer BHT (Product name: Sumitomo Chemical Co., Ltd.) ・ MARK AO-20 (Product name: ADEKA ARGUS) ・ MARK AO-30 (Product name: ADEKA ARGUS) ・ MARK AO-330 (Product name: ADEKA ARGUS) ・ Irganox 245 (Product name: Ciba-Geigy) ・ Antioxidant HPM-12 (Product name: SFO) ・ MARK AO-23 (Product name: ADEKA ARGUS) ・ Sumilyzer TP-D (trade name: Sumitomo Chemical) (H ₂₅ C ₁₂ SCH ₂ CH ₂ COOCH ₂ ) ₄ C ・ Sumilyzer TPL-R (trade name: Sumitomo Chemical) ・ Sumilyzer TPS (Product name: Sumitomo Chemical) ・ Sumilyzer MB (Product name: Sumitomo Chemical Co., Ltd.) Production Example 1 3.4 g (0.01 mol) of 3-thienylethylidene-2-adamantylidene succinic anhydride of the following formula And glycine-methyl ester of the following formula 17.8 g (0.02 mol) Was dissolved in toluene and heated at 50 ° C. for 2 hours under a nitrogen atmosphere. After the reaction, remove the solvent and dissolve in acetyl chloride,
The mixture was refluxed for 1 hour and cyclized. The obtained compound was refluxed in O-dichlorobenzene for 6 hours to be rearranged to the following fulgimidation compound (1). This compound was purified by chromatography on silica gel using benzene and ether as eluents and was obtained in 27% yield as pale yellow needles from chloroform and hexane. The elemental analysis value of this compound is C66.78%, H6.09%, N3.36
%, O15.8%, a S7.96%, C67.15% is calculated values for _{C 23 H 25 O 4 NS,} H6.08%, N3.41%, O15.6%, S7.79 % Was extremely well matched. Further, the proton nuclear magnetic resonance spectrum was measured. As a result, a peak of 2H due to an aromatic proton was observed near δ = 7.0 to 8.0 ppm, a peak of 3H due to a proton of a C—CH ₃ bond at δ2.7 ppm, and δ3.7 ppm.
In the vicinity 3H peak due to the proton of the bound methyl group, δ1.2
~ 2.5ppm based on the proton group of the adamantylidene group 14
The peak of H, the peak of 3H based on the protons rearranged 1 to 5 at ε3 to 5 ppm and the N-CH ₂ -bond, was shown.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C-NMR was measured to find that the peak due to the carbon of the adamantylidene group and the carbon of the methylene chain was around δ27 to 70 ppm, and the peak around the carbon of the methyl group was around δ15.6 ppm. , A peak based on carbon of thiophene ring near δ110-160ppm, δ160-170ppm
A peak based on the carbon of the C = 0 bond appears in the vicinity.

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

Production Example 2 3.4 g (0.01 mol) of the fulgimide compound of the following formula Is dissolved in tetrahydrofuran and 1 g of metallic potassium is added to it.
Was reacted at room temperature to obtain 3 g of imide potassium having the following formula.

The following fulgimide compound (2) was obtained by reacting this with bromoacetonitrile 1.2 g (0.01 mol) BrCH ₂ CN of the following formula in dimethylformamide. This compound was purified by chromatography on silica gel using chloroform and hexane as eluents and was obtained in 57% yield as pale yellow crystals from hexane. The elemental analysis values of this compound are C69.81%, H5.80%, N7.44%, O8.50%, S
8.46%, which is the calculated value for C ₂₂ H ₂₂ N ₂ O ₂ S C6
It was in very good agreement with 9.84%, H5.82%, N7.41%, O8.47%, S8.47%. Further, the proton nuclear magnetic resonance spectrum was measured, and it was found that the peak of 2H based on the proton of the thiophene ring was around δ7.0 to 7.5 ppm, and N-CH ₂ CN was around δ4.5 ppm.
2H peak due to bound protons, around δ3.7ppm 1.
5 1H peak based on rearranged protons, 3H peak based on protons of --CH ₃ bond near δ 2.7 ppm, δ 1.3 to 2.
At around 5 ppm, 14H peaks of the proton of the —CH ₂ — bond and the proton based on the adamantylidene group were shown.

Furthermore, when ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C-NMR) was measured, a peak due to the carbon of the adamantylidene group at δ 27 to 70 ppm, a peak due to the carbon of the methyl group at δ 15.6 ppm, and δ 110 to 160 ppm. A peak based on the carbon of the thiophene ring appears in the vicinity, and a peak based on the carbon of the C = 0 bond appears near δ160 to 170 ppm.

From the above results, it was confirmed that the isolated product was the fulgimide compound (2) represented by the following structural formula.

Production Examples 3 to 44 The fulgide compounds or fulgimide compounds shown in Table 1 were synthesized in the same manner as in Production Examples 1 and 2.

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

Example 1 100 parts by weight of benzene, 10 parts of polymethylmethacrylate, the fulgimide compound (44) obtained in Production Example 44, Ciazove
0.2 parts each of UV1084 and Sanol LS2626 were added and dissolved, and a cast film was made on a slide glass (11.2 × 3.7 cm).

The thickness was adjusted to 0.1 mm. The fatigue life of this photochromic film was measured with a Xenon long life fade meter FAL-25AX-HC manufactured by Suga Test Instruments Co., Ltd. Fatigue life (T 1/2) is defined as the time required for the color density to decay to half its initial value when the film is exposed to a fade meter. The results are shown in Table 2.

Examples 2-39 The procedure of Example 1 was repeated except that the combination of the UV stabilizers used in Example 1 was changed.

The results are shown in Table 2.

Comparative Examples 1 to 3 The same procedure as in Example 1 was carried out except that 0.4 parts of Sheasorb UV1084, Chinupin 765 and Sumilizer GA-80 were individually added.

Examples 40 to 78 The fulgimide compound used in Example 1 was prepared according to Production Example 43.
The procedure of Example 1 was repeated except that the compound (43) obtained in. Was used. The results are shown in Table 3.

Comparative Examples 4 to 6 The same procedure as in Example 40 was carried out except that 0.4 parts of Sheasorb UV1084, Tinuvin 765 and Sumilizer GA-80 were added singly in Example 40.

Examples 79 to 95 As the ultraviolet stabilizer used in Example 1, three kinds of hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based secondary antioxidants described below were used.
The same procedure as in Example 1 was carried out except that the UV stabilizer was changed to 2 parts by weight. The results are shown in Table 4.

Comparative Examples 7 to 9 All of Example 1 except that the ultraviolet stabilizer as described below was added separately by 0.6 parts each.
Same as.

Examples 96 to 100 All of Examples 1 to 88 were the same as Examples 1 and 88 except that the composition ratio of the ultraviolet stabilizer was changed. The results are shown in Table 5.

(However, the composition ratio of the ultraviolet stabilizer in Table 5 shows each part by weight when the fulgimide compound is 100 parts by weight.) Examples 101 to 103 In Example 88, except that the hindered amine light stabilizer, the hindered phenol antioxidant, and the singlet oxygen quencher were used in equal parts by weight, respectively, and the total addition amount was changed as shown in Table 6. Were all the same as in Example 88. The results are shown in Table 6.

Examples 104 to 145 The procedure of Example 88 was repeated except that the fulgide compound or the fulgimide compound was used in place of Example 88. The results are shown in Table 7.

Claims (1)

[Claims] 1. A photochromic composition comprising (a) 100 parts by weight of a fulgide compound or fulgimide compound and (b) a total of 0.01 to 10,000 parts by weight of two or more kinds of ultraviolet stabilizers.