JPH09302336A - Photochromic curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition suitably useful as a photochromic cured material slight in color blur even when used for many hours. SOLUTION: This photochromic curable composition comprises (A) 100 pts.wt. of a radical-polymerizable monomer, (B) 1-30 pts.wt. of a polymerizable monomer containing at least one epoxy group in one molecule, (C) 0.01-0.2 pts.wt. based on 100 pts.wt. of the total of the components A and B of a chromene, (D) 0.04-0.1 pts.wt. based on 100 pts.wt. of the total of the components A and B of a fulgimide compound and (E) 0.03-0.1 pts.wt. based on 100 pts.wt. of the total of the components A and B of a spirooxazine compound in the ratio of the components D to E of <2.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic curable composition capable of suppressing color shift due to deterioration of the photochromic cured product.

[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 and proposed, but no special common skeleton is recognized in the structure. A fulgide or fulgimide compound is known as a photochromic compound.

The color tone of the fulgide or fulgimide compound at the time of color development is orange to blue. On the other hand, chromene compounds,
Alternatively, spirooxazine compounds are also well known as photochromic compounds, and the color tones of these compounds are generally orange to yellow for chromene compounds and reddish purple to blue for spirooxazine compounds.

Generally, in a photochromic lens,
Gray, amber and brown are preferred as the color tone when the color is developed. However, when the above compounds are used alone, there are many cases in which the desired neutral color cannot be obtained. As a method for obtaining an intermediate color, a chromene compound, a fulgide or fulgimide compound, and a spirooxazine compound having different color tones can be mixed at an arbitrary composition ratio. For example, in JP-A-3-124790, it is known that an intermediate color is obtained by mixing a chromene compound and a fulgimide compound, and in JP-A-5-9469, by mixing a chromene compound and a spirooxazine compound. . In addition, DE432515
4 proposes that, as a result of mixing a spirooxazine compound, a chromene compound and a fulgimide compound, various intermediate colors such as gray, amber and brown are developed.

An important physical property of the photochromic lens is durability of the photochromic property. The term "durability" as used herein refers to the decrease in the initial color density (hereinafter referred to as absolute durability) and the change in the initial color tone (hereinafter referred to as color misregistration) due to the deterioration of the photochromic compound after long-term use. means. In general, absolute durability is good
When used as a photochromic lens for a long time, it means that the change in initial color density is small, and when the color shift is small, it means that when used for a long time, there is little change in color tone from the initial color tone. . As described above, when an intermediate color is obtained by mixing several kinds of photochromic compounds, when there is a difference in absolute durability of each photochromic compound, after a long time use, a color shift different from the initial color tone occurs. . For example, when the absolute durability of a photochromic compound exhibiting a yellow color is higher than the absolute durability of a photochromic compound exhibiting a blue color tone, after a long period of use, the color tone becomes a yellow color stronger than the initial color tone. . As a means for suppressing such color shift, there is a method of aligning the absolute durability of a chromene compound with the absolute durability of a fulgimide compound by adding a phosphite compound as described in JP-A-6-172748. . Further, JP-A-7-13017 describes a method of suppressing color shift by combining a photochromic compound having a different coloring color tone with a compound having a low coloring durability and a compound having the same coloring color tone and a high absolute durability. .

[0006]

When a chromene compound, a fulgimide compound and a spirooxazine compound are combined as the photochromic compound to obtain a photochromic lens that develops an intermediate color, the absolute durability in the yellow region is It is often higher than absolute durability. Therefore, when used for a long time, color shift occurs.

[0007]

Therefore, as a result of intensive studies, the inventors of the present invention have determined that the mixing ratio of the fulgimide compound and the spirooxazine compound is within a specific range so that the absolute durability in the yellow region and the blue color are improved. It has been found that the absolute durability of the regions can be made almost the same and the color shift when used for a long time can be suppressed, and the present invention has been completed.

That is, the present invention comprises (A) 100 parts by weight of a radical polymerizable monomer, (B) 1 to 30 parts by weight of a polymerizable monomer having at least one epoxy group in one molecule,
0.01 to 0.2 parts by weight of the (C) chromene compound per 100 parts by weight of the total of (A) and (B), and 100 parts by weight of the total of (A) and (B) of the (D) fulgimide compound. On the other hand, 0.04 to 0.1 part by weight and (E) the spirooxazine compound in an amount of 0.
A photochromic curable composition comprising 03 to 0.1 part by weight and having a weight ratio of (D) to (E) of less than 2.0.

The component (A) in the photochromic curable composition of the present invention is a radically polymerizable monomer having a radically polymerizable group. As the radically polymerizable group, a vinyl group, an allyl group, an acroyl group and a methacryloyl group can be generally mentioned, but an acryloyl group or a methacryloyl group is preferable in order to obtain good photochromic properties. A compound that can be preferably used in the present invention is represented by the following general formula (1) or (2)
Can be indicated by

[0010]

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

[0012]

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(Wherein k is 0 or 1), and n is an integer of 2 to 20. ]

[0014]

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[Wherein R ¹ is a hydrogen atom or a methyl group, R ⁴ 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 above formulas (1) and (2), the number of carbon atoms represented by R ² is 1
Alkylene group and 4 are methylene, ethylene, propylene, iso- propylene, butylene, iso- butylene, trimethylene group, can be exemplified tetramethylene group, a hydroxyl group represented by R ⁴ Examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxylethyl group, and a hydroxylpropyl group.
Examples of the aralkyl group having 7 to 10 carbon atoms which may be substituted with a halogen atom include a benzyl group, a phenethyl group, a chlorobenzyl group, a bromobenzyl group, a trichlorobenzyl group and a tribromobenzyl group.

Specific examples of the compounds that can be preferably used in the present invention as the radically polymerizable monomer include methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, tribromophenyl methacrylate and ethylene glycol. Diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, etc. Of acrylic acid and methacrylic acid ester compounds. These monomers can be used alone or in combination of two or more.

Addition of α-methylstyrene dimer to the radical-polymerizable monomer improves the moldability of the photochromic curable composition and makes it possible to obtain the photochromic curable composition in good yield. Further, addition of a monofunctional radically polymerizable monomer having a polymerization adjusting ability further improves the moldability of the photochromic curable composition. Examples of the added monofunctional radically polymerizable monomer having a polymerization adjusting ability include α-methylstyrene and the like.

Among the above radical-polymerizable monomers, a combination of propylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, α-methylstyrene dimer, 2,2-bis (4-methacryloyloxyethoxypheny) propane, triethylene glycol dimer. Methacrylate, α-methylstyrene, 2-hydroxyethyl methacrylate, α-styrene dimer combination, triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate, α-methyl styrene, 2-hydroxyethyl methacrylate, α
It is preferable from the viewpoints of moldability, refractive index and various physical properties of the photochromic curable composition that a combination of methylstyrene dimer and the like can be obtained.

The component (B) in the photochromic curable composition of the present invention is a polymerizable monomer having at least one epoxy group and radically polymerizable group in one molecule. The polymerizable monomer is essential to improve the durability of the photochromic compound in the obtained cured product.

As the radically polymerizable group, a vinyl group, an allyl group, an acryloyl group and a methacryloyl group can be generally mentioned, but an acryloyl group or a methacryloyl group is preferable in order to obtain a good photochromic property. The polymerizable monomer that can be preferably used in the present invention can be represented by the following general formula.

[0021]

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(However, R ¹ and R ⁵ are each a hydrogen atom or a methyl group, and R ⁶ and R ⁷ are each an alkylene having 1 to 4 carbon atoms which may be substituted with the same or different hydroxyl groups. Group or below

[0023]

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And m and n are 0 or 1, respectively. Examples of the alkylene group represented by R ⁶ and R ⁷ in the above formula include a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group and a tetramethylene group. Further, these groups may be substituted with a hydroxyl group.

As the polymerizable monomer having at least one epoxy group in one molecule, specific examples of the polymerizable monomer that can be preferably used in the present invention are glycidyl acrylate, glycidyl methacrylate and β. -Methylglycidyl acrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxybutyl methacrylate, 3- (glycidyl-2-oxyethoxy)
2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3- (glycidyloxy-
2-hydroxypropyloxy) -2-hydroxypropyl acrylate and the like methacrylate compounds or acrylate compounds can be mentioned. Among these, glycidyl methacrylate and glycidyl acrylate are preferable in order to further improve the durability of the photochromic action. The polymerizable monomer having at least one epoxy group in one molecule is usually added in an amount of 1 to 30 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the radical polymerizable monomer. If it is less than 1 part by weight, the effect of improving the durability of the photochromic action is small,
If the amount is more than parts by weight, the heat resistance decreases, so the above range is preferred.

The component (C) in the present invention is a chromene compound. As the chromene compound, a known compound having a chromene skeleton and having photochromic properties can be used without any limitation. For example, the chromene compound represented by the following general formula (3) is preferably used.

[0027]

[Chemical 6]

[Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are the same or different hydrogen atoms, alkyl groups, aryl groups, unsaturated heterocyclic groups, substituted amino groups or saturated heterocyclic groups; ¹⁰ and R ¹¹ may together form a ring,

[0029]

[Chemical 7]

The groups represented by each have 1 to 20 carbon atoms.
Is an alkyl group, or an aromatic hydrocarbon group or an unsaturated heterocyclic group which may be substituted with an alkoxy group having 1 to 20 carbon atoms. ] In the general formula (3), the alkyl group and aryl group represented by R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a methyl group, an ethyl group,
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as propyl group, and an aryl group having 6 to 10 carbon atoms such as phenyl group and naphthyl group, and the substituted amino group includes a methylamino group, an ethylamino group and a dimethylamino group. , An amino group in which at least one hydrogen atom is substituted with an alkyl group or an aryl group such as a phenylamino group and a naphthylamino group, and the unsaturated heterocyclic group includes a pyrrole ring, a pyridine ring, an indoline ring, and a furan ring. A ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, or the like, including a nitrogen atom, an oxygen atom, or a sulfur atom as a ring-constituting atom, 1 to 2 5
Examples include monovalent groups such as a 6-membered ring or a benzo ring, a tetrahydrobenzothiophene ring, a benzofuran ring, and a tetrahydrobenzofuran ring derived from a condensed ring of the 6-membered ring and a benzene ring or a cyclohexane ring. The cyclic group is a monovalent 5- or 6-membered ring containing 1-2 nitrogen atoms, oxygen atoms or sulfur atoms as ring-constituting atoms such as a pyrrolidine ring, an imidazolidine ring, a piperidine ring, a piperazine ring and a morpholine ring. The following groups can be mentioned.

In the general formula (3), the ring formed by R ¹⁰ and R ¹¹ together includes a norbornylidene group, a bicyclo [3.3.1] 9-nonylidene group and the like.

In the above general formula (3),

[0033]

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Examples of the aromatic hydrocarbon group or unsaturated heterocyclic group represented by: include a divalent group derived from one benzene ring or two or three condensed rings thereof, and
The divalent unsaturated heterocyclic group is a 5- to 7-membered ring containing 1 to 2 nitrogen atom, oxygen atom or sulfur atom as a ring-constituting atom or a condensed ring of the same with a benzene ring or a cyclohexane ring. Mention may be made of valence groups. Specific examples of the divalent aromatic include a group having 6 to 14 carbon atoms derived from a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring or the like, and a divalent unsaturated heterocycle. Specific examples of the group include carbon numbers derived from a pyridine ring, a quinoline ring, an isoquinoline ring, a pyrrole ring, an indole ring, a furan ring, a benzofuran ring, a tetrahydrobenzofuran ring, a thiophene ring, a benzothiophene ring, and a tetrahydrobenzothiophene ring. 4-
There may be mentioned 9 groups. The substituent of each of these groups is not particularly limited, but examples thereof include halogen atoms such as chlorine, bromine and iodine: C1 to C20 such as methyl and ethyl groups.
Alkyl group: 1 to 1 carbon atoms such as methoxy group and ethoxy group
20-alkoxy group: C6-C10 aryl group such as phenyl group, tolyl group, xylyl group and the like: C7-C14 alkoxyaryl group (C6-C4 substituted with C1-C4 alkoxy group) 10 aryl groups): amino groups:
A nitro group: a cyano group etc. can be illustrated.

As the chromene compound, in the general formula (3), R ⁸ and R ⁹ are both hydrogen atoms, and R ¹⁰ and R ¹¹ are the same or different alkyl groups having 1 to 4 carbon atoms and 6 carbon atoms, respectively. 10 is an aryl group or an unsaturated heterocyclic group, or is a bicyclo [3.3.1] 9-nonylidene group or norbornylidene group formed by combining them.

[0036]

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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 chromene compounds that can be preferably used in the present invention include the following compounds. Chromene compound: (1) Spiro (norbornane-2,2 '-(2H) benzo (h) chromene) (2) Spiro (bicyclo [3.3.1] nonane-9,
2 ′-(2H) benzo (h) chromene) (3) 7′-methoxyspiro (bicyclo (3.3.1)
Nonane-9,2 ′-(2H) benzo (h) chromene) (4) 7′-methoxyspiro (norbornane-2,2 ′)
-(2H) benzo (h) chromene) (5) 2,2-dimethyl-7-octoxy (2H) benzo (f) chromene (6) 2,2- (2'-difuryl) (2H) benzo (f) Chromene (7) 2,2- (phenyl-2'-furyl) (2H) benzo (f) chromene (8) 9-morpholino-2,2-diphenyl (2H) benzo (f) chromene (D) in the present invention. The component is a fulgimide compound.
As the fulgimide compound, a known compound having a fulgimide skeleton and having photochromic properties can be used without any limitation. For example, the fulgimide compound represented by the following general formula (4) is preferably used.

[0039]

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[However,

[0041]

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Is a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group, and R ¹² is an alkyl group, a cycloalkyl group, an aryl group or a monovalent group. Is a heterocyclic group of

[0043]

[Chemical 12]

Is a norbornylidene group, a bicyclononylidene group or an adamantylidene group, and X is an oxygen atom, a group> N-R ¹³ , a group> N-A ₁ -B _1- (A ₂ )-(B
₂₎ -R ^14, groups> N-A ₃ -A ₄ or a group> N-A _3,
-R ¹⁵ (wherein R ¹³ is a hydrogen atom, an alkyl group, an aryl group or a cyano group, A ₁ , A ₂ and A ₃ are the same or different and are an alkylene group, an alkylidene group, a cycloalkylene group. A group or an alkylcycloalkane-diyl group, B ₁ and B ₂ are the same or different,

[0045]

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And m and n each independently represent 0 or 1, but when m is 0, n is 0 and R ¹⁴
Is an alkyl group, a naphthyl group or a naphthylalkyl group, A ₄ is a naphthyl group, and R ¹⁵ is a halogen atom, a cyano group or a nitro group. )] In the general formula (4),

[0047]

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The divalent aromatic hydrocarbon group or divalent unsaturated heterocyclic group represented by is the same as the group in the above general formula (3).

In the above general formula (4), the alkyl group, aryl group and heterocyclic group represented by R ¹² are the alkyl groups having 1 to 4 carbon atoms and the 6 to 10 carbon atoms exemplified in the general formula (3). An aryl group, a 5- to 7-membered ring containing 1-2 oxygen atoms, nitrogen atoms, or sulfur atoms as ring-constituting atoms or a monovalent heterocyclic group derived from a condensed ring of the ring with a benzene ring or a cyclohexane ring; Can be mentioned. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.

In the general formula (4), when X is a group containing a nitrogen atom, the alkyl group and aryl group represented by R ¹³ are the same as R ¹² . 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. A group having 2 to 4 carbon atoms such as a group, a propylidene group and an isopropylidene group, and
The cycloalkylene group is preferably a cyclohexylene group, and the alkylcycloalkane-diyl group is preferably a dimethylcyclohexane-diyl group. Also, R ¹⁴
In the alkyl groups represented are the same as above R ^12, naphthyl alkyl group, naphthylmethyl group, preferably a number from 11 to 14 group atoms such as a naphthylethyl group.

Among the fulgide compounds represented by the above general formula (4), R ¹² is an alkyl group or a cycloalkyl group, X is> N—R, and R is R, considering the durability of photochromic action. Is a cyanoalkyl group having 1 to 4 carbon atoms, a cyano group, a nitroalkyl group having 1 to 4 carbon atoms, or an alkoxycarbonylalkyl group having 3 to 9 carbon atoms (alkoxy group having 1 to 4 carbon atoms and 1 to 4 carbon atoms). Including an alkylene group of),

[0052]

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Is an adamantylidene group,

[0054]

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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 heterocyclic group which may be substituted with an aryl group having 6 to 10 carbon atoms which is substituted with an alkoxy group, especially a furan ring,
Compounds that are groups derived from the thiophene ring are preferred.

Specific examples of the fulgimide 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 ^3,7 ] decane) (2) N-cyanomethyl-6,7-dihydro-2- (p
- methoxyphenyl) -4- methylspiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^{3, 7]} decane) (3) N-cyano-6, 7-dihydro-4-methyl-2
-Phenylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.
1 ^3,7] decane) (4) N-cyano-6,7-dihydro-4- Mechirurusupiro (5,6-benzo [b] flange carboximidoyl -7,2- tricyclo [3.3.1.1 ^{3 , 7]} decane) (5) N-cyano-4-cyclopropyl-6,7-dihydro-spiro (5,6-benzo [b] flange carboximidoyl -7,2- tricyclo [3.3.1.1 ^{3 , 7} ] decane) (6) N-cyano-6,7-dihydro-4-methylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.1 ^{3, 7} ] decane) (7) N-cyano-4-cyclopropyl-6,7-dihydrospiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.
1 ^3,7 ] decane) The component (E) in the present invention is a spirooxazine compound. As the spirooxazine compound, a known compound having a spirooxazine skeleton and having photochromic properties can be used without any limitation. For example, the following general formula (5)
The spirooxazine compound represented by is preferably used.

[0058]

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[Wherein R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different alkyl groups, cycloalkyl groups, alkyleneoxyalkyl groups, alkoxycarbonyl groups, alkoxycarbonylalkyl groups, aryl groups, aralkyl groups, alkylenethioalkyl groups. , R ¹⁷ and R ¹⁸ may together form a ring, and R ¹⁶ , R ¹⁷ and R ¹⁸ may each have a substituent,

[0060]

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The group represented by is a divalent aromatic hydrocarbon group which may be substituted, or a divalent unsaturated heterocyclic group,

[0062]

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The groups represented by are divalent aromatic hydrocarbon groups which may be substituted or divalent unsaturated heterocyclic groups. In the general formula (5), as the alkyl group and aryl group represented by R ¹⁶ , R ¹⁷ and R ¹⁸ , the alkyl group and aryl group described in the section of the general formula (3) are adopted. Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclobutyl group and cyclohexyl group, and the alkyleneoxyalkyl group includes methyleneoxymethyl group, methyleneoxyethyl group, ethyleneoxymethyl group and the like. An alkyleneoxyalkyl group having 2 to 10 carbon atoms can be mentioned, an alkoxycarbonyl group can be an alkoxycarbonyl group having 2 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group, and an alkoxycarbonylalkyl group can be Examples thereof include alkoxycarbonylalkyl groups having 3 to 15 carbon atoms such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group and methoxycarbonylethyl group. The aralkyl group includes phenylmethyl group, phenylethyl group, naphthylmethyl group and the like. Examples thereof include an aralkyl group having 7 to 20 carbon atoms, and examples of the alkylenethioalkyl group include alkylenethioalkyl groups having 2 to 10 carbon atoms such as a methylenethiomethyl group, a methylenethioethyl group and an ethylenethiomethyl group. Examples of the acyl group include an acetyl group, an ethylcarbonyl group and other acyl groups having 2 to 10 carbon atoms,
The alkylcarbonyloxy group may have 2 to 10 carbon atoms such as methylcarbonyloxy group and ethylcarbonyloxy group. Examples of such a substituent include a halogen atom, a nitro group, a cyano group, or a heterocyclic group, in addition to the above groups.

In the above general formula (5),

[0065]

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The optionally substituted divalent aromatic hydrocarbon group or divalent unsaturated heterocyclic group is the same as the group in the above general formula (3).

In the above general formula (5),

[0068]

[Chemical 21]

The optionally substituted divalent aromatic hydrocarbon group or divalent unsaturated heterocyclic group is the same as the group in the above general formula (3).

As such a substituent, the same groups as those mentioned above for R ¹⁶ , R ¹⁷ and R ¹⁸ can be selected.

[0071]

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(Provided that R ¹⁹ and R ²⁰ are an optionally substituted alkyl group, an alkoxy group or an aryl group, and R ¹⁹ and R ²⁰ are bonded to each other and cyclized to form a nitrogen-containing heterocycle. .) Are preferred substituents.

Among the spirooxazine compounds represented by the above general formula (5), R ¹⁶ is an alkyl group or an alkoxycarbonylalkyl group, and R ¹⁷ and R ¹⁸ are cycloalkyl groups which together form a ring. ,

[0074]

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Is preferably an aromatic hydrocarbon group which may be partially or wholly substituted, and is an aromatic hydrocarbon group partially or wholly substituted with a halogen atom, especially fluorine. Preferably,

[0076]

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Is preferably an optionally substituted aromatic hydrocarbon group, particularly a naphthalene ring substituted with an amino group.

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

Spirooxazine compound; (1) 1 ', 5'-dimethyl-6'-fluoro-6 "-
Morpholinodispiro (cyclohexane-1,3 '-(3
H) indole-2 '-(2H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine (2) 6'-fluoro-1'-methoxycarbonylethyl-8" -methoxy -6 "-piperidinodisspiro (cyclohexane-1,3 '-(3H) indole-2'-
(2H), 3 "-(3H) naphtho (3,2-a) (1,
4) Oxazine (3) 1 '-(2- (dioxan-2-yl) ethyl)
-6′-Fluoro-6 ″-(4-methylpiperazino) disspiro (cyclohexane-1,3 ′-(3H) indole-2 ′-(2H), 3 ″-(3H) naphtho (3,2
-A) (1,4) Oxazine (4) 5 ', 7'-difluoro-1'-methyl-6 "-
Morpholinodispiro (cyclohexane-1,3 '-(3
H) indole-2 '-(2H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine (5) 1'-isobutyl-5'-methyl-6'-fluoro-6 "-Morpholinodispiro (cyclohexane-1,
3 '-(3H) indole-2'-(2H), 3 "-
(3H) Naphtho (3,2-a) (1,4) oxazine In the present invention, the blending amount of the chromene compound is 0.01 to 0.2 with respect to 100 parts by weight of the total of (A) and (B). It is preferably 0.04 to 0.2 parts by weight, more preferably 0.04 to 0.2 parts by weight. If it is less than 0.01 part by weight, the color density of the photochromic curable composition of the present invention upon irradiation with light will be low, resulting in 0.2
If the amount is more than parts by weight, the use amount of the fulgimide compound and the spirooxazine compound is increased to obtain a neutral color, and the effects as described below are increased. The blending amount of the fulgimide compound is 0.04 to 0.1 part by weight, and further 0.05 to 0.08.
It is preferably in parts by weight. If it is less than 0.04 part by weight, the color density of the photochromic curable composition of the present invention upon irradiation with light will be low, and if it exceeds 0.1 part by weight, it will be colored yellow before light irradiation. The amount of the spirooxazine compound added is preferably 0.03 to 0.1 part by weight, more preferably 0.04 to 0.06 part by weight. When it is less than 0.03 part by weight, the durability of the photochromic curable composition of the present invention is lowered, and when it exceeds 0.1 part by weight, it is colored blue due to the effect of the initial coloration of the compound itself. The desired color tone can be obtained by optionally mixing the chromene compound, the fulgimide compound and the spirooxazine compound within the above range, but in the present invention, the weight ratio of the spirooxazine compound to the fulgimide compound should be kept below 2.0. Is mandatory. The ratio is 2.0
When it is above, the photochromic curable composition has a large color shift when deteriorated.

The method for mixing the photochromic curable composition of the present invention is not particularly limited, and the components A, B, C, D and E may be mixed in any order and dissolved.

The polymerization method for obtaining a polymer from the photochromic curable composition of the present invention is not particularly limited, and a known radical polymerization method can be adopted. The polymerization can be carried out by using a radical polymerization initiator such as various peroxides or azo compounds, irradiation with ultraviolet rays, α rays, β rays, γ rays or the like, or a combination thereof. To exemplify a typical polymerization method, the photochromic curable composition of the present invention containing a radical polymerization initiator in advance is injected between molds held by an elastomer gasket or a spacer and polymerized in a heating furnace. rear,
Detachable cast polymerization can be employed.

The radical polymerization initiator is not particularly limited and known ones can be used. Typical examples thereof include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, Diallyl peroxide such as acetyl peroxide; t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate, t-butylperoxyiso Peroxyesters such as butyrate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate; percarbonates such as diisopropylperoxycarbonate and di-sec-butylperoxydicarbonate;
Examples thereof include azo compounds such as azobisisobutyronitrile. Among these, t-butyl peroxyneodecanate, t-butylperoxyneodecanate / t-
A combination of butylperoxyisobutyrate and t-butylperoxyneodecanate / 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate is preferred in terms of polymerization efficiency and polymer hardness.

The photochromic curable composition of the present invention can be used in a wide range of fields. For example, various recording memory materials, copying materials, printing photoconductors, cathode ray tube recording materials, laser photosensitizers that replace silver salt photosensitive materials can be used. It can be used as various recording materials such as materials. In addition, the photochromic curable composition of the present invention can also be used as materials for photochromic lens materials, optical filter materials, display materials, photometers, decorations and the like.

[0084]

EFFECTS OF THE INVENTION The photochromic curable composition of the present invention has a reduced color shift when the cured product is deteriorated. In particular, when used as a photochromic lens, the combination of each photochromic compound enables color development of various intermediate tones, and the color tone does not change even after long-term use.

[0085]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. “Parts” in the examples is “parts by weight”.

Radical polymerizable monomer 3PG: tripropylene glycol dimethacrylate (trade name: NK ester 3PG, Shin Nakamura Chemical Co., Ltd.)
3G: triethylene glycol dimethacrylate (trade name: NK ester 3G, Shin Nakamura Chemical Co., Ltd.) 4G: tetraethylene glycol dimethacrylate (trade name: NK ester 4G, Shin Nakamura Chemical Co., Ltd.) ) BPE-100N: 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (trade name: NK ester BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.) MS: α-methylstyrene MSD: α-methylstyrene Dimer HEMA: 2-hydroxyethylmethacrylate BzMA: benzylmethacrylate Polymerizable monomer having at least one epoxy group in one molecule GMA: Glycidylmethacrylate Radical polymerization initiator Perbutyl ND: t-butylperoxyneodecanate (commodity) Name: Perbutyl ND, Nippon Oil Fats Co., Ltd.) Perocta O: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate (trade name: Perocta O, NOF Corporation) Chromene compound: (1) Spiro (norbornane-2,2 ′-(2H) benzo (h) chromene) (2) Spiro (bicyclo [3.3.1] nonane-9,
2 ′-(2H) benzo (h) chromene) (3) 7′-methoxyspiro (bicyclo (3.3.1)
Nonane-9,2 ′-(2H) benzo (h) chromene) (4) 7′-methoxyspiro (norbornane-2,2 ′)
-(2H) benzo (h) chromene) (5) 2,2-dimethyl-7-octoxy (2H) benzo (f) chromene (6) 2,2- (2'-difuryl) (2H) benzo (f) Chromene (7) 2,2- (phenyl-2'-furyl) (2H) benzo (f) chromene (8) 9-morpholino-2,2-diphenyl (2H) benzo (f) chromene Flugimide compound (1) N -Cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.
3.1.1 ^3,7 ] decane) (2) N-cyanomethyl-6,7-dihydro-2- (p
- methoxyphenyl) -4- methylspiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^{3, 7]} decane) (3) N-cyano-6, 7-dihydro-4-methyl-2
-Phenylspiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.
1 ^3,7] decane) (4) N-cyano-6,7-dihydro-4- Mechirurusupiro (5,6-benzo [b] flange carboximidoyl -7,2- tricyclo [3.3.1.1 ^{3 , 7} ] decane) (5) N-cyano-4-cyclopropyl-6,7-dihydrospiro (5,6-benzo [b] furandcarboximido-7,2-tricyclo [3.3.1.1]
^3,7] decane) (6) N-cyano-6,7-dihydro-4-methylspiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^{3 ,
7} ] decane) (7) N-cyano-4-cyclopropyl-6,7-dihydrospiro (5,6-benzo [b] thiophenedicarboximide-7,2-tricyclo [3.3.1.
1 ^3,7 ] decane) Spirooxazine compound; (1) 1 ′, 5′-dimethyl-6′-fluoro-6 ″-
Morpholinodispiro (cyclohexane-1,3 '-(3
H) indole-2 '-(2H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine (2) 6'-fluoro-1'-methoxycarbonylethyl-8" -methoxy -6 "-piperidinodisspiro (cyclohexane-1,3 '-(3H) indole-2'-
(2H), 3 "-(3H) naphtho (3,2-a) (1,
4) Oxazine (3) 1 '-(2- (dioxan-2-yl) ethyl)
-6′-Fluoro-6 ″-(4-methylpiperazino) disspiro (cyclohexane-1,3 ′-(3H) indole-2 ′-(2H), 3 ″-(3H) naphtho (3,2
-A) (1,4) Oxazine (4) 5 ', 7'-difluoro-1'-methyl-6 "-
Morpholinodispiro (cyclohexane-1,3 '-(3
H) indole-2 '-(2H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine (5) 1'-isobutyl-5'-methyl-6'-fluoro-6 "-Morpholinodispiro (cyclohexane-1,
3 '-(3H) indole-2'-(2H),
3 ″-(3H) naphtho (3,2-a) (1,4) oxazine Example 1 0.045 part of chromene compound (2), 0.084 part of fulgimide compound (2), spirooxazine compound (1)
0.054 parts, 4G 70 parts, 3G 15 parts, GMA
10 parts of HEMA, 5 parts of HEMA, and 1 part by weight of perbutyl ND as a polymerization catalyst were added, and they were sufficiently mixed until completely dissolved. This mixed solution was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and heated in an air oven at 35 ° C to 90 ° C for 20 hours for polymerization. After the polymerization was completed, the polymer was removed from the mold glass mold and post-cured at 100 ° C. for 2 hours.

The obtained photochromic cured product was subjected to the following acceleration experiment to compare and evaluate the color tone before and after deterioration.

The following tests were conducted as a method of promoting deterioration.
The obtained photochromic cured product was irradiated with sunlight for 30 minutes to develop a color, and then subjected to a cycle of fading under a fluorescent lamp for 1 hour three times a day, for a total of 30 days.

As a method of evaluating the photochromic property before and after deterioration, the above photochromic cured product was prepared by using a xenon lamp L-2480 (300W) SHL manufactured by Hamamatsu Photonics.
-100 through an aeromass filter (manufactured by Corning) at 20 ± 1 ° C., beam intensity on the surface of the photochromic cured product 365 nm = 2.4 nW / cm2,254 nm
= 24 μW / cm 2 for 120 seconds for color development, and the color development spectra of the initial (T ₀ ) and after 30 days of the accelerated experiment (T ₃₀ ) were measured. In each color development spectrum of T ₀ and T ₃₀ , the absorbance at the maximum absorption wavelength at 450 to 470 nm and the absorbance at the maximum absorption wavelength at 580 to 590 nm were obtained, respectively. The absorbance at the maximum absorption wavelength of 450 to 470 nm indicates the yellow color density, and the absorbance at the maximum absorption wavelength of 580 to 590 nm indicates the blue color density. Therefore, the durability of yellow and the durability of blue are expressed as follows.

Durability (%) of yellow = Yellow color density at T ₀ / Yellow color density at T ₃₀ × 100 Blue durability (%) = Blue color density at T ₀ / T ₃₀ Blue color density x 100 The difference in color tone (color shift) before and after deterioration is expressed by the following formula. The results are shown in Table 1.

Color shift (%) = durability of yellow (%)-durability of blue (%) Further, the photochromic cured products of T ₀ and T ₃₀ are colored by sunlight, and the color tone at that time is visually observed. Evaluated. The results are shown in Table 1.

Examples 2 to 7 The procedure of Example 1 was repeated, except that the chromene compound, the fulgimide compound and the spirooxazine compound were replaced by the compositions shown in Table 1. The results are shown in Table 1.

Example 8 In Example 1, 0.05 part of the chromene compound (2), 0.06 part of the fulgimide compound (1), 0.02 part of the fulgimide compound (3) and the spirooxazine compound (1).
0.06 parts, 4G 60 parts, 3G 15 parts, GMA 1
Example 1 was repeated except that 0 part, 5 parts of HEMA, 9 parts of MS, and 1 part of MSD were used. The results are shown in Table 1.

Examples 9 to 15 Example 9 was repeated except that the chromene compound, the fulgimide compound and the spirooxazine compound were replaced by the compositions shown in Table 1. The results are shown in Table 1.

Comparative Examples 1 to 3 For comparison, chromene compounds, fulgimide compounds and spirooxazine compounds were used in combination as shown in Table 1. The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

In Comparative Example 1, the weight ratio of the fulgimide compound / spirooxazine compound was 2.5 and the numerical value of the color shift was 3.
0%, the color tone when deteriorated is yellow. On the other hand, in Example 5, the weight ratio of the fulgimide compound / spirooxazine compound is 1.33, the numerical value of the color shift is 11, and the color tone upon deterioration is kog tea, which is an improvement over Comparative Example 1. .

[0097]

[Table 1]

Example 16 0.05 part of chromene compound (2), 0.05 part of fulgimide compound (2) and spirooxazine compound (1)
0.055 parts, BPE-100N 70 parts, BzMA
20 parts, GMA 9 parts, MSD 1 part It carried out like Example 1 except having replaced perbutyl ND / per octa O 0.5 / 0.4 weight part as a polymerization catalyst. The results are shown in Table 2.

Examples 17 to 24 The same procedure as in Example 16 was repeated, except that the chromene compound, the fulgimide compound and the spirooxazine compound in Example 16 were replaced by the compositions shown in Table 2. The results are shown in Table 2.

Comparative Examples 4 to 6 For comparison, chromene compounds, fulgimide compounds and spirooxazine compounds were used in combination as shown in Table 2. The evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

In Comparative Example 6, the weight ratio of the fulgimide compound / spirooxazine compound was 4.0 and the numerical value of the color shift was 3.
5%, the color tone when deteriorated is yellow. On the other hand, in Example 23, the weight ratio of the fulgimide compound / spirooxazine compound was 1.33, the numerical value of the color shift was 11, and the color tone upon deterioration was brown, which is an improvement over Comparative Example 1.

[0102]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08K 5/34 C08K 5/34 C08L 33/14 LHX C08L 33/14 LHX G03C 1/00 531 G03C 1 / 00 531

Claims (3)

[Claims] 1. A radical polymerizable monomer (A) 100 parts by weight, (B) 1 to 30 parts by weight of a polymerizable monomer having at least one epoxy group in one molecule, and (C) a chromene compound. 0.01 to 0.2 parts by weight based on 100 parts by weight of the total of (A) and (B), and 0.04 to about 4 parts by weight of the fulgimide compound (D) based on 100 parts by weight of the total of (A) and (B).
0.1 parts by weight and (E) the spirooxazine compound in an amount of 0.03 to 100 parts by weight of the total of (A) and (B).
A photochromic curable composition comprising 0.1 part by weight and having a weight ratio of (D) to (E) of less than 2.0. 2. The photochromic curable composition according to claim 1, wherein the radically polymerizable monomer (A) comprises a polyalkylene glycol di (meth) acrylate monomer and α-methylstyrene dimer. . 3. The radically polymerizable monomer (A) is a polyalkylene glycol di (meth) acrylate monomer, α
-The photochromic curable composition according to claim 1, comprising a methylstyrene dimer and a monofunctional radically polymerizable monomer.