JPH07278535A - Photochromic composition - Google Patents

Abstract

(57) [Summary] [Purpose] Suppresses the change in color tone of the mixed color of fulgimide compound and chromene compound, and there is no change in color tone for a long time.
A photochromic composition having excellent photochromic durability is obtained. [Structure] (A) Chromene compound, for example, spiro [norbornane-2,2 '-[2H] benzo [h] chromene]
100 parts by weight of (B) fulgimide compound, for example, N-cyanomethyl-
6,7-dihydro-2- (p-methoxyphenyl) -4
-Methylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.
1] Decane) 0.01 to 10000 parts by weight (C) General formula (1) (However, R ₁ and R ₂ are the same or different hydrogen atoms or alkyl groups respectively, R ₃ is an alkyl group or an aryl group, and n is a positive integer.) 0.01-1000
0 parts by weight, and preferably further comprises an ultraviolet stabilizer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic composition having a small change in color tone with long-term use.

[0002]

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

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

When these compounds are 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 compounds alone. Then, as a result of mixing the above-mentioned chromene compound and the fulgimide compound, the present inventors succeeded in developing various mixed colors such as gray, amber and brown.

[0005]

However, the mixed color of these two photochromic compounds exhibits excellent reversible durability, but the color tone gradually changes with continued use. I understood. As a result of examination by the present inventors regarding this cause, the following two points were found to be the main causes.

Since the durability of the above-mentioned fulgimide compound in repeated coloring and fading is different from that of the chromene compound, the color tone changes with the long-term use.

The fulgimide compound deteriorates and yellows after long-term use.

[0008] Therefore, the present inventors have made it possible to maintain the color tone for a long period of time by making the durability of the fulgimide compound repeated coloring and fading almost equal to that of the chromene compound and preventing the yellowing due to the deterioration of the fulgimide compound. It was believed that a mixture with no change could be obtained. By combining the fulgimide compound and the chromene compound with the phosphite compound and the ultraviolet stabilizer, the durability of these two compounds becomes almost the same, and the yellowing due to the deterioration of the fulgimide compound is reduced. He found out what he could do and filed as Japanese Patent Application No. 4-323460.

According to the method of this Japanese Patent Application No. 4-323460, the color tone of the photochromic composition is stable without causing color misregistration or the like even over a considerably long period of time, but its use is even longer. When it reached, a slight change in color tone was still found. From these things,
It is an object of the present invention to propose a photochromic composition having further improved stability of color tone due to long-term use.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted extensive research in view of the above problems. As a result, they have found that the color tone of the photochromic composition obtained by combining the fulgimide compound and the chromene compound with the specific phosphite compound represented by the general formula (1) is extremely stable, and completed the present invention. Came to do.

That is, the present invention provides (A) a chromene compound
100 parts by weight (B) fulgimide compound 0.01
To 10,000 parts by weight and (C) general formula (1)

[0012]

[Chemical 2]

(Wherein R ₁ and R ₂ are the same or different hydrogen atoms or alkyl groups respectively, R ₃ is an alkyl group or an aryl group, and n is a positive integer). Acid ester compound
The photochromic composition comprises 0.01 to 10000 parts by weight.

The first component of the photochromic composition of the present invention is a chromene compound. As the chromene compound, a known compound having a chromene skeleton and having photochromic properties can be adopted without any limitation. The second component of the photochromic composition of the present invention is a fulgimide compound. The fulgimide compound is a compound having a structure in which an amine reacts with a compound having a fulgide skeleton, and known compounds having photochromic properties can be adopted without any limitation.

The above-mentioned fulgimide compound and chromene compound are disclosed in JP-A-2-28154 and JP-A-2-69.
No. 471, No. 3-11074, No. 3
Compounds known in JP-A-11075 and JP-A-3-284683 can be preferably used. The fulgimide compound that can be preferably used in the present invention is represented by the following formula (2).

[0016]

[Chemical 3]

[However,

[0018]

[Chemical 4]

Is a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group, and R ₁ has an alkyl group, an aryl group or a substituent. Which may be a cyclopropyl group or a monovalent heterocyclic group,

[0020]

[Chemical 5]

[0021] is a norbornylidene group or adamantylidene group, X is a group> N-R _{2, group> N-A 1 -B 1 -} (A 2) m- (B 2) n-R 3, group> N-a ₃ -A ₄ or a group> a N-a ₃ -R _4,, (wherein, R ₂ is a hydrogen atom, an alkyl group or an aryl group, a _1, a ₂ and a ₃ Are the same or different and are an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group, B
₁ and B ₂ are the same or different,

[0022]

[Chemical 6]

And m and n each independently represent 0 or 1, but when m is 0, n is 0 and R ₃
Is an alkyl group, a naphthyl group or a naphthylalkyl group, A ₄ is a naphthyl group, and R ₄ is a halogen atom, a cyano group or a nitro group. )] The above formula (2)
During,

[0024]

[Chemical 7]

As the divalent aromatic hydrocarbon group represented by, there can be mentioned a divalent group derived from one benzene ring or two or three condensed rings thereof. Examples of the saturated heterocyclic group include a divalent group derived from a 5- to 7-membered ring containing 1 to 2 oxygen atoms, nitrogen atoms, or sulfur atoms as ring-constituting atoms or a condensed ring thereof with a benzene ring. be able to. Specific examples of the divalent aromatic hydrocarbon group include 6 carbon atoms derived from a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring or the like.
Groups of 14 to 14 and specific examples of the divalent unsaturated heterocyclic group include furan ring, benzofuran ring, pyridine ring, quinoline ring, isoquinoline ring, pyrrole ring, thiophene ring and benzothiophene. A group having 4 to 9 carbon atoms derived from a ring or the like can be mentioned.

The substituents are not particularly limited, but examples thereof include halogen atoms such as chlorine, bromine and iodine:
Alkyl group having 1 to 4 carbon atoms such as methyl group and ethyl group: Alkoxy group having 1 to 4 carbon atoms such as methoxy group and ethoxy group: 6 carbon atoms such as phenyl group, tolyl group and xylyl group
10 aryl groups: C7-C14 alkoxyaryl groups (C6-10 aryl groups substituted by C1-4 alkoxy groups): Amino groups: Nitro groups: Cyano groups, etc. You can

In the above formula (2), the alkyl group, the aryl group and the heterocyclic group represented by R _{1 have 1} to 1 carbon atoms as described above.
4 alkyl groups, 6-10 carbon aryl groups, and 5- to 7-membered rings containing 1-2 oxygen atoms, nitrogen atoms, or sulfur atoms as ring-constituting atoms or condensed rings of these and benzene rings Mention may be made of derived monovalent groups.

[0028] In the above formula (2), an alkyl group, an aryl group represented by R ₂ is the same as the above-mentioned R _1. The alkylene group represented by A ₁ , A ₂ and A ₃ is preferably a group having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, trimethylene group and tetramethylene group, and the alkylidene group is ethylidene group. Group, a propylidene group, an isopropylidene group or the like is preferably a group having 2 to 4 carbon atoms, the cycloalkylene group is preferably a cyclohexylene group, and the alkylcycloalkane-diyl group is a dimethylcyclohexane-diyl group. Is preferred.

In the above formula (2), the alkyl group represented by R ₃ is the same as R ₁ above, and the naphthylalkyl group is a naphthylmethyl group, a naphthylethyl group or the like having 1 carbon atom.
It is preferably a group of 1 to 14.

Among the fulgide compounds represented by the above formula, R in consideration of durability of photochromic action and the like.
₁ is an alkyl group and a cyclopropyl group, and X is> N
-R, R is a cyanoalkyl group having 1 to 4 carbon atoms, a nitroalkyl group having 1 to 4 carbon atoms, or an alkoxycarbonylalkyl group having 3 to 9 carbon atoms (an alkoxy group having 1 to 4 carbon atoms and a carbon number of 1 to 4). Including 1 to 4 alkylene groups),

[0031]

[Chemical 8]

Is an adamantylidene group,

[0033]

[Chemical 9]

Is an aryl group having 6 to 10 carbon atoms or an alkoxyaryl group having 7 to 14 carbon atoms (having 1 to 4 carbon atoms).
A compound which is a heterocyclic group optionally substituted with an aryl group having 6 to 10 carbon atoms and which is substituted with an alkoxy group, especially a group derived from a thiophene ring is preferable.

The chromene compound which can be preferably used can be represented by the following formula (3).

[0036]

[Chemical 10]

[Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different hydrogen atoms, alkyl groups, aryl groups, substituted amino groups or saturated heterocyclic groups, and R ₃ and R ₄ are They may together form a ring,

[0038]

[Chemical 11]

The group represented by is an optionally substituted aromatic hydrocarbon group or unsaturated heterocyclic group. In the above formula (3), as the alkyl group and aryl group represented by R ₁ , R ₂ , R ₃ and R ₄ , the alkyl group and aryl group described for the above formula (2) can be adopted, and the substituted amino group is , An amino group in which at least one of hydrogen atoms is substituted with an alkyl group or an aryl group as described above, and the saturated heterocyclic group is a pyrrolidine ring, an imidazolidine ring, a piperidine ring, a piperazine ring,
A monovalent group derived from a 5- or 6-membered ring containing 1 to 2 nitrogen atoms, oxygen atoms, or sulfur atoms such as morpholine rings as ring-constituting atoms can be given.

In the above formula (3), the ring formed by R ₃ and R ₄ together forms a norbornylidene group, bicyclo [3.3.1] 9-nonylidene group, 2-bicyclo [3.
3.1] 9-Nonelidene group and the like can be mentioned.

In the above formula (3),

[0042]

[Chemical 12]

The aromatic hydrocarbon group or unsaturated heterocyclic group represented by is the same as the group in the above formula (2), and the substituent of each of these groups is not particularly limited, and examples thereof include chlorine, bromine, Halogen atom such as iodine: Alkyl group having 1 to 20 carbon atoms such as methyl group and ethyl group: Alkoxy group having 1 to 20 carbon atoms such as methoxy group and ethoxy group: Carbon number such as phenyl group, tolyl group and xylyl group 6-10 aryl groups: amino group: nitro group: cyano group etc. can be illustrated.

In the chromene compound, R ₁ and R ₂ are both hydrogen atoms, and R ₃ and R ₄ are the same or different alkyl groups having 1 to 4 carbon atoms,
Bicyclo [3.3.
1] 9-nonylidene group, 2-bicyclo [3.3.1] 9
-A nonelidene group or a norbornylidene group,

[0045]

[Chemical 13]

A compound which is a group derived from a naphthalene ring which may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms can be preferably used.

Specific examples of the fulgimide compound and the chromene compound that can be preferably used in the present invention include the following compounds.

Flugimide compound: 1) N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.
1.1] decane) 2) N-cyanomethyl-6,7-dihydro-2- (p-
Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1] decane) 3) N-cyanomethyl-6,7-dihydro-4 -Methylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1] decane) 4) 6,7-dihydro-N-methoxycarbonylmethyl-4-methyl- 2-Phenylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1] decane) 5) 6,7-dihydro-4-methyl-2- (p -Methylphenyl) -N-nitromethylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1] decane) 6) N-cyanomethyl- 6,7-Dihydro-4-cyclopropyl-3-methylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1] decane) 7) N-cyanomethyl- 6,7-Dihydro-4-cyclopropyl-spiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.
1] Decane) Chromene compound: 1) Spiro [norbornane-2,2 '-[2H] benzo [h] chromene] 2) Spiro [bicyclo [3.3.1] nonane-9,2'
-[2H] benzo [f] chromene] 3) 7'-methoxyspiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [f] chromene] 4) 7'-methoxyspiro [ Norbornane-2,2'-
[2H] benzo [f] chromene] 5) 2,2-dimethyl-7-octoxy [2H] benzo [h] chromene 6) spiro [2-bicyclo (3.3.1) nonene-9,
2 '-(2H) benzo (h) chromene] 7) spiro [2-bicyclo (3.3.1) nonene-9,
2 ′-(2H) benzo (f) chromene] The third component of the photochromic composition of the present invention is a phosphite compound represented by the following formula (1).

[0049]

[Chemical 14]

(However, R ₁ and R ₂ are the same or different hydrogen atoms or alkyl groups, R ₃ is an alkyl group or an aryl group, and n is a positive integer.) In the present invention, As the phosphoric acid ester compound, in particular, by using a compound having the above-mentioned specific structure, the repeated durability of the fulgide compound and the chromene compound is almost the same, and when a phosphorous acid ester compound having a different structure is used. In particular, the yellowing due to the deterioration of the fulgimide compound can be remarkably reduced, and as a result, the color tone of the photochromic composition can be remarkably stabilized.

In the above formula (4), the alkyl group of R ₁ and R ₂ has 1 to 1 carbon atoms such as methyl group and ethyl group.
It is preferred that it is a group 3 and preferably a methyl group. R ₃
Examples of the alkyl group include an ethyl group, an octyl group, a decyl group, a tridecyl group, a hexadecyl group, an octadecyl group, and the like, and examples of the aryl group include a phenyl group and 2-methylphenyl group. Group, 4-methylphenyl group, 2-isopropylphenyl group, 4-dodecylphenyl group, 4-nonylphenyl group, 2,4-dimethylphenyl group, 4-t-butylphenyl group, 2,4
A group having 6 to 18 carbon atoms such as -t-butylphenyl group can be mentioned, but an aryl group is preferable. Further, n is not particularly limited, but is preferably 3 to 15 and preferably 5 to 13.

Specific examples of the phosphite compound that can be preferably used in the present invention include the following compounds.

[0053]

[Chemical 15]

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

The above-mentioned amounts of the chromene compound, the fulgimide compound and the phosphite compound are 0.06 parts by weight of the fulgimide compound based on 100 parts by weight of the chromene compound.
1 to 10000 parts by weight, and 0.01 to 10000 parts by weight of the phosphite compound. The blending ratio of the fulgimide compound may be determined according to the desired color tone of the photochromic composition, but generally, when a good mixed color is expected by mixing with the chromene compound, it is 0.
It is preferable to select from the range of 05 to 200 parts by weight.

When the amount of the phosphite compound is less than 0.01 parts by weight, the effect of preventing color shift due to long-term use is hardly recognized, and when it exceeds 10,000 parts by weight, the photochromic compound in the resin described later is used. Aggregation of the photochromic compound occurs when the composition is dispersed, and the durability of the photochromic property is sharply reduced. In particular, from the viewpoint of photochromic properties of the obtained photochromic composition, the phosphite compound is preferably in the range of 50 to 400 parts by weight.

In the photochromic composition of the present invention, good color tone stability can be obtained by blending the above-mentioned phosphite compound, but in order to make the change in color tone smaller, an ultraviolet stabilizer is further added. It is preferable to mix them. As the ultraviolet stabilizer, known ultraviolet stabilizers added to various plastics can be used without any limitation. In the present invention, taking into consideration the yellowing prevention due to the deterioration of the mixed color of the chromene compound and the fulgimide compound and the deterioration of the fulgimide compound, among various ultraviolet stabilizers, a hindered amine light stabilizer (in one molecule (Including a light stabilizer having a hindered amine structure and a hindered phenol structure), a singlet oxygen quencher, a hindered phenol antioxidant, and a sulfur-based antioxidant are preferably used.

Of these, light stabilizers having a hindered amine structure and a hindered phenol structure in one molecule are most preferable, and then other hindered amine light stabilizers, singlet oxygen quenchers, and hindered phenol antioxidants. , With almost the same effect. Further, two or more kinds of these UV stabilizers may be combined. In addition, good results can also be obtained by combining three kinds of light stabilizers having a hindered amine structure and a hindered phenol structure in one molecule with other hindered amine light stabilizers and singlet oxygen quenchers. The singlet oxygen quencher preferably used in the present invention is a complex of Ni and an organic ligand, cobalt (III) -tris-di-n-butyldithiocarbamate, iron (III) -diisopropyldithiocarbamate. And cobalt (II) -diisopropyldithiocarbamate. Among these singlet oxygen quenchers, a complex of Ni and an organic ligand is particularly preferable. Specific examples of such a complex are as follows.

[0063]

[Chemical 21]

[2,2-thiobis (4- (1,1,3,
3-tetramethylbutyl) phenolato) butylamine)
nickel,

[0065]

[Chemical formula 22]

Nickel-bis [O-ethyl (3,5-di-tert-butyl-4-hydroxybenzyl)] phosphonate,

[0067]

[Chemical formula 23]

Nickel-dibutyldithiocarbamate,

[0069]

[Chemical formula 24]

Bis [2,2'-thiobis-4- (1,
1,3,3-Tetramethylbutyl) phenolato] nickel Others, UV-Chek A from Ferro Corporation
M105, UV-check M126 and UV-check AM
The Ni complex marketed under the trade name of 205 can be mentioned.

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

[0072]

[Chemical 25]

[0073]

[Chemical formula 26]

[0074]

[Chemical 27]

[0075]

[Chemical 28]

[0076]

[Chemical 29]

[0077]

[Chemical 30]

[0078]

[Chemical 31]

[0079]

[Chemical 32]

[0080]

[Chemical 33]

[0081]

[Chemical 34]

(However, the above formulas (e), (f), (ki),
Among (K), (K), (K), (SA), (SI), (S) and (SE), 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 alkyl groups, 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 (CO), (SA), (SI), (SU) and (CE) is not particularly limited in the number of carbon atoms, but generally 1 to 1 for reasons such as availability of these compounds. It is preferably in the range of 12.

Further, as the hindered amine light stabilizer, Sumisorb LS- manufactured by Sumitomo Chemical Co., Ltd.
2000 and LS-2001 (both are trade names).

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

[0085]

[Chemical 35]

[0086]

[Chemical 36]

[0087]

[Chemical 37]

[0088]

[Chemical 38]

[0089]

[Chemical Formula 39]

[0090]

[Chemical 40]

[0091]

[Chemical 41]

[0092]

[Chemical 42]

[0093]

[Chemical 43]

[0094]

[Chemical 44]

[0095]

[Chemical formula 45]

[0096]

[Chemical formula 46]

(However, the above equation, (so), (ta),
(H), (t), (te), (to), (na), (d),
In (nu), (ne), (no) and (c), 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, R ₁₉ is a hydrogen atom, an alkyl group or an acryloyl group, and n is a positive integer. is there. ) Above (se), (so), (ta), (chi), (tsu),
(Te), (to), (na), (d), (nu), (ne),
In (no) and (c), the alkyl group is not particularly limited in the number of carbon atoms, but in general, it is preferably in the range of 1 to 20 for reasons such as easy availability of these compounds.

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

[0099]

[Chemical 47]

[0100]

[Chemical 48]

[0101]

[Chemical 49]

[0102]

[Chemical 50]

[0103]

[Chemical 51]

(However, the above equations (H), (F), (F),
In (e) and (m), R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇
Is an alkyl group, and R ₃ is a hydrogen atom or an alkyl group. ) Above (C), (C), (C), (C), (C), (C)
In (and (m)), the alkyl group is not particularly limited in the number of carbon atoms, but in general, it is preferably in the range of 1 to 20 for reasons such as easy availability of these compounds.

The blending amount of such an ultraviolet stabilizer is usually
0.01-10 with respect to 100 parts by weight of the chromene compound
It is preferably in the range of 000 parts by weight. Particularly, from the viewpoint of the photochromic property of the obtained photochromic composition, the ultraviolet stabilizer is preferably in the range of 50 to 400 parts by weight.

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. The synthetic resin that constitutes the polymer matrix used by dispersing the photochromic composition in the present invention may be any one that can uniformly disperse the chromene compound and the fulgimide compound, and may be optically transparent. .

Especially when a synthetic resin obtained by polymerizing a composition containing a monomer having a radically polymerizable group represented by the following general formulas (I), (II), (III) and (IV) is used as a polymer matrix. The effect of the present invention, which is particularly effective in preventing the color misregistration of the mixed color of the two photochromic compounds, can be obtained, and the dark color density and the fast fading speed of the photochromic compound can be obtained, and further the photochromic action can be obtained. The reversible durability of can be improved. Also, practical physical properties, for example,
It is suitable for the present invention because a photochromic resin having good transparency, surface hardness, heat resistance and the like can be obtained. Of the monomers having a radically polymerizable group represented by the following formula, it is of course possible to use a mixture of two or more thereof.

[0108]

[Chemical 52]

(Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 1 to 4 carbon atoms, or

[0110]

[Chemical 53]

(However, R ₃ is a hydrogen atom or a methyl group, X is a halogen atom, k and m are integers of 0 to 2, and a is an integer of 0 to 4 which represents the number of substitutions of the halogen atom. K is 0-5. ), N is an integer of 1 to 20. ) In the general formula (I), the alkylene group having 1 to 4 carbon atoms represented by R ₂ is a methylene group, an ethylene group, a propylene group,
Examples thereof include butylene group, trimethylene group, tetramethylene group and the like.

[0112]

[Chemical 54]

(Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group, or a carbon atom which may be substituted with a halogen atom). An aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms which may be substituted with a halogen atom.) In the general formula (II), it may be substituted with a hydroxyl group represented by R _2. Examples of the preferable alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, a hydroxypropyl group and the like, and a carbon number of 6 which may be substituted with a halogen atom. ~ 1
The aryl group of 0 is a phenyl group, a naphthyl group, a chlorophenyl group, a bromophenyl group, a trichlorophenyl group,
Examples thereof include tribromophenyl group, and
The aralkyl group having 7 to 10 carbon atoms which may be substituted with a halogen atom is a benzyl group, a phenethyl group, a chlorobenzyl group, a bromobenzyl group, a trichlorobenzyl group,
A tribromobenzyl group etc. can be illustrated.

[0114]

[Chemical 55]

(Wherein R ₁ and R ₄ are each a hydrogen atom or a methyl group, and R ₂ and R ₃ are each an alkylene having 1 to 4 carbon atoms which may be substituted with the same or different hydroxyl groups. Group, or

[0116]

[Chemical 56]

And m and n are 0 or 1, respectively. ) The alkylene group represented by R ₂ and R ₃ in the above formula (III) is a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, a tetramethylene group, or a group in which these groups are substituted with a hydroxyl group. Can be illustrated.

[0118]

[Chemical 57]

(Provided that R ₁ , R ₂ , R ₃ and R ₄ are the same or different halogen atoms, and X ₁ , X ₂
And X ₃ are each an oxygen atom or a sulfur atom, j, k and m are 0 or 1, respectively, and k
When j = 0, j = 0, and when m = 0, k =
When j = 0, m = k = 1 and j = 0, X ₁ and X ₂ do not become sulfur atoms at the same time, and m =
When k = j = 1, X ₁ , X ₂ and X ₃ cannot be sulfur atoms at the same time. The following compounds can be exemplified as monomers that can be preferably used in the present invention. Formula (I) above
Examples of the compound include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl). ) Propane 2,
2-bis (4-methacryloyloxyethoxyphenyl) propane: Examples of the compound of the above formula (II) include methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, n-butyl methacrylate,
Methacrylic acid t-butyl tribromophenyl methacrylate, 2-hydroxyethyl methacrylate: As the compound of the above formula (III), glycidyl acrylate,
Glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxybutyl methacrylate: As the compound of the above formula (IV), bis-4-vinylbenzyl ether, bis -4-vinylbenzyl sulfide, 1,
2- (p-vinylbenzyloxy) ethane, 1,2-
Mention may be made of (p-vinylbenzylthio) ethane and bis- (p-vinylbenzyloxyethyl) sulfide.

Further, as a monomer copolymerizable with the monomer represented by the above general formula, acrylic acid, methacrylic acid,
Unsaturated carboxylic acids such as maleic anhydride and fumaric acid; acrylic acid and methacrylic acid esters such as butanediol dimethacrylate, hexamethylenediol dimethacrylate and urethane acrylate; fumaric acid such as monomethyl fumarate, diethyl fumarate and diphenyl fumarate. Ester compounds; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl epoxysuccinate, diallyl malate, allyl cinnamate,
Allyl compounds such as allyl isocyanate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate; styrene, chlorostyrene, α-methylstyrene, α-methylstyrene dimer, vinylnaphthalene, isopropenylnaphthalene, bromostyrene, divinyl Examples thereof include aromatic vinyl compounds such as benzene. These monomers may be used alone or in combination of two or more.

Among the various monomers described above, considering the physical properties such as the durability of the photochromic property and the speed of decoloring of the resin obtained by polymerizing the mixture of the photochromic composition of the present invention and the monomer, 30 to 90% by weight of the compound of the above formula (I) or (IV), the above formula (II)
Alternatively, 0.1 to 50% by weight of the compound (III), and 0.1 to 50% by weight of a monomer copolymerizable with these monomers, α-methylstyrene, α-methylstyrene dimer, and the like are blended. Preference is given to using monomer compositions.

The addition amount of the photochromic composition of the present invention dispersed in such a monomer may be appropriately determined according to the concentration of the photochromic compound at the time of color development.
Usually from 0.001 to 10 per 100 parts by weight of monomer
Suitably, the amount is in the range of 0.01 to 1 part by weight.

The photochromic composition of the present invention is particularly preferably used for photochromic lenses. The method for producing the photochromic lens is not particularly limited as long as it is a method capable of obtaining uniform light control performance, and a known radical polymerization method can be adopted. Polymerization initiation means is the use of radical polymerization initiators such as various peroxides and azo compounds, or
It can be performed by irradiation with ultraviolet rays, α rays, β rays, γ rays or the like, or a combination of both. As a typical polymerization method, a photochromic composition of the present invention containing a radical polymerization initiator is injected between molds held by an elastomer gasket or a spacer, and the mixture is oxidized in an air furnace and then removed. Polymerization is employed.

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

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

Of the polymerization conditions, the temperature particularly affects the properties of the obtained photochromic resin. This temperature condition cannot be unconditionally limited because it is influenced by the type and amount of the initiator and the type of the monomer, but generally the polymerization is started at a relatively low temperature, the temperature is slowly raised, and the polymerization is performed. It is preferable to perform a so-called taper type two-stage polymerization in which curing is performed at a high temperature at the end. Since the polymerization time also depends on various factors like the temperature, it is preferable to determine the optimum time in advance according to these conditions, but generally, the conditions are selected so that the polymerization is completed in 2 to 40 hours. Is preferred.

Needless to say, various stabilizers and additives such as a releasing agent, an ultraviolet absorber, an antioxidant, a coloring preventing agent, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance, etc. may be added, if necessary, in the polymerization. It can be selected and used.

Further, the photochromic resin obtained by the above method may be subjected to the following treatments depending on its use. That is, dyeing using a dye such as a disperse dye, a silane coupling agent, a hard coating agent containing sol such as silicon, zirconium, antimony, aluminum, tin, or tungsten as a main component, SiO, TiO, Z
It is also possible to perform processing such as antireflection treatment and antistatic treatment by vapor deposition of a thin film of a metal oxide such as rO or coating of a thin film of an organic polymer, and secondary treatment.

[0129]

As described above, the photochromic composition of the present invention is dispersed evenly in various resins, so that the photochromic composition can be changed from colorless to colored by light containing ultraviolet rays such as sunlight or light of mercury lamp. The change is reversible and has excellent dimmability. Further, the present invention, chromene compound, and by blending a phosphite compound with a phosphite compound of a specific structural formula, a mixed color is easily obtained, and further, when the phosphite compound has a long-term use In the above, the effect of suppressing the color tone change of the mixed color is remarkably improved.

Therefore, the resin containing the photochromic composition of the present invention is useful as an organic glass having photochromic properties, and can be suitably used for photochromic lenses and the like.

[0131]

EXAMPLES Hereinafter, the present invention will be described in 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 photochromic compounds used in the following examples are the following compounds.

Flugimide compound: (1) N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.
3.1.1] decane) (2) N-cyanomethyl-6,7-dihydro-2- (p
-Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1] decane) (3) N-cyanomethyl-6,7-dihydro -4-Methylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1] decane) (4) 6,7-dihydro-N-methoxycarbonylmethyl-4 -Methyl-spiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.
3.1.1] decane) (5) 6,7-dihydro-4-methyl-2- (p-methylphenyl) -N-nitromethylspiro (5,6-benzo [b] thiophenedicarboximide-7 , 2-tricyclo [3.3.1.1] decane) (6) N-cyanomethyl-6,7-dihydro-4-cyclopropyl-3-methylspiro (5,6-benzo [b]
Thiophene dicarboximide-7,2-tricyclo [3.3.1.1] decane) chromene compound: (1) Spiro [norbornane-2,2 '-[2H] benzo [h] chromene] (2) Spiro [ Bicyclo [3.3.1] nonane-9,
2 '-[2H] benzo [f] chromene] (3) 7'-methoxyspiro [bicyclo [3.3.1]]
Nonane-9,2 '-[2H] benzo [f] chromene] (4) 3'-methylspiro [norbornane-2,2'-
[2H] benzo [f] chromene] (5) 2,2-dimethyl-7-octoxy [2H] benzo [h] chromene (6) Spiro [2-bicyclo [3.3.1] nonene-
The 9,2 '-[2H] benzo [f] chromene] phosphite compound is the following compound.

(1) HBP (trade name: manufactured by Johoku Chemical Industry Co., Ltd.)

[0135]

[Chemical 58]

(However, n is 6 to 8.) (2)

[0137]

[Chemical 59]

(However, n is 6 to 8.) (3)

[0139]

[Chemical 60]

(However, n is 6 to 8.) (4)

[0141]

[Chemical formula 61]

(However, n is 10 to 12.) (5)

[0143]

[Chemical formula 62]

(However, n is 6 to 8.) (6) ADEKA STAB 1500 (trade name: manufactured by Asahi Denka Kogyo Co., Ltd.)

[0145]

[Chemical formula 63]

(However, R is an alkyl group having 12 to 15 carbon atoms.) (7) PEP-36 (trade name: manufactured by Asahi Denka Co., Ltd.)

[0147]

[Chemical 64]

(8) ADEKA STAB 3010 (trade name: manufactured by Asahi Denka Kogyo Co., Ltd.)

[0149]

[Chemical 65]

(9) JPP-613M (trade name: manufactured by Johoku Chemical Industry Co., Ltd.)

[0151]

[Chemical formula 66]

(10) JPS-312 (trade name: manufactured by Johoku Chemical Industry Co., Ltd.)

[0153]

[Chemical formula 67]

(11) JPH-3800 (trade name: manufactured by Johoku Chemical Industry Co., Ltd.)

[0155]

[Chemical 68]

The UV stabilizer is the following compound.

(1) Sanol LS-2626 (trade name: manufactured by Sankyo Co., Ltd.)

[0158]

[Chemical 69]

(2) SANOL LS-744 (trade name:
Sankyo Co., Ltd.)

[0160]

[Chemical 70]

(3) ADEKA STAB LA-82 (trade name: manufactured by Asahi Denka Kogyo Co., Ltd.)

[0162]

[Chemical 71]

(4) ADEKA STAB LA-87 (trade name: manufactured by Asahi Denka Co., Ltd.)

[0164]

[Chemical 72]

(5) ADEKA STAB LA-63 (trade name: manufactured by Asahi Denka Kogyo Co., Ltd.)

[0166]

[Chemical formula 73]

Example 1 80 parts of tetraethylene glycol dimethacrylate and 10 parts of glycidyl methacrylate α-methylstyrene 10
Part, 0.5 part of the chromene compound shown in Table 1, 0.5 part of the fulgimide compound shown in Table 1, 0.5 part of the phosphite compound (1), 0.5 part of the ultraviolet stabilizer (1), 0.5 parts by weight of t-butylperoxy-2-ethylhexanate was added as a radical polymerization initiator and mixed well. This mixed solution was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. Polymerization is carried out in an air oven at 30 ° C to 90 ° C.
18 hours, gradually raise the temperature to 90 ° C for 2
Held for hours. After the polymerization was completed, the mold was removed from the air furnace, allowed to cool, and then the weight body was removed from the glass mold of the mold.

The photochromic resin thus obtained was stored at room temperature in the dark for 6 months, and a xenon fade meter FAC-25AX- manufactured by Suga Test Instruments Co., Ltd. was used.
Fatigue life was measured by HC. The yellowness was determined by measuring the YI of the sample with a color difference meter (SM-4 type) manufactured by Suga Test Instruments Co., Ltd. In addition, the change in color tone was visually observed. The fatigue life (T _1/2 ) was expressed as the time required for the absorbance at the maximum absorption wavelength based on the fulgimide compound to drop to 1/2 of the initial (T ₀ ) absorbance. However, the absorbances of T ₀ and T _1/2 are both values obtained by subtracting the absorbance of the unirradiated resin at the maximum absorption wavelength based on the fulgimide compound. The results are shown in Table 1.

[0169]

[Table 1]

Example 2, Comparative Example 1 In Example 1, 0.5 part of the chromene compound (2) and 0.5 part of the fulgimide compound (2) were used, and the types of the phosphite compound and the ultraviolet stabilizer are shown in Table 2. All were the same as in Example 1 except that the above was changed. The results are shown in Table 2.

[0171]

[Table 2]

Example 3 40 parts of bis-4-vinylbenzyl ether and 40 parts of benzyl methacrylate were used as the monomer components in Example 1.
Parts, 20 parts of glycidyl methacrylate, 0.5 parts of chromene compound (2) and 0.5 parts of fulgimide compound (6), the kinds of phosphite compound and ultraviolet stabilizer are changed as shown in Table 3, and The procedure of Example 1 was repeated except that the amount of the phosphite compound was 0.3 part. The results are shown in Table 3.

[0173]

[Table 3]

Example 4 In Example 1, 2,2-bis (4
-Methacryloyloxyethoxy propane 60 parts, methyl methacrylate 20 parts, glycidyl methacrylate 2
0 part, chromene compound (2) 0.3 part, and fulgimide compound (2) 0.5 part were used, and the types of the phosphite ester compound and the ultraviolet stabilizer were changed as shown in Table 4. The procedure of Example 1 was repeated except that the amount of the ester compound was 1.0 part. The results are shown in Table 4.

[0175]

[Table 4]

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[Procedure amendment]

[Submission date] May 25, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0108

[Correction method] Change

[Correction content]

[0108]

[Chemical 52]

Claims (1)

[Claims] 1. A chromene compound (A)
100 parts by weight (B) fulgimide compound 0.01
-10000 parts by weight and (C) general formula (1) (However, R ₁ and R ₂ are the same or different hydrogen atoms or alkyl groups respectively, R ₃ is an alkyl group or an aryl group, and n is a positive integer.) 0.01-1000
A photochromic composition comprising 0 parts by weight.