JPH11209749A - Photochromic curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of providing a photochromic material having solved the problems of initial coloring and reduction in durability of photochromism, by including a specific monomer, a prescribed chromene compound, a specified compound, or the like. SOLUTION: This composition comprises (A) a polyfunctional (meth)acrylate monomer (e.g. triethylene glycol dimethacrylate), (B) a chromene compound of the formula [R' is a substituted amino or an alkoxy; R<2> and R<3> are each a (non)substituted alkyl, a (non)substituted aryl, a (non)substituted aromatic heterocyclic group or R<2> and R<3> are mutually bonded to form a ring; any carbon atom at the 5, and 7-10 positions of the benzochromene ring may contain a substituent group] e.g. 3,3-bis(3-fluoro-4-methoxyphenyl)-6-morpholino-3H- benzo[f]chromene}, (C) a compound containing one or more epoxy groups in one molecule (e.g. glycidyl methacrylate) and (D) a polymerization initiator.

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 which gives a cured product having excellent photochromic action.

[0002]

2. Description of the Related Art Photochromism is a phenomenon that has attracted attention for several years. When a compound is irradiated with light such as sunlight or light from a mercury lamp, the color changes rapidly, and the irradiation of light is stopped. It is a reversible action that returns to the original color when placed in a dark place. Compounds having such properties are called photochromic compounds, and compounds having various structures have been synthesized in the past. However, these photochromic compounds are resistant to photochromism when the above-described reversible changes are repeatedly performed. Many have problems with gender.

Therefore, spirooxazine-based photochromic compounds (hereinafter simply referred to as oxazine compounds), fulgimide-based photochromic compounds (hereinafter simply referred to as fulgimide compounds), and chromene-based photochromic compounds (hereinafter referred to simply as fulgimide compounds) are mentioned as the photochromic compounds having improved photochromic durability. Hereinafter, these are simply referred to as chromene compounds) and the like (US Pat. No. 4,882,43).
8, USP 4,960,678, USP 5,130,0
58, JP-A-62-288830, US Pat.
6,998, JP-A-2-28154, JP-A-3-11
074, JP-A-3-133988).

[0004] These photochromic compounds exhibit excellent photochromic durability. In particular, the above-mentioned chromene compound is generally hardly deteriorated by light, and when continuously irradiated with sunlight or light similar to sunlight, the color-forming performance of the compound is small and the photochromic durability is excellent.

However, in a case where a photochromic material such as a photochromic spectacle lens is to be obtained by mixing and polymerizing the above chromene compound with a polymerizable monomer (monomer), the photochromic compound itself has a particular problem. Despite not being seen, there was a case where a problem occurred in the obtained photochromic material. That is, according to the study of the present inventors, a polyfunctional (meth) acrylate monomer widely used as a monomer for providing a photochromic material such as an eyeglass lens has a substituted amino group or an alkoxy group at the 6-position as a photochromic compound. When a specific 3H-benzo [f] chromene compound having the following formula is used, there is a problem that a photochromic material having good photochromism durability cannot be obtained, and the photochromic material itself is colored without being irradiated with light. (Hereinafter, also referred to as "initial coloring"). This problem of initial coloring is an important problem for photochromic materials such as eyeglass lenses that strongly reflect the tastes of end users, and a photochromic material without initial coloring is required.

As a method for improving the photochromic durability of a photochromic material containing a chromene compound,
WO 96/37576 describes a method of adding a hindered amino ether-based light stabilizer to a thermoplastic resin such as polyvinyl chloride or polycarbonate containing a benzochromene compound. However, when the above-mentioned specific chromene compound was added to a commercially available polyfunctional (meth) acrylate together with the above-mentioned hindered amino ether-based light stabilizer and polymerized and cured, the effect of improving photochromism durability was found. It was not sufficient, and the occurrence of the initial coloring could not be suppressed.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a compound of the above invention comprising a polyfunctional (meth) acrylate monomer and the above-mentioned 6-substituted amino or 6-alkoxy-3H-benzo [f] chromene compound. It is an object of the present invention to solve the problem of initial coloring and the problem of reduced photochromic durability, which are peculiar to a photochromic material obtained by curing a photochromic curable composition.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that polyfunctional (meth)
A photochromic curable composition obtained by adding an epoxy compound to a photochromic curable composition comprising an acrylate monomer and a 3H-benzo [f] chromene compound having a substituted amino group or an alkoxy group at the 6-position is cured. The inventors have found that the photochromic material has little initial coloring and high photochromism durability, and has completed the present invention.

That is, the present invention provides a polyfunctional (meth) acrylate monomer represented by the following general formula (1):

[0010]

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(Wherein R ¹ is a substituted amino group or an alkoxy group, and R ² and R ³ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted An aromatic heterocyclic group,
R ² and R ³ may be linked to each other to form a ring, and the carbon at any of the 5-, 7, 8-, 9-, or 10-positions of the naphthopyran ring may have a substituent. Good. ), A compound having at least one epoxy group in a molecule (hereinafter, also simply referred to as an epoxy compound), and a photochromic curable composition comprising a polymerization initiator. is there.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The photochromic curable composition of the present invention comprises a chromene compound represented by the above general formula (1), a polyfunctional (meth) acrylate monomer, and at least one epoxy group in the molecule. And a polymerization initiator.

First, the polyfunctional (meth) acrylate monomer which is the first component of the photochromic curable composition of the present invention will be described.

The polyfunctional (meth) acrylate monomer used in the present invention is not particularly limited as long as it is a (meth) acrylate monomer having two or more polymerizable groups such as (meth) acryloyl groups in the molecule. Instead, a known polyfunctional (meth) acrylate monomer generally used as a monomer for spectacle lenses can be used.

Representative examples of polyfunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) Acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2′-bis (4-methacryloyl) Acrylic or methacrylic acid ester compounds of oxyethoxyphenyl) propane, 2,2′-bis (4
-Methacryloyloxy-polyethoxyphenyl) propane acrylic or methacrylic acid ester compounds,
Acrylic acid or methacrylic acid ester compound of 2,2′-bis (4-methacryloyloxypropoxyphenyl) propane, acrylic acid or methacrylic acid ester compound of 2,2′-bis (4-methacryloyloxy-polypropoxyphenyl) propane, Acrylic acid or methacrylic acid ester compound of 2,2′-bis [(3,5-dibromo-4-methacryloyloxyethoxy) propane, acrylic acid or methacrylic acid ester compound of hydrogenated bisphenol A ethylene oxide or propylene oxide adduct, Dimethylol tricyclodecane di (meth) acrylate, dimethylol tricyclodecane polyethoxydi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acyl Rate, ethylene glycol or polyethylene glycol with glycidyl (meth)
Reaction product of acrylate, reaction product of propylene glycol or polypropylene glycol and glycidyl (meth) acrylate, reaction product of bisphenol A ethylene oxide or propylene oxide adduct and glycidyl (meth) acrylate, hydrogenated bisphenol A ethylene oxide or propylene A reaction product of an oxide adduct and glycidyl (meth) acrylate is exemplified.

These polyfunctional (meth) acrylate monomers may be used alone or in combination of two or more.
Alternatively, the polymer may be partially polymerized in advance and used in the form of an oligomer.

In the photochromic curable composition of the present invention, in order to improve the mechanical properties of the photochromic material obtained by curing the curable composition, the photochromic curable composition may be used as a copolymerizable monomer in the above-mentioned polyfunctional (meth) acrylate. In addition, other known monomers can be blended as needed. Examples of suitably used copolymer monomers include:
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth)
Acrylate, benzyl (meth) acrylate, (meth)
Phenyl acrylate, tribromophenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate,
Monofunctional (meth) acrylates such as alkoxy polypropylene glycol (meth) acrylate, aromatic vinyl compounds such as styrene, chlorostyrene, α-methylstyrene, α-methylstyrene dimer, vinylnaphthalene, isopropenylnaphthalene, bromostyrene, divinylbenzene And the like. These copolymerized monomers can be used alone or as a mixture of two or more kinds, and the compounding amount may be appropriately determined according to the intended use, but generally, all the monomers in the photochromic curable composition of the present invention are used. ｛Note: The polyfunctional (meth) acrylate monomer and the copolymerized monomer. When a polymerizable compound described later is used as the epoxy compound, the epoxy compound is also included. Hereinafter, it is simply referred to as “all monomers”. It is usually 0.5 to 80 parts by weight based on 100 parts by weight. When the amount of the copolymerized monomer is in the range of 0.5 to 30 parts by weight based on 100 parts by weight of all the monomers, the heat resistance of the obtained photochromic material is increased, which is particularly preferable.

Next, the chromene compound which is the second component of the photochromic curable composition of the present invention will be described.

The chromene compound used in the present invention is represented by the above general formula (1) and is characterized by having a substituted amino group or an alkoxy group at the 6-position of the benzochromene ring. When the chromene compound is polymerized and cured by mixing with the above-mentioned polyfunctional (meth) acrylate monomer without adding a compound having an epoxy group in the molecule, the problem such as initial coloring occurs.

In the general formula (1), R ¹ is a substituted amino group or an alkoxy group. The substituted amino group is
For example, the following equation (2)

[0021]

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(Wherein R ⁴ and R ⁵ may be different hydrogen atoms, substituted or unsubstituted carbon atoms having 1 to 1 carbon atoms)
0 alkyl group, substituted or unsubstituted carbon number of 6 to 10
Is an aryl group or a heterocycle. ) Or the following formula (3)

[0023]

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(Wherein the ring may have a hetero atom, and the ring may be further condensed with a hetero ring and / or an aromatic ring). Can be exemplified.

As the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, the substituted or unsubstituted aryl group having 6 to 10 carbon atoms or the heterocyclic ring represented by R ⁴ and R ^{5 in} the above formula (2), The group can be used without any limitation,
Preferred are alkyl groups 4 to 4, phenyl group, naphthyl group and the like. Specific examples of the substituted amino group represented by the formula (2) include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group,
Examples thereof include a methylethylamino group, a 2-hydroxyethylamino group, a di (2-hydroxyethyl) amino group, a di (cyanomethyl) amino group, a diphenylamino group, and an aziridinyl group.

In the cyclic amino group represented by the above formula (3), the number of carbon atoms constituting the cyclic amino group is not particularly limited, but is 2 to 10, preferably 3 to 6. The hetero atom that may be present in the ring of the cyclic amino group is not particularly limited, but is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. The hetero ring and the aromatic ring which may be condensed to the ring are not particularly limited, but are preferably a hetero ring or an aromatic ring having 4 to 10 carbon atoms. Examples of the hetero ring and the aromatic ring include a benzene ring, a naphthalene ring,
(Tetrahydro) thiophene ring, (tetrahydro) furan ring and the like.

Specific examples of the cyclic amino group represented by the above formula (3) include a piperidino group, a 2,2,6,6-tetramethylpiperidino group, a morpholino group, a 2,6-dimethylmorpholino group, Examples thereof include a pyrrolidinyl group, an N-methylpiperazinyl group, a thiomorpholino group, an indolinyl group, a methylindolinyl group, and a tetrahydroquinolinyl group.

The alkoxy group represented by R ¹ in the general formula (1) is, for example, the following formula (4)

[0029]

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Wherein R ⁶ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms or a heterocyclic ring. Examples can be given.

As the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, the substituted or unsubstituted aryl group having 6 to 10 carbon atoms or the heterocyclic ring represented by R ^{6 in} the above formula (4), any known groups can be used. Although used without limitation, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, and the like are preferable. Specific examples of the alkoxy group represented by the above formula (4) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a t-butoxy group,
Phenoxy group, naphthoxy group and the like can be mentioned.

In the general formula (1), R ² and R ³ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aromatic heterocyclic group; R ² and R ³ may be linked together to form a ring. In the case of forming the R ² and R ³ are bonded to each other ring in order to form a bond for linking, R ² and R ³ consists of one each of the foregoing groups are hydrogen from both groups A structure in which atoms or substituents are eliminated is obtained.

As the above-mentioned alkyl group, a known group can be used without any limitation, but is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, t
-Butyl group, cyclohexyl group and the like.

As the above-mentioned aryl group, a known group is used without any limitation, but an aryl group having 6 to 10 carbon atoms is preferable. Specific examples of the aryl group include:
Examples include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

As the above-mentioned aromatic heterocyclic group, a known group is used without any limitation, but an aromatic heterocyclic group having 2 to 9 carbon atoms is preferable. Specific examples of the aromatic heterocyclic group include a furyl group, a benzofuranyl group, a thienyl group,
Examples include a benzothienyl group, an N-methylpyrrolyl group, an indolyl group, a pyridinyl group, a quinolyl group, and an isoquinolyl group.

Further, as the ring formed by R ² and R ³ linked together, in addition to the above-mentioned linked alkyl group, aryl group or aromatic heterocyclic group, a norbornylidene group, bicyclo [3. 3.1] 9-nonylidene group, adamantylidene group and the like.

An alkyl group represented by R ² and R ³ above,
The aryl group and the aromatic heterocyclic group may have a substituent. Examples of suitable substituents include an alkyl group, an alkoxy group, an aralkyl group, an acyl group, an alkoxycarbonyl group, a substituted amino group, an aryl group, an acyloxy group, a nitro group, a hydroxy group, a cyano group, and a halogen atom. Can be.

The alkoxy group and the substituted amino group as the above substituents include the same groups as those described above for R ¹ .

The alkyl group as the above substituent is not particularly limited, but generally has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
To 4 alkyl groups. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a t-butyl group.

The aralkyl group as the above substituent is not particularly limited, but is generally an aralkyl group having 7 to 16, preferably 7 to 10 carbon atoms. Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, and a phenylbutyl group.

The acyl group as the substituent is not particularly limited, but is generally 1 to 15 carbon atoms, preferably 1 to 7 carbon atoms.
Is an acyl group. Specific examples of the acyl group include:
Examples include a formyl group, an acetyl group, a propionyl group, a butyryl group, and a benzoyl group.

The alkoxycarbonyl group as the above substituent is not particularly limited, but generally has 1 to 10 carbon atoms.
Preferably they are 1 to 7 alkoxycarbonyl groups. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group and a butoxycarbonyl group.

The aryl group as the above substituent is not particularly limited, but is generally an aryl group having 6 to 15, preferably 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group.

The acyloxy group as the above substituent is not particularly limited, but is generally an acyloxy group having 2 to 15, preferably 2 to 6 carbon atoms. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, a benzoyloxy group, and a (meth) acryloyloxy group.

The halogen atom as the substituent is not particularly limited, but specific examples of the halogen atom preferably used in the present invention include a fluorine atom, a chlorine atom and a bromine atom.

The 5 of the naphthopyran ring in the general formula (1)
Any of the carbons at the 7th, 8th, 9th and 10th positions may have a substituent. Examples of suitable substituents include an alkyl group, an alkoxy group, an aralkyl group, an acyl group, an alkoxycarbonyl group, a substituted amino group, an aryl group, an acyloxy group, a nitro group, a hydroxy group, a cyano group, and a halogen atom. Can be. As these substituents, those exemplified as the substituents of the alkyl group, aryl group and aromatic heterocyclic group represented by R ² and R ³ can be employed as they are.

In the present invention, the following compounds can be exemplified as specific examples of chromene compounds that can be suitably used.

1) 3,3-bis (3-fluoro-4-methoxyphenyl) -6-morpholino-3H-benzo [f] chromene 2) 3,3-bis (4-methoxyphenyl) -6-morpholino- 3H-benzo [f] chromene 3) 3- (3-trifluoromethyl-4-methoxyphenyl) -3- (4-methoxyphenyl) -6-piperidino-3H-benzo [f] chromene 4) 3- (2 -Thienyl-4-methoxyphenyl) -6
-Thiomorpholino-3H-benzo [f] chromene 5) 3,3-bis (4-methoxyphenyl) -6-N-
Methylpiperazino-3H-benzo [f] chromene 6) 3- (2-furyl) -3-methyl-6-morpholino-3H-benzo [f] chromene 7) 3- (2-naphthyl) -3-methyl-6 Morpholino-3H-benzo [f] chromene 8) 3,3-bis (4-methoxyphenyl) -6,8-
Dimethoxy-3H-benzo [f] chromene 9) 6-morpholinospiro [fluorene-9,3'-3
H-benzo [f] chromene] 10) 6-dimethylaminospiro [bicyclo [3.3.
1] Nonane-9,3'-3H-benzo [f] chromene] The blending amount of the chromene compound represented by the general formula (1) in the photochromic curable composition of the present invention is not particularly limited, and depends on the use. Can be determined appropriately. The photochromic curable composition of the present invention is often used for optical lenses such as eyeglass lenses, and the amount of the chromene compound used in such applications is generally 0.001 to 100 parts by weight based on 100 parts by weight of all monomers. The amount is 10 parts by weight. In general, the color density of a cured product obtained by curing the photochromic curable composition of the present invention is proportional to the blending amount of the chromene compound to a certain extent. Not only that, photochromism durability may be impaired. From the viewpoint of the cost performance with respect to the color density and the effect of the present invention, the amount of the chromene compound is 0.01 to 5 parts by weight based on 100 parts by weight of all the monomers.
More preferably, it is in the range of 0.01 to 1 part by weight.

Next, the epoxy compound as the third component of the photochromic curable composition of the present invention will be described.

As the epoxy compound used in the present invention, known compounds can be used without any limitation as long as they have at least one epoxy group in the molecule. For example, a reaction product of an alcoholic hydroxyl group-containing compound such as a monohydric, dihydric or trihydric alcohol or a phenolic hydroxyl group-containing compound such as phenol and hydroquinone with epichlorohydrin; a carboxylic acid such as benzoic acid and terephthalic acid and epichlorohydrin Reaction products with hydrin; and the like.

However, in the present invention, it is preferable to use an epoxy compound having at least one unsaturated double bond group in the molecule for the following reasons. That is, when an epoxy compound having at least one unsaturated double bond group in a molecule is used, when the photochromic curable composition of the present invention is polymerized and cured, the epoxy compound becomes a polyfunctional (meth) compound. This is because the copolymer is copolymerized with another monomer such as an acrylate monomer and fixed to the polymer matrix, so that the physical properties of the obtained cured product are not impaired.

Examples of the unsaturated double bond group contained in the epoxy compound include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, and the like. In order to obtain good photochromic properties, an acryloyl group is used. Or a methacryloyl group is preferred.

Among the epoxy compounds that can be used in the present invention,
Examples of epoxy compounds having no unsaturated double bond group in the molecule include ethylene glycol glycidyl ether,
Propylene glycol glycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether,
Butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A
Or propylene oxide adduct of hydrogenated bisphenol A, terephthalic acid diglycidyl ester, spiroglycol diglycidyl ether, hydroquinone diglycidyl ether and the like can be mentioned.

Among the epoxy compounds, epoxy compounds having at least one unsaturated double bond in the molecule which can be particularly preferably used in the present invention are exemplified by glycidyl acrylate, glycidyl methacrylate, β-methyl Glycidyl acrylate, β-methyl glycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxybutyl methacrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3-
(Glycidyloxy-1-isopropyloxy) -2-
Examples thereof include methacrylate compounds and acrylate compounds such as hydroxypropyl acrylate and 3- (glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate.

The compounding amount of the epoxy compound in the photochromic curable composition of the present invention depends on the polyfunctional (meth) used.
What is necessary is just to determine suitably according to the kind and mixing ratio of an acrylate and a chromene compound, and the kind of an epoxy compound to be used. When a commercially available polyfunctional (meth) acrylate is used, the epoxy compound is used in an amount of at least 1 part by weight, preferably from 1 to 100 parts by weight of all monomers, regardless of the types of the chromene compound and the epoxy compound used.
When 20 parts by weight is used, the problem of initial coloring is suppressed, and the photochromic durability becomes practical. However, when an epoxy compound having no unsaturated double bond group is used, if the amount is too large, curing tends to be delayed. It is preferable that the amount be 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight.

Next, the polymerization initiator which is the fourth component of the photochromic polymerizable composition of the present invention will be described.
The polymerization initiator is a polymerization catalyst for polymerizing and curing the photochromic polymerizable composition of the present invention, and the polymerization is started by heating the composition or irradiating the composition with an active energy ray.

The polymerization initiator used in the present invention is not particularly limited as long as it functions as described above, and known polymerization initiators can be used. As a typical polymerization initiator that can be used in the present invention, examples of the thermal polymerization catalyst include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide;
Peroxyesters such as -butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate; diisopropylperoxydicarbonate, di-sec-butyl Percarbonates such as peroxydicarbonate; azo compounds such as azobisisobutyronitrile; and the like. Examples of the photopolymerization catalyst include 1-phenyl-2-hydroxy-2-methylpropan-1-one, Acetophenone-based compounds such as hydroxycyclohexylphenyl ketone and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one; α-diacids such as 1,2-diphenylethanedione and methylphenylglyoxylate Carbonyl compounds; 2,6-dimethyl Reuben benzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine acid methyl ester,
Acylphosphine oxide compounds such as 2,6-dichlorobenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine oxide can be mentioned. One of these polymerization catalysts,
Alternatively, two or more kinds may be used as a mixture. In addition, a thermal polymerization catalyst and a photopolymerization catalyst can be used in combination. When a photopolymerization initiator is used, a known polymerization accelerator such as a tertiary amine can be used in combination.

The amount of the polymerization initiator used depends on the polymerization conditions, the type of the initiator, and the composition of other components in the photochromic curable composition of the present invention, and cannot be limited unconditionally. The range is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the monomer.

In the photochromic curable composition of the present invention, various additives are added to enhance the performance of the photochromic material obtained by polymerizing and curing the composition in a range that does not impair the effects of the present invention. Can be blended. For example, the chromene compound used in the present invention generally mainly develops a yellowish color.However, in applications such as eyeglass lenses, intermediate color development such as gray or brown is preferred, and such a demand is satisfied. For this purpose, other photochromic compounds other than the oxazine compound and the fulgimide compound can be added. Examples of the above fulgimide compound and oxazine compound include USP
4,882,438, USP 4,960,678, USP 513
0058, US Pat. No. 4,913,544, EP 0600669
Known compounds described in, for example, can be used.

Specific examples of fulgide compounds and oxazine compounds which can be suitably used in the present invention include:
The following compounds can be mentioned.

Flugimide compound: 1) N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.
1.1] Decane) 2) N-cyanomethyl-6,7-dihydro-2- (p-
Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 3) N-cyanomethyl-6,7-dihydro-4 -Methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 4) 6,7-dihydro-N-methoxycarbonylmethyl-4-methyl- 2-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 5) 6,7-dihydro-4-methyl-2- (p -Methylphenyl) -N-nitromethylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 6) N-cyanomethyl- 6,7-dihydro-4-cyclopropyl-3-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 7) N-cyanomethyl- 6,7-dihydro-4-cyclopropyl-spiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.
1] Decane) Oxazine compound: 1) 1'-methoxycarbonylmethyl-8 "-methoxy-6"-(4-methylpiperazino) dispiro (cyclohexane-1,3 '-(3H) indole-2'-(1 '
H), 3 ''-(3H) naphtho (3,2-a) (1,4)
Oxazine) 2) 6'-fluoro-1 ', 5'-dimethyl-6''-morpholinodispiro(cyclohexane-1,3'-(3
H) Indole-2 '-(1'H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine) 3) 6'-Fluoro-5'-methyl-1'- Isobutyl-6 ″ -morpholinodispiro (cyclohexane-1,
3 '-(3H) indole-2'-(1'H), 3 ''-
(3H) naphtho (3,2-a) (1,4) oxazine) 4) 3 ′, 3′-dimethyl-1′-isopropyl-6 ″
-Indolinospiro- (3H) indole-2'-
(1′H), 3 ″-(3H) naphtho (3,2-a)
(1,4) oxazine 5) 3 ′, 3′-dimethyl-1′-isobutylspiro-
(3H) indole-2 '-(1'H), 3''-(3
H) Naphtho (3,2-a) (1,4) oxazine These oxazine compounds or fulgide compounds may be added alone or as a mixture of several different types. When the oxazine compound or the fulgide compound is added to the photochromic curable composition of the present invention, the addition amount is usually 0.0
The range is from 0.01 to 10 parts by weight, preferably from 0.01 to 1 part by weight.

The photochromic curable composition of the present invention is preferably used by mixing an ultraviolet stabilizer. By blending an ultraviolet stabilizer, the durability of the photochromic compound in the photochromic curable composition of the present invention or the polymerized cured product of the composition can be improved. In particular, when a fulgide compound is used in combination as a photochromic compound, the effect of improving the durability is large. For this reason, when the oxazine compound, the fulgide compound, and the chromene compound as described above are mixed and used so as to form an intermediate color, it is possible to satisfactorily prevent the temporal change of the intermediate color during color formation. it can.

At this time, the usable ultraviolet stabilizer includes:
A hindered amine light stabilizer, a hindered phenol light stabilizer, a sulfur-based antioxidant, and a phosphite compound can be preferably used. In particular, a hindered amine light stabilizer having a hindered amine structure in a molecule is preferable. .

The amount of the above-mentioned ultraviolet stabilizer is not particularly limited, but is usually 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight, based on 100 parts by weight of all monomers. It is preferred that there be.

Further, when an infrared absorber is mixed with the photochromic curable composition of the present invention, a photochromic cured product having an infrared absorbing ability in addition to the photochromic action can be obtained. As the infrared absorber, a polymethine compound, a diimonium compound, a cyanine compound, an anthraquinone compound, or an aluminum compound can be used, but a diimonium compound having a large molecular extinction coefficient and exhibiting an effect with a small amount of addition is preferable. . The general amount of the infrared absorber is 10
The amount is 0.0001 to 1 part by weight with respect to 0 part by weight, and a more preferable blending amount is 0.001 to 0.01 part by weight.

The photochromic curable composition of the present invention may contain, if necessary, a releasing agent, an ultraviolet absorber, an antioxidant, an anti-colorant, an antistatic agent in addition to the above-mentioned ultraviolet stabilizer and infrared absorber. And various additives such as fluorescent dyes, dyes, pigments, and fragrances.

Next, a method of polymerizing and curing the photochromic curable composition of the present invention to obtain the photochromic material of the present invention will be described.

The method for polymerizing and curing the photochromic polymerizable composition of the present invention is not particularly limited, and a known radical polymerization method can be employed. That is, the photochromic polymerizable composition is heated depending on the type of the polymerization initiator used, or the composition is irradiated with ultraviolet rays, α rays, β rays, active energy rays such as γ rays, or a combination thereof. be able to.

As a typical polymerization method, for example, the photochromic composition of the present invention, in which various additives are blended and mixed as necessary, is injected between a mold held by an elastomer gasket or a spacer. Depending on the type of initiator, that is, by irradiating with active energy rays when the polymerization initiator is a photopolymerization initiator, or with active energy rays when the polymerization initiator is a thermal radical polymerization initiator Cast polymerization in which the polymer is heated and polymerized and cured under non-irradiation. When the radical polymerization initiator is a mixture of a photopolymerization initiator and a thermal radical polymerization initiator, the active energy ray does not necessarily need to be irradiated during heating, and may be temporarily irradiated before heating. . After polymerization in a heating furnace, a cast polymerization to be removed can be employed.

In the casting polymerization using the above thermal polymerization initiator, the heating temperature condition affects the properties of the obtained cured product. This heating temperature condition is affected by the type and amount of the initiator and the type of the monomer, and thus cannot be unconditionally limited, but generally, the polymerization is started at a relatively low temperature, and the temperature is gradually increased. It is preferable to perform a so-called taper type two-stage polymerization in which polymerization is cured by holding at a high temperature for a certain period of time. Since the polymerization time also varies depending on various factors like the temperature, it is preferable to determine an optimum time in advance according to these conditions, but in general, the conditions are selected so that the polymerization is completed in 2 to 40 hours. Is preferred.

The photochromic material of the present invention obtained by such a method can be subjected to the following treatment depending on the use. That is, dyeing using a dye such as a disperse dye, a silane coupling agent and silicon, zirconium,
Antimony, aluminum, tin, or a hard coat agent composed mainly of sol such as tungsten, SiO _2, Ti
Processing such as antireflection treatment and antistatic treatment by vapor deposition of a thin film of a metal oxide such as O ₂ or ZrO ₂ or application of a thin film of an organic polymer, and secondary treatment can also be performed.

[0072]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

The abbreviations of the compounds used in Examples and Comparative Examples are shown below.

[Epoxy Compound] GMA: glycidyl methacrylate GA: glycidyl acrylate MGMA: β-methyl glycidyl methacrylate MGA: β-methyl glycidyl acrylate BPMGMA: bisphenol A-monoglycidyl ether methacrylate GBMA: 4-glycidyloxybutyl methacrylate GEHPMA: 3- (Glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate GIHPA: 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate EGGE: ethylene glycol glycidyl ether PGGE: propylene glycol glycidyl ether FDGE: terephthalic acid di Glycidyl ester HDGE: Hydroquinone diglycidyl ether GE: butyl glycidyl ether HDGE: 1,6-hexanediol diglycidyl ether [polyfunctional (meth) acrylate] 3G: triethylene glycol dimethacrylate (trade name: NK ester 3G, manufactured by Shin-Nakamura Chemical Co., Ltd.) 4G: Tetraethylene glycol dimethacrylate (a mixture of polyethylene glycol and a monomer having an average number of moles of ethylene oxide chain of 4) (trade name: NK ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.) 3PG: Tri Propylene glycol dimethacrylate (trade name: NK Ester 3PG, Shin-Nakamura Chemical Co., Ltd.)
BP-2EM: methacrylic acid ester compound of 2,2'-bis (4-methacryloyloxypolyethoxyphenyl) propane (a mixture having an average number of moles of ethylene oxide chain of 2.2) (trade name: light ester BP-
2EM, manufactured by Kyoeisha Chemical Co., Ltd.) BR-MA: 2,2′-bis [(3,5-dibromo-4)
-Methacryloyloxyethoxy) propane methacrylate compound (trade name: light ester BR-M)
A, manufactured by Kyoeisha Chemical Co., Ltd.) TEGDMA: triethylene glycol dimethacrylate (trade name: TEGDMA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 3EG: triethylene glycol dimethacrylate (trade name: Light Ester 3EG, Kyoeisha Chemical ( PRO-631: methacrylic acid ester compound of 2,2'-bis (4-methacryloyloxy polyethoxyphenyl) propane (trade name: PRO-631, manufactured by Sartomer Co., Ltd.) [Copolymerized monomer] MMA: methyl methacrylate MS: α-methylstyrene MSD: α-methylstyrene dimer BzMA: benzyl methacrylate HEMA: 2-hydroxyethyl methacrylate [chromene compound] C1: 3,3-bis (3-fluoro-4-methoxyphenyl) ) -6-morpholino-3H- Benzo [f] chromene C2: 3,3-bis (4-methoxyphenyl) -6-morpholino-3H-benzo [f] chromene C3: 3- (3-trifluoromethyl-4-methoxyphenyl) -3- ( 4-methoxyphenyl) -6-piperidino-3H-benzo [f] chromene C4: 3,3-bis (4-methoxyphenyl) -6-N
-Methylpiperazino-3H-benzo [f] chromene C5: 3- (2-furyl) -3-methyl-6-morpholino-3H-benzo [f] chromene C6: 3- (2-naphthyl) -3-methyl-6 -Morpholino-3H-benzo [f] chromene C7: 3,3-bis (4-methoxyphenyl) -6,8
-Dimethoxy-3H-benzo [f] chromene C8: 6-morpholinospiro [fluorene-9,3'-
3H-benzo [f] chromene] [oxazine compound] SP1: 6'-fluoro-1'-methyl-8 "-methoxy-6" -morpholinodispiro (cyclohexane-1,
3 '-(3H) indole-2'-(1'H), 3 ''-
(3H) naphtho (3,2-a) (1,4) oxazine) SP2: 6′-fluoro-1 ′, 5′-dimethyl-6 ″
-Morpholinodispiro (cyclohexane-1,3'-
(3H) indole-2 '-(1'H), 3''-(3
H) Naphtho (3,2-a) (1,4) oxazine) SP3: 6′-fluoro-1′-isobutyl-6 ″ -morpholinodispiro (cyclohexane-1,3 ′-(3
H) Indole-2 ′-(1′H), 3 ″-(3H) naphtho (3,2-a) (1,4) oxazine) SP4: 3 ′, 3′-dimethyl-1′-isobutyl- Dispiro ((3H) indole-2 '-(1'H), 3''
-(3H) naphtho (3,2-a) (1,4) oxazine) [fulgimide compound] F1: N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [ b] Thiophenedicarboximide-7,2-tricyclo [3.
3.1.1] Decane) F2: N-cyanomethyl-6,7-dihydro-2- (p
-Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) F3: N-cyanomethyl-6,7-dihydro- 4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) Example 1 "3G as a multifunctional (meth) acrylate monomer "
To 90 parts by weight, 10 parts by weight of the epoxy compound "GMA" was added, and the mixture was stirred at room temperature for 2 hours. In the mixed solution,
0.05 parts by weight of the chromene compound “C1” and 1 part by weight of t-butylperoxy-2-ethylhexanate as a polymerization initiator were added and mixed well. The color of the mixed solution after dissolving the chromene compound was hardly changed. This mixture 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. The polymerization was carried out in an air furnace at 30 ° C. to 90 ° C. for 18 hours, and the temperature was gradually increased.
It was kept at 0 ° C. for 2 hours. After the polymerization was completed, the mold was removed from the air oven, and after cooling, the cured product was removed from the glass mold of the mold.

The obtained photochromic cured product (thickness 2
mm) was measured by the following method.

(1) Coloring density A xenon lamp L-2480 (300 W) SHL-10 manufactured by Hamamatsu Photonics was applied to the obtained cured product (2 mm thick).
0 through an aeromass filter (manufactured by Corning Incorporated) at 20 ° C. ± 1 ° C., with a beam intensity of 365 nm on the cured body surface =
Irradiation was performed at 2.4 mW / cm2, 245 nm = 24 μW / cm2 for 120 seconds to develop color. ε (120) −ε (0)
Was determined as the color density (T). Where ε (120)
Is the absorbance at the maximum absorption wavelength of the photochromic compound when irradiated with light for 120 seconds under the above conditions and colored, and ε (0) is the absorbance at the same wavelength as that at the time of color development before light irradiation. is there. Before the test (3) described later, the initial color density (T ₀ ) and the initial color tone were evaluated.

(2) Initial coloring ε (0) measured under the above conditions is shown. It should be noted that if the absorbance is usually more than 0.1, the coloring can be clearly recognized visually.

(3) Photochromism durability Xenon fade meter FA-2 manufactured by Suga Test Instruments Co., Ltd.
The measurement was performed using 5AX-HC. After irradiating the obtained cured product with the xenon fade meter for 200 hours, the cured product was colored by the method described in (1) above,
The color density (T ₂₀₀ ) was determined from the absorbance at the maximum absorption wavelength based on the color of the photochromic compound at that time. The photochromism durability was represented by T ₂₀₀ / T ₀ (%).

Examples 2 to 22 In Example 1, as shown in Table 1, the polyfunctional (meth) acrylate monomer and epoxy compound used were changed in the type and amount of the present invention, or In some cases, a cured product was obtained in the same manner as in Example 1 except that a comonomer was further added. Then, the same measurement as in Example 1 was performed for the obtained cured product, and the photochromism durability and the initial coloring were evaluated. Table 1 shows the results.

[0080]

[Table 1]

Examples 23 to 31 A cured product was obtained in the same manner as in Example 4 except that the chromene compound used was changed to the chromene compound shown in Table 2, and the photochromic durability and the cured product of the cured product were obtained. The initial coloring was evaluated. Table 2 shows the results.

[0082]

[Table 2]

Examples 32-35 In Example 4, as shown in Table 3, the type and amount of the chromene compound used were changed, and the curing was carried out in the same manner as in Example 4 except that the flugimide compound and the xazine compound were further added. A cured product was obtained, and the photochromic durability and initial coloring of the cured product were evaluated. Table 3 shows the results.

[0084]

[Table 3]

Comparative Examples 1 to 7 Without using an epoxy compound, 1 part by weight of t-butyl peroxy-2-ethylhexanate was added as a polymerization initiator to each composition shown in Table 4. The mixture was mixed well to obtain a curable composition. Each of the obtained curable compositions was cured in the same manner as in Example 1, and each cured product was evaluated for photochromic durability and initial coloring in the same manner as in Example 1. Table 4 shows the results.

[0086]

[Table 4]

The cured product obtained in each of the comparative examples has significantly larger initial coloring and the photochromic durability is significantly reduced as compared with the cured product obtained in each of the above examples. In addition, when the epoxy compound is not added, the color tone is changed as compared with when the epoxy compound is added, and the color tone changes depending on the type of the monomer.

[0088]

The photochromic curable composition of the present invention can provide a photochromic material which has less initial coloring and excellent photochromism durability and can be suitably used for eyeglass lenses and the like.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C08F 234/02 C08F 234/02 C08L 33/08 C08L 33/08 G03F 7/004 507 G03F 7/004 507

Claims (2)

[Claims] 1. A polyfunctional (meth) acrylate monomer,
The following general formula (1) (Wherein R ¹ is a substituted amino group or an alkoxy group,
R ² and R ³ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aromatic heterocyclic group, and R ² and R ³ are linked to each other to form a ring; May be formed, and any carbon at the 5-position, 7-position, 8-position, 9-position, or 10-position of the benzochromene ring may have a substituent. A photochromic curable composition comprising a chromene compound represented by the formula (1), a compound having at least one epoxy group in a molecule, and a polymerization initiator. 2. A photochromic material obtained by curing the photochromic curable composition according to claim 1.